TW202239800A - Polymer composition, liquid crystal aligning agent, resin film, liquid crystal alignment film, method for manufacturing liquid crystal display element, and liquid crystal display element - Google Patents

Abstract

Provided is a polymer composition that is suitable for a liquid crystal aligning agent from which a liquid crystal alignment film having excellent resistance to an AC afterimage and high film strength can be obtained. This polymer composition is characterized by containing the following (A) component and (B) component. The (A) component is at least one polymer (A) selected from the group consisting of a polyimide precursor having a repeating unit represented by formula (a) and a polyimide that is an imidized product of the polyimide precursor. The (B) component is a polyurethane that has a repeating unit represented by formula (1) but does not have the repeating unit represented by formula (a) and an imidized structure thereof. Formula (a) (The definition of each symbol is as described in the specification.) Formula (1) (The definition of each symbol is as described in the specification.).

Description

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

The present invention relates to a polymer composition, a liquid crystal alignment agent, a resin film, a liquid crystal alignment film, a manufacturing method of a liquid crystal display element, and a liquid crystal display element.

Liquid crystal display elements used in LCD TVs, navigators, smart phones, etc., usually have a liquid crystal alignment film inside the element to control the alignment state of the liquid crystal. The liquid crystal alignment film has the function of controlling the alignment of liquid crystal molecules in a certain direction in the 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 by liquid crystal alignment films formed on respective surfaces of a pair of substrates. The liquid crystal molecules are aligned in a certain direction by the liquid crystal alignment film, and respond by applying a voltage to the electrodes arranged between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element can display a desired image by utilizing the change in alignment of the liquid crystal molecules in response. So far, the liquid crystal alignment film mainly uses polyamide acid (polyamide acid) and other polyimide precursors, and a solution of soluble polyimide as the main component of the liquid crystal alignment agent coated on a glass substrate, etc. and calcined. Polyimide-based liquid crystal alignment film. In recent years, with the high performance of liquid crystal display elements, in addition to large-screen and high-definition LCD TVs and other applications, it is still used in vehicle applications, such as: car navigation systems, instrument panels, surveillance cameras, screens of medical cameras, etc. For liquid crystal display elements, due to the requirement of viewing angle characteristics, transverse electric field methods such as IPS (In Plane Switching) method and FFS (fringe field switching) method have been studied (Patent Document 1). [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2019-082975

(Problem to be solved by the invention)

The liquid crystal alignment film used in the liquid crystal display elements of the IPS driving method and the FFS driving method needs an alignment regulation force to suppress image sticking (hereinafter also referred to as AC image sticking) caused by long-term AC driving. In the liquid crystal display elements that are rapidly becoming more high-definition, high display quality is regarded as important, and the specifications for display defects called "image sticking" are becoming increasingly strict. Also, in the reliability test of liquid crystal display elements for automotive use, a panel vibration test is performed. In this vibration test, it is required that no bad phenomena such as bright spots occur. Furthermore, the rubbing alignment treatment applied in the manufacture of the liquid crystal alignment film, when the alignment characteristics are exhibited by the rubbing treatment, there is a problem that dust is easily generated due to the scraping of the liquid crystal alignment film. If dust is generated, not only dust will adhere to the surface of the liquid crystal alignment film to cause display defects, but also damage the circuit of the TFT element and cause a decrease in yield.

In view of the above circumstances, the present invention aims to provide a polymer composition suitable for a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film having excellent resistance to AC image sticking and high film strength, the liquid crystal alignment agent, the liquid crystal alignment film, and a liquid crystal alignment film having The liquid crystal display element of the liquid crystal alignment film. (How to solve the problem)

As a result of diligent research to achieve the above-mentioned problems, the inventors of the present invention found that forming a resin film using a polymer composition containing a specific component is effective for achieving the above-mentioned object, and completed the present invention.

X表示4價有機基。Y表示來自二胺之2價有機基。2個R各自獨立地表示氫原子或1價有機基。2個Z各自獨立地表示氫原子或1價有機基。 [化2]

A ₁係來自二異氰酸酯之2價有機基。A ₂係從有機二醇取走2個羥基中含有的氫原子而成的2價有機基。A ₁及A ₂中之至少一者具有下式(EG)表示之2價有機基。 [化3]

n為5以上之整數。R表示氫原子或甲基。 (發明之效果) This invention is based on this knowledge, and makes the following matters into summary. A polymer composition characterized by containing the following (A) component and (B) component, (A) component: is selected from polyimide precursors having repeating units represented by the following formula (a) and is the polyimide Polymer (A) of at least one of the group consisting of polyimides of imides of imide precursors, (B) component: has a repeating unit represented by the following formula (1) and does not have the aforementioned The repeating unit represented by the formula (a) and the polyurethane of its imidized structure, [Chem. 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. The two Zs each independently represent a hydrogen atom or a monovalent organic group. [Chem 2]

A ₁ is a divalent organic group derived from diisocyanate. A ₂ is a divalent organic group obtained by removing hydrogen atoms contained in two hydroxyl groups from an organic diol. At least _one of A1 and A2 has a divalent organic group represented by the following _formula (EG). [Chem 3]

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

According to the liquid crystal alignment agent of the present invention, the polymer composition of the liquid crystal alignment agent suitable for obtaining a liquid crystal alignment film with excellent resistance to AC image sticking and high film strength, the liquid crystal alignment agent, the liquid crystal alignment film, and A liquid crystal display element with the liquid crystal alignment film. In addition, this liquid crystal display element has high display quality with few display defects. Although the mechanism by which the present invention achieves the above-mentioned effects is not yet clear, it can roughly be speculated as follows. That is to say, when the polymer composition contains specific polyurethane, the strength of the film will be improved due to hydrogen bonding, and it is considered that by introducing a specific ethylene glycol chain into the specific polyurethane, the extension of the film Sexual enhancement, so the above-mentioned effects can be obtained.

The components contained in the liquid crystal alignment agent of the present disclosure and other components that can be arbitrarily blended as needed will be described below. In addition, in the present specification, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

＜Polymer (A)＞ The polymer composition of the present invention comprises a polyimide precursor selected from repeating units represented by the above formula (a) (hereinafter also referred to as polyimide precursor (A).) and the polyimide At least one polymer (A) of the group consisting of polyimide which is an imide of an amine precursor. The polymer (A) may be one type or two or more types.

(repeating unit represented by formula (a)) In the above formula (a), Y represents a divalent organic group derived from diamine. Moreover, the divalent organic group derived from diamine includes, for example, a divalent organic group obtained by removing two amine groups from diamine. The following diamines are mentioned as this diamine. These diamines may be used alone or in combination of two or more.

Diamines represented by the following formula (O); diamines with photoalignment groups such as 4,4'-diaminoazobenzene or diaminodiphenylacetylene; the following formulas (h-1)~(h- 6) Diamines with amide bonds or urea bonds, such as diamines; 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diamine Aminodiphenylmethane, 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 ); it is selected from the group consisting of nitrogen-containing heterocycle, secondary amino group and tertiary amino group Diamines with at least one structure containing a nitrogen atom (hereinafter also referred to as a specific structure containing a nitrogen atom); 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamine Aminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 4,4'-diamino-3,3'-dihydroxybiphenyl, 2,4- Diamines having carboxyl groups such as diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and diamines represented by the following formula (3b-1) ~ formula (3b-4) ; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H -Indane-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; 2-methacrylic acid (2,4-diaminophenoxy)ethyl ester and 2,4-diamino-N,N-diallylaniline and other diamines with photopolymerizable groups at the end; cholestanyloxy- 3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid Cholesteryl esters, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate and 3,6-bis(4-aminobenzoyloxy)cholesteryl Diamines with a steroid skeleton such as steranes; diamines represented by the following formulas (V-1)~(V-6); groups such as the following formulas (5-1)~(5-11) "-N(D) -"(D represents a protecting group that will be removed by heating and replaced by a hydrogen atom, preferably tertiary butoxycarbonyl); 1,3-bis(3-aminopropyl)-tetramethyl Diamines with siloxane bonds such as disiloxane and diamines represented by the following formula (Ds-1); diamines with oxazoline structures such as the following formulas (Ox-1)~(Ox-2); Xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), any of the formulas (Y-1) to (Y-167) described in International Publication No. 2018/117239 The ones represent diamines, etc., in which two amine groups are bonded.

Ar表示2價苯環、聯苯結構、或萘環。2個Ar可相同也可不同，上述苯環、聯苯結構、或萘環之任意氫原子也可被1價基取代。p為0或1之整數。Q ₂表示-(CH ₂) _n-(n為2~18之整數。)、或該-(CH ₂) _n-之-CH ₂-之至少一部分被-O-、-C(＝O)-或-O-C(＝O)-中之任一者取代而得之基。 [chemical 4]

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

[chemical 5]

m有2個以上時，2個以上之m可各相同也可不同。苯環上之1個以上之氫原子也可被1價基取代。 [chemical 6]

When there are two or more m, each of the two or more m may be the same or different. One or more hydrogen atoms on the benzene ring may be substituted by a monovalent group.

式(3b-1)中，A ¹表示單鍵、-CH ₂-、-C ₂H ₄-、-C(CH ₃) ₂-、-CF ₂-、-C(CF ₃) ₂-、-O-、-CO-、-NH-、-N(CH ₃)-、-CONH-、-NHCO-、-CH ₂O-、-OCH ₂-、-COO-、-OCO-、-CON(CH ₃)-或-N(CH ₃)CO-，m1及m2各自獨立地為0~4之整數且m1＋m2為1~4之整數。式(3b-2)中，m3及m4各自獨立地為1~5之整數。式(3b-3)中，A ²表示碳數1~5之直鏈或分支烷基，m5為1~5之整數。式(3b-4)中，A ³及A ⁴各自獨立地表示單鍵、-CH ₂-、-C ₂H ₄-、-C(CH ₃) ₂-、-CF ₂-、-C(CF ₃) ₂-、-O-、-CO-、-NH-、-N(CH ₃)-、-CONH-、-NHCO-、-CH ₂O-、-OCH ₂-、-COO-、-OCO-、-CON(CH ₃)-或-N-(CH ₃)CO-，m6為1~4之整數。 [chemical 7]

In formula (3b-1), A ¹ represents 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-, 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 1-5. In the formula (3b-3), A ² represents a linear or branched alkyl group with 1 to 5 carbon atoms, and m5 is an integer of 1 to 5. In formula (3b-4), A ³ and A ⁴ each independently represent 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-, m6 is an integer of 1-4.

式(V-1)~(V-6)中，X ^v1~X ^v4、X ^p1~X ^p2各自獨立地表示-(CH ₂) _a-(a為1~15之整數。)、-CONH-、-NHCO-、-CON(CH ₃)-、-NH-、-O-、-CH ₂O-、-CH ₂OCO-、-COO-、或-OCO-，X ^v5表示-O-、-CH ₂O-、-CH ₂OCO-、-COO-、或-OCO-。X _aは、單鍵、-O-、-NH-、或-O-(CH ₂) _m-O-(m表示1~6之整數。)，R ^v1~R ^v4、R ^1a~R ^1b各自獨立地表示碳數1~20之烷基、碳數1~20之烷氧基或碳數2~20之烷氧基烷基。2個k可相同也可不同。 [化9]

式(5-1)~(5-11)中，Boc表示第三丁氧基羰基。 [化10]

[chemical 8]

In formulas (V-1) to (V-6), X ^v1 to X ^v4 and X ^p1 to X ^p2 each independently represent -(CH ₂ ) _a -(a is an integer of 1 to 15.), -CONH- , -NHCO-, -CON(CH ₃ )-, -NH-, -O-, -CH ₂ O-, -CH ₂ OCO-, -COO-, or -OCO-, X ^v5 means -O-, - _CH2O- , _-CH2OCO- , -COO-, or -OCO-. X _aは, single bond, -O-, -NH-, or -O-(CH ₂ ) _m -O- (m represents an integer of 1 to 6.), R ^v1 ~ R ^v4 , R ^1a ~ R ^1b each independently represent an alkyl group having 1 to 20 carbons, an alkoxy group having 1 to 20 carbons, or an alkoxyalkyl group having 2 to 20 carbons. The two k's may be the same or different. [chemical 9]

In formulas (5-1) to (5-11), Boc represents a tertiary butoxycarbonyl group. [chemical 10]

[chemical 11]

In the above formula (d _o ), the above-mentioned monovalent groups include halogen atoms, alkyl groups with 1 to 10 carbons, alkenyl groups with 2 to 10 carbons, alkoxy groups with 1 to 10 carbons, and alkoxy groups with 1 to 10 carbons. Fluoroalkyl, fluoroalkenyl with 2 to 10 carbons, fluoroalkoxy with 1 to 10 carbons, carboxyl, hydroxyl, alkoxycarbonyl with 1 to 10 carbons, cyano, nitro, etc. For the diamine represented by the above formula (d _o ), considering the viewpoint of improving the liquid crystal alignment, it is preferable to use the diamine represented by the following formula (d _o -1) ~ (d _o -6), 3,3'-diamine group Diphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether are preferable. [chemical 12]

In the diamine represented by the above formula (O), arbitrary hydrogen atoms of a benzene ring, a biphenyl structure, or a naphthalene ring may be substituted with a monovalent group. The above monovalent groups, for example: halogen atom, alkyl group with 1~10 carbons, alkenyl group with 2~10 carbons, alkoxyl group with 1~10 carbons, fluoroalkyl group with 1~10 carbons, Fluoroalkenyl with 2 to 10 carbons, fluoroalkoxy with 1 to 10 carbons, alkoxycarbonyl with 1 to 10 carbons, cyano, nitro, etc.

Regarding the diamine represented by the above formula (O), considering the viewpoint of improving liquid crystal alignment, the diamines represented by the following formulas (o-1) to (o-16) are preferred.

[chemical 13]

[chemical 14]

式(o-14)中，2個m可相同或不同。 [chemical 15]

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

The above-mentioned diamines with a specific nitrogen-containing structure may also have nitrogen-containing heterocycles, such as: pyrrole, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridine, pyridine, indole, benzimidazole , purine, quinoline, isoquinoline, ketidine, quinoline, phthalein 𠯤, three 𠯤, carbazole, acridine, piperidine, piper 𠯤, pyrrolidine, hexamethyleneimine, etc. Among these, pyridine, pyrimidine, pyridine, piperidine, piperidine, quinoline, carbazole or acridine are preferable.

上式(n)中，R表示氫原子或碳數1~10之1價烴基。「＊」表示鍵結於烴基之原子鍵，且至少一者鍵結於芳香族烴基。 The secondary and tertiary amino groups that the above-mentioned diamine having a specific nitrogen atom-containing structure may also have are, for example, represented by the following formula (n). [chemical 16]

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

Monovalent hydrocarbon groups of R in the above formula (n), for example: alkyl groups such as methyl, ethyl, and propyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups and methylphenyl groups, etc. R is preferably a hydrogen atom or a methyl group.

Specific examples of the above-mentioned diamines with a specific nitrogen-containing structure, such as: 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminopyridine, Aminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperone, 3,6-diaminoacridine, N- Ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, diamine represented by the following formula (Dp-1)~(Dp-8), the following formula (z -1) ~ the diamine represented by formula (z-18).

[chemical 17]

[chemical 18]

[chemical 19]

The above-mentioned Y is preferably selected from diamines represented by the above formula (O), diamines having amide bonds or urea bonds, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane Phenylmethane, 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 above formula (d _o ), 4-(2-(methylamino)ethyl)aniline , 4-(2-aminoethyl)aniline, and the group "-N(D)-" (D represents a protecting group that is removed by heating and replaced by a hydrogen atom, preferably tertiary butoxycarbonyl. ) is preferably a divalent organic group of diamines in the group consisting of diamines of ). The above-mentioned Y is preferable because it can obtain the effect of reducing afterimages caused by long-term AC driving by conforming to this configuration.

In the above formula (a), X represents a tetravalent organic group. X preferably represents a tetravalent organic group derived from tetracarboxylic dianhydride or a derivative thereof. Also, a quaternary organic group derived from tetracarboxylic dianhydride or derivatives thereof, for example: a quaternary organic group in which 4 carboxyl groups have been removed from the corresponding tetracarboxylic acid. The 4-valent organic group can be exemplified by a 4-valent organic group derived from acyclic aliphatic tetracarboxylic dianhydride or a derivative thereof, a 4-valent organic group derived from an alicyclic tetracarboxylic dianhydride or a derivative thereof, or a 4-valent organic group derived from an aromatic Quaternary organic group of tetracarboxylic dianhydride or its derivatives. Here, the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups bonded to a chain hydrocarbon structure. However, it does not need to consist only of a chain hydrocarbon structure, and may have an alicyclic structure or an aromatic ring structure partly. Alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecularly dehydrating four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. However, these four carboxyl groups are not bonded to the aromatic ring. Moreover, it does not need to consist only of an alicyclic structure, and a part may have a chain hydrocarbon structure and an aromatic ring structure. Aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. As a derivative of the said tetracarboxylic dianhydride, a tetracarboxylic acid dihalide, a tetracarboxylic-acid dialkyl, or a tetracarboxylic-acid dialkyl dihalide is mentioned. The said tetracarboxylic dianhydride or its derivative(s) may be used individually by 1 type, and may use it in combination of 2 or more types.

For the above-mentioned non-cyclophatic aliphatic or alicyclic tetracarboxylic dianhydrides, or their derivatives, in view of improving the alignment of liquid crystals, it is preferable to have a tetracarboxylic acid dianhydride selected from cyclobutane ring structure, cyclopentane ring structure and Tetracarboxylic dianhydrides of at least one substructure in the group formed by the cyclohexane ring structure or derivatives thereof are preferred.

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

式中X ₁係選自下式(X1-1)~(X1-25)之結構。＊表示原子鍵。 [chemical 20]

_In the formula, X1 is selected from the structures of the following formulas (X1-1)~(X1-25). * Indicates an atomic bond.

[chem 21]

[chem 22]

[chem 23]

[chem 24]

In the formulas (X1-1)~(X1-4), R1~ _R21 each independently represent a hydrogen atom, a halogen atom, an alkyl group with ₁ ~6 carbons, an alkenyl group with 2~6 carbons, or an alkenyl group with 2 carbons. ~6 alkynyl groups, monovalent organic groups with 1 to 6 carbon atoms containing fluorine atoms, or phenyl groups. * Indicates an atomic bond. Considering the viewpoint of improving liquid crystal alignment, R ₁ to R ₂₁ are preferably hydrogen atoms, halogen atoms, methyl groups, or ethyl groups, and hydrogen atoms or methyl groups are more preferable. In the formulas (X1-24)~(X1-25), j and k are integers of ₀ or ₁ , and A1 and A2 each independently represent a single bond, -O-, -CO-, -COO-, phenylene group, sulfonyl group, or amido group. A plurality of A ₂ may each be the same or different.

Specific examples of the formula (X1-1) include the following formulas (1-1) to (1-6). In view of improving the liquid crystal alignment, formulas (1-1) and (1-2) are particularly preferable. *Same as above.

[chem 25]

[化27]

Desirable specific examples of the above formulas (X1-24) and (X1-25) include the following formulas (X1-26) to (X1-41). *Same as above. [chem 26]

[chem 27]

Considering the point of view of improving liquid crystal alignment, the above X1 is the above formula (X1-1)~( _X1-10 ), (X1-18)~(X1-23), (X1-24)~(X1-25), Or (X1-26)~(X1-30) is more ideal, for the above formula (X1-1), (X1-5), (X1-7)~(X1-10), (X1-21), (X1 -23), (X1-24)~(X1-25), or (X1-26)~(X1-30) are better, for the above formula (1-1), (1-2), (X1-5 ), (X1-7), (X1-9), or (X1-26)~(X1-30) are more ideal.

The monovalent organic groups of R and Z in the above formula (a) include monovalent hydrocarbon groups with 1 to 20 carbon atoms, and the methylene groups of the hydrocarbon groups are substituted with -O-, -S-, -CO-, -COO -, -COS-, -NR ³ -(only R ³ is a hydrogen atom or a monovalent hydrocarbon group with 1~10 carbons.), -CO-NR ³ -(only R ³ is a hydrogen atom or a carbon number 1~10 Monovalent hydrocarbon group.), -Si(R ³ ) ₂ - (except that R ³ is a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbons.), -SO ₂ - and other monovalent group A, monovalent hydrocarbon group Or at least one of the hydrogen atoms bonded to the carbon atom of the monovalent group A is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxyl, alkoxy, nitro, amino, mercapto, Monovalent group substituted by nitroso group, alkyl silyl group, alkoxy silyl group, silanol group, sulfinic acid group, phosphino group, carboxyl group, cyano group, sulfo group, acyl group, etc. 1 valence basis. The monovalent organic groups of R and Z in the above formula (a), and alkyl groups with 1 to 10 carbons, alkenyl groups with 2 to 10 carbons, alkynyl groups with 2 to 10 carbons, tertiary butoxy A carbonyl group or a 9-fenylmethoxycarbonyl group is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is more preferable. From the standpoint 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 above formula (a), each of X, Y, R, and Z may be one type, or two or more types. The content ratio of the polymer (A) is preferably 70 to 99 parts by mass, 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 selected from a polyimide precursor having a repeating unit represented by the above formula (a) and a polyimide that is an imide of the polyimide precursor At least one polymer of the group of . The polymer (A) may also have a repeating unit and a terminal group represented by the above formula (a).

Here, the terminal group refers to a group bonded to the terminal of the repeating unit constituting the above-mentioned polymer (A). Terminal groups such as amine group, carboxyl group, acid anhydride group, isocyanate group or derivatives thereof. Amino groups, carboxyl groups, acid anhydride groups, and isocyanate groups can be obtained by a usual condensation reaction, and the above-mentioned derivatives can be obtained, for example, by blocking the terminal groups with a blocking agent as described later.

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

U ₁為2價有機基，U _1’為來自二胺之2價有機基，C ₁及C _1’各自獨立地為氫原子或1價有機基。 (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). [chem 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 U1 include divalent organic groups derived from diisocyanate. These diisocyanates may be used alone or in combination of two or more. Here, diisocyanate, for example: aromatic diisocyanate, aliphatic diisocyanate. Here, "aromatic diisocyanate" means a diisocyanate having at least one aromatic group. Moreover, "aliphatic diisocyanate" means the diisocyanate which has an aliphatic group and does not have an aromatic group. For U ₁ , for example: (i) divalent organic divalent organic diisocyanates derived from aromatic diisocyanates in the diisocyanate structure (O=C=NRN=C=O) where R is an organic group with at least one benzene ring having 6 to 30 carbon atoms. or (ii) from the aliphatic diisocyanate in the diisocyanate structure (O=C=NRN=C=O) where R is an organic group with an aliphatic group and an organic group with 4 to 30 carbon atoms that does not have an aromatic group Valence organic base. Also, the aliphatic group includes both acyclic aliphatic groups and alicyclic groups. Specific examples _of U1 can include those derived from o-phenylenediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, toluene diisocyanate (for example: toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, isocyanate), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 4,4'-diisocyanate diphenyl ether, 2,2'-bis(4-diisocyanatophenyl)propane, 4,4'-diisocyanate diphenylmethane (4,4'-diphenyl Methyl methane diisocyanate), 4,4'-Diphenyl diisocyanate, 4,4'-Diphenyl diisocyanate, 3,3'-Diphenyl diisocyanate and 2,2 Divalent organic groups of aromatic diisocyanates such as '-diisocyanate diphenyl ketone, derived from isophorone diisocyanate, norcamphene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate Divalent organic groups of aliphatic diisocyanate such as isocyanate and tetramethylene diisocyanate.

In the above formula (U), U _1' is a divalent organic group derived from diamine. As diamine, the diamine illustrated for the said repeating unit (a) is mentioned, and the ideal aspect is the same as above.

Examples of the C ₁ and C _1′ monovalent organic groups in the above formula (U) include structures exemplified by R and Z of the above repeating unit (a). Regarding C ₁ and C _1' , from the standpoint of obtaining the effect of the present invention, it is preferably independently 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), each of U ₁ , U _1' , C ₁ , and C _1' may be one type or two or more types.

When the polymer (A) in the present invention has a repeating unit represented by the above formula (U), the content ratio of the repeating unit represented by the formula (U) is considered to obtain the effect of the present invention. ), the imidization structure of the repeating unit (a) and the total 100 mol% of the repeating unit represented by the above formula (U) is preferably 1-30 mol%, more preferably 2-25 mol%.

<Polyurethane> The polymer composition of the present invention contains polyurethane having a repeating unit represented by the above formula (1) and not having a repeating unit represented by the above formula (a) and its imidized structure esters. At least one of A1 and A2 in the above _formula ( ₁ ) has a divalent organic group represented by the above formula (EG). One type of polyurethane may be used alone or two or more types may be used in combination.

(Repeating unit represented by formula (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. These diisocyanates may be used alone or in combination of two or more. Here, the diisocyanate includes, for example, diisocyanate (DI _EG ) having a divalent organic group represented by the above formula (EG), aromatic diisocyanate and aliphatic diisocyanate other than diisocyanate (DI _EG ). Here, "aromatic diisocyanate" refers to a diisocyanate having at least one aromatic group. Moreover, "aliphatic diisocyanate" means the diisocyanate which has an aliphatic group and does not have an aromatic group. The aforementioned diisocyanate (DI _EG ) includes, for example, the diisocyanates shown below. [chem 29]

Aromatic diisocyanate and aliphatic diisocyanate other than diisocyanate (DI _EG ), for example: (i) R in the diisocyanate structure (O=C=NRN=C=O) does not have the formula (EG) An aromatic diisocyanate with a divalent organic group and an organic group with at least one benzene ring having 6 to 30 carbon atoms, or (ii) R in the diisocyanate structure (O=C=NRN=C=O) is aliphatic An aliphatic diisocyanate that does not have a divalent organic group represented by the above formula (EG) and an organic group with 4 to 30 carbon atoms in the aromatic group. Also, 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, toluene diisocyanate (e.g. : Toluene 2,4-diisocyanate, toluene 2,6-diisocyanate), 1,4-diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 3,3'-Dimethyl-4,4'-diisocyanate biphenyl, 4,4'-diisocyanate diphenyl ether, 2,2'-bis(4-diisocyanatophenyl)propane, 4,4'-diisocyanate Diphenylmethane isocyanate (4,4'-diphenylmethane diisocyanate), 4,4'-diphenylmethane diisocyanate, 3,3'-diphenylmethane diisocyanate and 2 , 2'-diisocyanate diphenyl ketone and other aromatic diisocyanates, isophorone diisocyanate, norcamphene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetra Aliphatic diisocyanates such as methylene diisocyanate.

In the above formula (1), A ₂ is a divalent organic group in which hydrogen atoms contained in two hydroxyl groups have been removed from the organic diol. These organic diols may be used alone or in combination of two or more. The organic diol can be exemplified: a diol having a divalent organic group represented by the above formula (EG); a diol not containing a divalent organic group represented by the above formula (EG), specifically, such as ethylene glycol, di Ethylene 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, 1,9-nonanediol Alcohol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and other alkylene glycols; dimethylolpropionic acid (2,2-bis( hydroxymethyl)propionic acid), dimethylolbutyric acid (2,2-bis(hydroxymethyl)butyric acid), 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5 - Carboxyl-containing diols such as dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid; polypropylene glycol; the combination of polypropylene glycol and neopentyl glycol Random copolymer; polyester diol obtained by reacting polyol and polybasic acid; polycarbonate diol with carbonate skeleton; γ-butyl lactone, ε-caprolactone, δ-valerolactone, etc. Polycaprolactone diol obtained by ring-opening addition of lactones; bisphenol A; ethylene oxide adducts of bisphenol A; ethylene oxide adducts of hydrogenated bisphenol A; bisphenols Propylene oxide adduct of A; hydrogenated bisphenol A; propylene oxide adduct of hydrogenated bisphenol A, etc.

Diols containing a divalent organic group represented by the above formula (EG) are not particularly limited as long as the molecule contains the above formula (EG), but they are diols and polyacids containing a divalent organic group represented by the above formula (EG) The polyester diol obtained by the reaction, or the diol of the above formula (EG) with hydrogen atoms bonded to both ends, is preferably the diol of the above formula (EG) with hydrogen atoms bonded to both ends. Among the diols with hydrogen atoms bonded to both ends of the above formula (EG), the upper limit of n is preferably set so that the upper limit of the weight average molecular weight of the diol becomes 5,000 or less, preferably set so that the weight average molecular weight of the diol The upper limit of the molecular weight is more preferably 4,000 or less, and the upper limit of the weight average molecular weight of the diol is more preferably 3,000 or less. Considering the improvement of liquid crystal alignment, the upper limit of n is preferably 40, more preferably 30, and most preferably 20. For the lower limit of n, considering the point of view of improving the liquid crystal alignment, 5 is more ideal, and 6 is more ideal. Diols containing divalent organic groups represented by the above formula (EG), more specifically, pentaethylene glycol, hexaethylene glycol, and Sanyo Chemical Industry Co., Ltd.'s trade names PEG-300, PEG-400, PEG- 600, PEG-1000, PEG-1500, PEG-2000, PEG-4000N, PEG-4000S, PEG-6000E, PEG-6000P, PEG-10000, PEG-13000, PEG-20000; product name PEG300 manufactured by Merck 、PEG1000、PEG2000、PEG4000、PEG6000、PEG8000、PEG10000、PEG12000、PEG20000、PEG35000；SIGMA-ALDRICH公司製之製品編號P2139、P3265、P3515、81210、81240、81260、81285、81310、181986、181994、182001、182028 、189456、202304、202312、202320、202339、202398、202421、202436、202444、202452、295906、309028、372773、372781、373001、412325、435406、435422、435457、637726；中日合成化學公司製之商品名SINOPOL PEG600, SINOPOL PEG1500, SINOPOL PEG4000; trade names PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#4000, PEG#6000M, manufactured by LION SPECIALITY CHEMICALS, Tokyo Commercially available from Kasei Kogyo Co., Ltd. as product names Polyethylene Glycol 400 and Polyethylene Glycol 600. Ideal specific examples of diols with hydrogen atoms bonded to both ends of the above formula (EG) include pentaethylene glycol, hexaethylene glycol, and trade names PEG-300, PEG-400, and PEG manufactured by Sanyo Chemical Industry Co., Ltd. -600, PEG-1000, product name PEG300 manufactured by Merck & Co., PEG1000, product name PEG300 manufactured by Merck & Co., Ltd., PEG1000 manufactured by Chunichi Chemical Co., Ltd., trade name SINOPOL PEG600, trade name PEG manufactured by LION SPECIALITY CHEMICALS #300, PEG#400, PEG#600, PEG#1000, Polyethylene Glycol represented by Polyethylene Glycol 400, Polyethylene Glycol 600, or Pentapropylene Glycol, Hexapropylene Glycol, Polypropylene Glycol (more preferably The average molecular weight is polypropylene glycol with an average molecular weight of 400~5,000.), a copolymer composed of ethylene oxide and propylene oxide with an average molecular weight of 500~5,000, etc. The aforementioned polyethylene glycol and polypropylene glycol may also be those obtained by subjecting ethylene oxide or propylene oxide to anionic ring-opening polymerization. The polymerization reaction can be carried out using a polymerization initiator (for example: water, ethylene glycol, propylene glycol, etc.) and a catalyst amount of alkali (for example: potassium hydroxide). In addition, the average molecular weight of the diols exemplified among diols containing divalent organic groups represented by (EG) above is the weight average obtained based on polystyrene as measured by gel permeation chromatography (GPC). molecular weight.

(repeating unit constituting polyurethane) The polyurethane in the present invention is a polyurethane having a repeating unit represented by the above formula (1) and not having a repeating unit represented by the aforementioned formula (a) and its imidized structure. The polyurethane in the present invention may have repeating units and terminal groups represented by the above formula (1). For terminal groups, the same as above.

The content ratio of the repeating unit represented by the above formula (1) is preferably 10 mol% or more, more preferably 20 mol% or more, based on the total repeating units constituting the polyurethane. Also, A2 is the content ratio of the repeating unit represented by the formula ( ₁ ) derived from the divalent organic group of the diol with hydrogen atoms bonded to both ends of the above formula (EG), and is preferably the repeating unit that constitutes the polyurethane. More than 10 mol% of the whole unit is more preferable, more preferably 20 mol% or more, more preferably 50 mol% or more.

In the above formula (1), A ₁ and A ₂ may each be one type or two or more types. The proportion of polyurethane in the present invention is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, in 100 parts by mass of the polymer composition.

<Manufacture of Polymer (A)> It is the polyimide precursor of the above-mentioned polymer (A), for example: polyamic acid, polyamic acid ester, etc. Polyamic acid (a polyimide precursor having a repeating unit represented by the formula (a) in which R in the above formula (a) is a hydrogen atom) can be produced by the following method. Specifically, the tetracarboxylic acid component containing the above-mentioned tetracarboxylic dianhydride or its derivatives and the diamine component containing the above-mentioned diamine can be mixed in the presence of an organic solvent at -20~150°C, preferably at 0~ Synthesize at 50°C for 30 minutes to 24 hours, preferably 1 to 12 hours (polycondensation). When the above-mentioned polyamic acid has the above-mentioned repeating unit (U), a diisocyanate compound represented by O=C=NU ₁ -N=C=O (U ₁ is the same as U ₁ in the formula (U)) can be obtained. It is synthesized by reacting with the above-mentioned tetracarboxylic acid component and the above-mentioned diamine component. Specific examples of the organic solvent used in the above reaction can include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N- Dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone. Also, when the solvent solubility of the 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 indicated. Two or more of these may be used in combination.

式[D-1]中，D ¹表示碳數1~3之烷基，式[D-2]中，D ²表示碳數1~3之烷基，式[D-3]中，D ³表示碳數1~4之烷基。 反應可於任意濃度進行，但較佳為1~50質量%，更佳為5~30質量%。反應初期於高濃度進行，之後追加溶劑亦可。反應時，二胺成分之合計莫耳數與四羧酸成分之合計莫耳數之比為0.8~1.2較佳。和通常的縮聚反應同樣，此莫耳比越接近1.0，則生成之聚醯胺酸之分子量越大。 [chem 30]

In formula [D-1], D ¹ represents an alkyl group with 1 to 3 carbons; in formula [D-2], D ² represents an alkyl group with 1 to 3 carbons; in formula [D-3], D ³ Indicates an alkyl group with 1 to 4 carbon atoms. The reaction can be performed at any concentration, but it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and a solvent may be added thereafter. During the reaction, the ratio of the total number of moles of the diamine components to the total number of moles of the tetracarboxylic acid components is preferably 0.8 to 1.2. Like the usual 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 injecting the reaction solution into a poor solvent while fully stirring the reaction solution to precipitate the polyamic acid. In addition, the precipitation can be carried out several times, and after washing with a poor solvent, it can be dried at room temperature or by heating to obtain a refined polyamic acid powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butylcytosol, acetone, and toluene.

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

[blocking agent] When synthesizing the polymer (A) of the present invention, a tetracarboxylic acid component containing tetracarboxylic dianhydride or its derivatives, a diamine component, and an optional diisocyanate compound can be used together to synthesize the terminal Capped polymer.

二碳酸二第三丁酯、二碳酸二烯丙酯等二碳酸二酯化合物；丙烯醯氯、甲基丙烯醯氯、菸鹼醯氯等氯羰基化合物；苯胺、2-胺基苯酚、3-胺基苯酚、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、環己胺、正丁胺、正戊胺、正己胺、正庚胺、正辛胺等單胺化合物；異氰酸乙酯、異氰酸苯酯、異氰酸萘酯、2-丙烯醯氧基乙基異氰酸酯及2-甲基丙烯醯氧乙基異氰酸酯等具有不飽和鍵之異氰酸酯等單異氰酸酯化合物；異硫氰酸乙酯、異硫氰酸烯丙酯等異硫氰酸酯化合物等。 Capping agent, such as acetic anhydride, maleic anhydride, nedylic anhydride, phthalic anhydride, itaconic anhydride, cyclohexane dicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, the following formula ( Compounds represented by m-1)~(m-6), 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6, 7-Tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride and other acid monoanhydrides; [Chemical 31]

Di-tert-butyl dicarbonate, diallyl dicarbonate and other dicarbonate diester compounds; chlorocarbonyl compounds such as acryl chloride, methacryl chloride, nicotinyl chloride, etc.; aniline, 2-aminophenol, 3- Aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclo Hexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and other monoamine compounds; ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloxy Monoisocyanate compounds such as isocyanates having unsaturated bonds such as ethyl isocyanate and 2-methacryloxyethyl isocyanate; isothiocyanate compounds such as ethyl isothiocyanate and allyl isothiocyanate, etc.

The usage ratio of the blocking agent is preferably 20 mole parts or less, more preferably 10 mole parts or less, based on 100 mole parts of the total of the diamine component used and the organic diol component used if necessary.

In addition, polyimide can be obtained by ring-closing (imidizing) the polyimide precursor (A) of the polymer (A). Also, the imidization rate referred to in this specification refers to the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxyl groups (or derivatives thereof) . The imidization rate does not necessarily have to be 100%, and can be adjusted arbitrarily according to the application and purpose.

The method of imidizing the polyimide precursor includes thermal imidization by directly heating the solution of the polyimide precursor or adding a catalyst to the solution of the polyimide precursor imidization.

When the polyimide precursor is thermally imidized in the solution, the temperature is preferably 100~400°C, more preferably 120~250°C, while discharging the water generated by the imidization reaction into the system It is better to do it outside.

Catalyzed imidization of polyimide precursor can be done by adding alkaline catalyst and acid anhydride to the solution of polyimide precursor, and preferably at -20~250℃, more preferably at 0~ Stir at 180°C to proceed. The amount of alkaline catalyst should be 0.5~30 mole times of amide acid group, more preferably 2~20 mole times, the amount of acid anhydride should be 1~50 mole times of amide acid group, more preferably 3~30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has a moderate basicity for the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, use of acetic anhydride is preferred because it facilitates purification after the reaction. The imidization rate of catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

When recovering the polyimide precursor or polyimide produced from the polyimide precursor or the polyimide reaction solution, the reaction solution may be poured into a solvent for precipitation. Solvents used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butylcytosol, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like. The polymer obtained by throwing in a solvent and precipitating it is collected by filtration, and then dried at normal temperature or under reduced pressure at normal temperature or by heating. In addition, if the polymer recovered by precipitation is redissolved in an organic solvent, and then recovered by precipitation, and this operation is repeated for example 2 to 10 times, the impurities in the polymer can be reduced. The solvent at this time is, for example, alcohols, ketones, or hydrocarbons. If three or more solvents selected from these are used, the refining efficiency can be improved, so it is ideal.

The molecular weight of the polymer (A) used in the present invention, when considering the strength of the liquid crystal alignment film obtained therefrom, the workability and coating properties of the film, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is 5,000~1,000,000 is ideal, more preferably 10,000~150,000.

n為5以上之整數。R表示氫原子或甲基。 <Manufacture of polyurethane> The above-mentioned polyurethane can be produced, for example, by combining (o) component containing an organic diol having two hydroxyl groups in the molecule with a compound containing two isocyanate groups in the molecule. (i) The ingredients are reacted to obtain. Here, at least one of the compounds constituting the above-mentioned (o) component and (i) component has a substructure represented by the following formula (EG) in the molecule. [chem 32]

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

(o) component and (i) component may each be 1 type, or may be 2 or more types.

(o) Components, for example: organic diols exemplified for the repeating unit represented by the above formula (1), include diol compounds represented by "HA ₂ -H" (A ₂ is the same as A ₂ in formula (1).) .

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

When a diol compound represented by "HA ₂ -H" is contained as component (o) and a diisocyanate compound represented by O=C=NA ₁ -N=C=O is contained as component (i), "HA ₂ -H" represents At least one of A ₂ in the diol compound and A ₁ in the diisocyanate compound represented by O=C=NA ₁ -N=C=O has the substructure represented by the above formula (EG) in the molecule . Preferable specific examples thereof are as described above.

The reaction of (o) component and (i) component is performed normally in an organic solvent. The organic solvent used at this time is not particularly limited as long as the generated polyurethane can be dissolved. Specific examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethyl Dimethyl urea, tetramethyl urea, pyridine, dimethyl urea, hexamethyl triamine phosphate, γ-butyrolactone, isopropanol, methoxymethyl pentanol, dipentene, ethyl pentanone, Methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellothreon, ethyl cellothreon, methyl cellothreon acetate, ethyl cellothreon acetate Ester, 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-tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, di Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate , tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl Diethyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate ester, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropionate Propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme or 4-hydroxy-4-methyl-2-pentanone, etc. These may be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve polyurethane, it can also be used in combination with the above-mentioned solvents. Also, the moisture in the organic solvent will hinder the polymerization reaction, so the organic solvent should be dehydrated and dried before use.

In the synthesis method of the polyurethane obtained by reacting the (o) component containing the organic diol and the (i) component containing the diisocyanate compound having 2 isocyanate groups in the molecule, the synthetic method of the polyurethane used in the present invention is to use The blending amount of the component (o) and the component (i) is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group/hydroxyl group = 0.8 to 1.2, preferably 0.9 to 1.2, more preferably 0.9 to 1.1. Reaction in organic solvents to obtain.

Also, when two or more organic diols are used, the reaction with the diisocyanate compound may be performed after mixing two or more organic diols, or each organic diol may be individually reacted with the diisocyanate compound. Also, after reacting an organic diol with a diisocyanate compound, the obtained terminal isocyanate compound is reacted with another organic diol compound, and then reacted with a diisocyanate compound. Moreover, it is the same when using 2 or more types of diisocyanate compounds. In this way, the desired polyurethane can be manufactured.

The reaction temperature of the component (o) and the component (i) is preferably 0 to 160°C, more preferably 10 to 150°C. The reaction time can be appropriately selected according to the scale of the reaction and the reaction conditions used. In addition, the reaction may be carried out in the presence of catalysts such as tertiary amines, alkali metals, alkaline earth metals, tin, zinc, titanium, cobalt, and other metals or semi-metallic compounds, if necessary. The concentration of the total amount of the component (o) and the component (i) is preferably 1 to 50% by mass, more preferably 5 to 30% by mass in the reaction solution. The initial stage of the reaction is carried out at a high concentration, and an organic solvent may be added thereafter.

The molecular weight of the polyurethane used in the present invention, when considering the strength of the liquid crystal alignment film obtained therefrom, the workability and coating properties of the film, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is 4,000~80,000 is ideal, more preferably 6,000~60,000.

The polymer composition of the present invention may contain other polymers other than the polymer (A) and polyurethane. If specific examples of other polymers are given, for example, polyimide precursors other than polymer (A) or imides thereof, polyurethanes other than the above-mentioned polyurethanes, and polysiloxanes , polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) Anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, polymers in the group consisting of poly(meth)acrylates, etc. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, 3000 (manufactured by Cray Valley Co.), GSM301 (manufactured by GIFUSHELLAC Co., Ltd.), and specific examples of poly(isobutylene-maleic anhydride) copolymers ISOBAM-600 (made by Kuraray) is mentioned, and the specific example of a poly(vinyl ether-maleic anhydride) copolymer includes GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by ISP Japan). The other polymers may be used alone or in combination of two or more. The content ratio of other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass, based on the total of 100 parts by mass of the polymers contained in the polymer composition.

The polymer composition of the present invention is preferably a liquid composition in which the above-mentioned polymer (A) and polyurethane are dissolved or dispersed in an organic solvent. Specifically, the organic solvent contained in the above-mentioned polymer composition is not particularly limited as long as the polymer components are uniformly dissolved, and examples thereof include: N,N-dimethylformamide, N,N-dimethylacetamide Amine, N,N-dimethyllactamide, N,N-dimethylacrylamide, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone, N -Ethyl-2-pyrrolidone, dimethylsulfene, γ-butyrolactone, 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 Base-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl - 2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (these may also be collectively referred to as "good solvent"). Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethyl Propanamide or γ-butyrolactone is preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, particularly preferably 30 to 80% by mass, of the entire solvent contained in the polymer composition.

In addition, the organic solvent contained in the polymer composition is preferably mixed with a solvent (also referred to as a poor solvent) that improves the coatability of the polymer composition and the surface smoothness of the coating film in addition to the above-mentioned solvents. Solvents are preferred. Specific examples of poor solvents used in combination are as follows, but are not limited thereto. The content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and most preferably 20 to 70% by mass, of the entire solvent contained in the polymer composition. The type and content of the poor solvent can be properly selected according to the liquid crystal alignment agent coating device, coating conditions, coating environment, etc.

Poor solvents, such as: diisopropyl ether, diisobutyl ether, diisobutylmethanol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Alcohol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl Diethyl ether, diethylene glycol dibutyl 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 mono Methyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetic acid Ester, 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 Diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate , propylene glycol monoethyl ether acetate, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate ester, 3-methoxypropyl propionate, 3-methoxybutyl propionate, n-butyl lactate, isopentyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-di Methyl-4-heptanone), etc.

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

The ideal combination of good solvent and poor solvent, such as N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether , N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4- Methyl-2-pentanone, N-ethyl-2-pyrrolidone and propylene glycol diacetate, N,N-dimethyl lactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and 3 -Ethoxyethyl propionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and dipropylene glycol mono Methyl ether, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate and diethylene glycol Monopropyl ether, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether, N,N-dimethyl lactamide and ethylene glycol monobutyl ether, N,N-dimethyl lactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and diethylene glycol monoethyl ether and butyl cellothreoacetate, N-methyl-2-pyrrolidone and Diethylene glycol monomethyl ether and butyl cellothracetate, N,N-dimethyl lactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-Hydroxy-4-methyl-2-pentanone and 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-pentanone 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, gamma-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 and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl Base ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether Butyl methanol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N -Ethyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and Propylene glycol monobutyl ether and propylene glycol diacetate, N-ethyl-2-pyrrolidone 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 and ethylene glycol monobutyl ether and ethylene glycol monobutyl ether Acetate, γ-butyrolactone and ethylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone and 4-methyl-2-pentyl acetate and ethylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and cyclohexyl acetate and diacetone alcohol, N,N-di Methacrylamide and 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylacrylamide and propylene glycol diacetate, tetramethylurea and 4-hydroxy-4-methyl -2-pentanone, tetramethylurea and propylene glycol diacetate, N,N-dimethylacrylamide and propylene glycol monobutyl ether, tetramethylurea and propylene glycol monobutyl ether, tetramethylurea and cyclohexyl Ketone and propylene glycol monomethyl ether, N,N-dimethylacrylamide and propylene glycol monomethyl ether, N,N-dimethylacrylamide and ethylene glycol monobutyl ether acetate, N,N-dimethylacrylamide Dimethylacrylamide and ethylene glycol monobutyl ether, tetramethylurea and propylene glycol monomethyl ether, N,N-dimethylacrylamide and cyclohexanone and diethylene glycol diethyl ether, N,N-diethyl 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 and propylene glycol monomethyl ether, N-methyl-2-pyrrolidone and cyclohexanone and propylene glycol monomethyl ether, etc.

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). The additive components, such as: crosslinking compounds, functional silane compounds, metal chelate compounds, hardening accelerators, surfactants, antioxidants, sensitizers, preservatives, used to adjust the dielectric constant of the resin film, Compounds of resistors, etc. The above-mentioned cross-linking compound, for example: selected from the group having at least one substituent selected from epoxy group, isocyanate group, oxetanyl group, cyclocarbonate group, blocked isocyanate group, hydroxyl group and alkoxyl group At least one crosslinking compound in the group consisting of a crosslinking compound (c-1) and a crosslinking compound (c-2) having a polymerizable unsaturated group. By containing the above-mentioned cross-linking compound, the following effects can be obtained: a liquid crystal display element can be obtained that reduces the occurrence of so-called flickering (flickering) that occurs when the backlight is irradiated on the liquid crystal display element when the liquid crystal is just driven.

Desirable specific examples of the above-mentioned crosslinkable compounds (c-1) and (c-2) include the following compounds. Compounds (c-1) having an epoxy group include: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Diglycidyl Ether, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycerin Diglycidyl Ether, 2,2-Dibromoneopentyl Glycol Diepoxide Propyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, bisphenol A epoxy resin such as EPIKOTE828 (manufactured by Mitsubishi Chemical Corporation), EPIKOTE807 (manufactured by Mitsubishi Chemical Corporation), etc. Bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), epoxy resin containing a biphenyl skeleton such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), EPPN-201 (manufactured by Japan Chemical Co., Ltd. Phenol novolak type epoxy resins such as those manufactured by pharmaceutical companies), EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.) etc. Methyl)methane, N,N,N',N'-tetraepoxypropyl-1,4-phenylenediamine, N,N,N',N'-tetraepoxypropyl-2,2'- Dimethyl-4.4'-diaminobiphenyl, 2,2-bis[4-(N,N-diepoxypropyl-4-aminophenoxy)phenyl]propane, N,N,N ',N'-tetraepoxypropyl-4,4'-diaminodiphenylmethane and other compounds bonded by tertiary nitrogen atoms and aromatic carbon atoms; N,N,N',N'-tetracyclic Oxypropyl-1,2-diaminocyclohexane, N,N,N',N'-tetraepoxypropyl-1,3-diaminocyclohexane, N,N,N',N '-Tetraepoxypropyl-1,4-diaminocyclohexane, Bis(N,N-Diepoxypropyl-4-aminocyclohexyl)methane, Bis(N,N-Diepoxypropylene 1,3-bis(N, N-Diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-Diglycidylaminomethyl)cyclohexane, 1,3-bis(N,N-Diglycidylaminomethyl)cyclohexane phenylmethyl)benzene, 1,4-bis(N,N-diepoxypropylaminomethyl)benzene, 1,3,5-paraffin(N,N-diepoxypropylaminomethyl)cyclohexane, Compounds with tertiary nitrogen atoms bonded to aliphatic carbon atoms such as 1,3,5-paraffin (N,N-dioglycidylaminomethyl)benzene, triglycidyl isopropyl groups such as TEPIC (manufactured by Nissan Chemical Co., Ltd.) Isocyanurate compounds such as cyanurate, compounds described in paragraph [0037] of JP-A-10-338880, compounds described in WO2017/170483, etc.; Compounds having isocyanate groups include the above-mentioned diisocyanate compounds, etc.; Compounds (c-1) having an oxetane group include 1,4-bis{[(3-ethyl-3-epoxypropylene)methoxy]methyl}benzene (ARON OXETANE OXT- 121(XDO)), bis[2-(3-epoxypropylene)butyl]ether (ARON OXETANE OXT-221(DOX)), 1,4-bis[(3-ethyloxetane- 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), paragraphs [0170]~[0175] of WO2011/132751, having two or more oxetanyl groups compounds, etc.; Compounds (c-1) having a cyclocarbonate group include N,N,N',N'-tetra[(2-oxo-1,3-dioxolane-4-yl) Methyl]-4,4'-diaminodiphenylmethane, N,N'-bis[(2-oxo-1,3-dioxolan-4-yl)methyl]-1, 3-phenylenediamine, compounds described in WO2011/155577, etc.; Compounds having blocked isocyanate groups include CORONATE AP STABLE M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (manufactured by Tosoh Corporation), TAKENATE B-830, B-815N, B- 820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (the above are manufactured by Mitsui Chemicals Co., Ltd.), paragraphs [0046]~[0047] of JP-A-2014-224978 Compounds with 2 or more protected isocyanate groups, compounds with 3 or more protected isocyanate groups described in paragraphs [0119]~[0120] of WO2015/141598, etc.; Compounds (c-1) having hydroxyl and/or alkoxy groups include: N,N,N',N'-tetra(2-hydroxyethyl)adipamide, 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-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, described in paragraph [0058] of International Publication No. 2015/072554 and JP-A-2016-118753 Compounds, compounds described in JP-A-2016-200798, compounds described in WO2010/074269, etc.; The crosslinkable compound (c-2) having a polymerizable unsaturated group includes glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-,1,3-body mixture), Glycerol Ginseng (Meth) Acrylate, Glycerin 1,3-Diglycerin Di(Meth) Acrylate, Neopentylthritol Tri(Meth) Acrylate, Diethylene Glycol Mono(Meth) Acrylate, Tri Ethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, and the like.

[化34]

More desirable specific examples of the above-mentioned crosslinkable compounds (c-1) and (c-2) include compounds represented by any one of the following formulas (CL-1) to (CL-12). [chem 33]

[chem 34]

The above is an example of the crosslinkable compound and is not limited thereto. Moreover, the crosslinkable compound used for the liquid crystal aligning agent of this invention may be 1 type or may combine 2 or more types. The content of the crosslinking compound in the liquid crystal alignment agent of the present 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.

The compound used to adjust the dielectric constant and resistance of the resin film mentioned above may include monoamines such as 3-picolylamine having an aromatic heterocyclic ring containing a nitrogen atom. When using a monoamine having a nitrogen-containing aromatic heterocyclic ring, it 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.

Ideal specific examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2- Aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-amino Ethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methoxysilane Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Methacryloxypropyl triethoxysilane, 3-acryloxypropyltrimethoxysilane, ginseng (3-trimethoxysilylpropyl) isocyanurate, 3-mercaptopropyl Methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. When using a functional silane compound, the usage-amount is preferably 0.1-30 mass parts with respect to 100 mass parts of polymer components contained in a polymer composition, More preferably, it is 0.1-20 mass parts.

The solid content concentration in the polymer composition (the ratio of the total mass of the components other than the solvent of the polymer composition to the total mass of the polymer composition) can be appropriately selected in consideration of viscosity, volatility, etc., preferably 1 ~10% by mass. That is, the polymer composition is coated on the surface of the substrate as described later, preferably by heating to form a resin film.

The particularly desirable range of solid content concentration varies depending on the method used when coating the polymer composition on the substrate. For example, when the spin coating method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. When using the printing method, the solid content concentration is in the range of 3 to 9% by mass, and the viscosity of the solution is preferably in the range of 12 to 50 mPa·s. When using the inkjet method, the solid content concentration is in the range of 1 to 5% by mass, and the viscosity of the solution is preferably in the range of 3 to 15 mPa·s. The temperature for preparing the polymer composition is preferably 10-50°C, more preferably 20-30°C.

＜Application and resin film＞ The polymer composition described above can be coated on a substrate, preferably by heat treatment to volatilize the solvent component to form a resin film, for example. The polymer composition and resin film of the present invention can be effectively used in various technical applications, such as liquid crystal alignment agents, electronic circuit materials, semiconductor materials, electrical insulation materials, wire coating materials, lighting applications, molding materials and other applications. Specifically, various resin films equipped with actuators such as display elements, semiconductor elements, and motors, piezoelectric sensors, and pyroelectric sensors, etc., such as liquid crystal alignment films (for retardation films) Liquid crystal alignment film, scanning antenna, liquid crystal alignment film for liquid crystal array antenna or liquid crystal alignment film for liquid crystal light adjustment element of transmission scattering type), protective film (for example: protective film for color filter), spacer film, Interlayer insulation film, antireflection film, wiring coating film, antistatic film, motor insulation film (gate insulation film for flexible displays), etc. Among them, the polymer composition of the present invention is suitable as a liquid crystal alignment agent.

＜Liquid crystal alignment agent＞ The liquid crystal alignment agent of the present invention is composed of the polymer composition of the present invention. That is, the liquid crystal alignment agent and the polymer composition of the present invention also contain the above-mentioned polymer (A) and polyurethane. Moreover, it is preferable to contain at least any one of other polymers, organic solvents, and additive components. For details such as the above-mentioned polymer (A), polyurethane, other polymers, organic solvents, and additive components, blending ratios, solid content concentrations, etc., the description of the above-mentioned polymer composition can be used.

[Liquid crystal alignment film and liquid crystal display element] By using the above-mentioned polymer composition or the above-mentioned liquid crystal alignment agent, it is possible to manufacture a liquid crystal alignment film as a resin film. Moreover, the liquid crystal display element of this invention is equipped with the liquid crystal alignment film formed using the said polymer composition or the said liquid crystal alignment agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited, and can be used in, for example, TN type, STN (Super Twisted Nematic) type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type (IPS type), FFS type, optical compensation bending type (OCB type) and other various operation modes.

The liquid crystal display element of the present invention can utilize the method that for example comprises following steps (1)～(4), the method comprising steps (1)～(2) and (4), comprising steps (1)～(3), ( 4-2) and (4-4), or a method including steps (1) to (3), (4-3) and (4-4).

<Step (1): The step of coating the liquid crystal alignment agent on the substrate> Step (1) is a step of coating the liquid crystal alignment agent of the present invention on the substrate. The specific example of step (1) is as follows. The liquid crystal alignment agent of the present invention is coated on one side of the substrate provided with the patterned transparent conductive film by appropriate coating methods such as roll coating method, spin coating method, printing method, and inkjet method. Here, the substrate is not particularly limited as long as it is highly transparent, and a plastic substrate such as a glass substrate, a silicon nitride substrate, an acrylic substrate, or a polycarbonate substrate may be used together. In addition, if the reflective liquid crystal display element has only one side substrate, opaque objects such as silicon wafers can also be used, and the electrodes at this time can also use materials that reflect light such as aluminum. Also, when manufacturing IPS-type or FFS-type liquid crystal display elements, a substrate provided with electrodes made of a comb-shaped transparent conductive film or metal film and an opposite substrate without electrodes are used.

The method of coating the liquid crystal alignment agent on the substrate and forming a film includes screen printing, offset printing, flexographic printing, inkjet method, or spraying method. Among them, the coating and film-forming methods by the inkjet method are preferable.

<Step (2): The step of calcining the coated liquid crystal alignment agent> Step (2) is a step of calcining the liquid crystal alignment agent coated on the substrate to form a film. The specific example of step (2) is as follows. Step (1) After coating the liquid crystal alignment agent on the substrate, the solvent can be evaporated by heating methods such as a hot plate, a heat circulation oven or an IR (infrared) oven, or polyamide acid or polyamide ester thermal imidization. The drying and calcining steps after coating the liquid crystal alignment agent of the present invention can be performed at any temperature and time, and can also be performed multiple times. Reducing the temperature of the solvent of the liquid crystal alignment agent can be carried out at, for example, 40~180°C. Considering the viewpoint of shortening the manufacturing process, it can also be carried out at 40~150°C. The calcination time is not particularly limited, for example, 1 to 10 minutes or 1 to 5 minutes. When thermal imidization of polyamic acid or polyamic acid ester is carried out, a calcining step can be added after the above step, for example, at a temperature range of 150~300°C or 150~250°C. The calcination time is not particularly limited, for example, 5-40 minutes, or 5-30 minutes of calcination time. If the film thickness of the calcined film is too thin, the reliability of the liquid crystal display element may be reduced, so 5~300nm is more ideal, and 10~200nm is more ideal.

<Step (3): The step of aligning the film obtained in step (2)> Step (3) is a step of performing alignment treatment on the film obtained in step (2) as the case may be. That is, in a liquid crystal display element of a horizontal alignment type such as an IPS method or an FFS method, an alignment ability-imparting treatment is performed on the coating film. On the other hand, in a vertical alignment type liquid crystal display device such as VA mode or PSA mode, the formed coating film can be directly used as a liquid crystal alignment film, but the coating film can also be subjected to an alignment ability imparting treatment. Alignment treatment methods for liquid crystal alignment films, such as rubbing treatment and photo-alignment treatment. The photo-alignment treatment method can include irradiating the surface of the above-mentioned membranous object with radiation deflected in a certain direction. Depending on the situation, it is better to conduct a heat treatment at a temperature of 150-250°C to impart liquid crystal alignment (also known as liquid crystal alignment ability) method. As the radiation, ultraviolet rays or visible rays having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays with a wavelength of 100 to 400 nm are preferred, and ultraviolet rays with a wavelength of 200 to 400 nm are more preferred.

The exposure dose of the above-mentioned radiation is preferably 1~10,000mJ/cm ² . Among them, 100~5,000mJ/cm ² is preferable. Moreover, when irradiating radiation, in order to improve liquid crystal alignment, you may irradiate while heating the board|substrate which has the said membranous thing at 50-250 degreeC. The liquid crystal alignment film fabricated in this manner can stably align liquid crystal molecules in a certain direction. Also, the liquid crystal alignment film irradiated with polarized radiation as described above may be subjected to contact treatment with water or a solvent, or the liquid crystal alignment film irradiated with radiation may be heat-treated.

The solvent used in the above-mentioned contact treatment is not particularly limited as long as it dissolves the decomposition product generated from the film-like material 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, butylcylonol, 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 are ideal in consideration of versatility and safety of solvents, water, 1-methoxy-2-propanol or lactic acid Ethyl esters are more desirable. A solvent may be used alone or in combination of two or more kinds.

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

＜Step (4): Steps for making liquid crystal cells＞ Two substrates on which the liquid crystal alignment film was formed as described above were prepared, and liquid crystals were arranged between the two substrates facing each other. Specifically, the following two methods are mentioned. In the first method, two substrates are arranged facing each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other. Then, the peripheral parts of the two substrates were bonded together using a sealant, and the liquid crystal composition was injected into the cell gap partitioned by the substrate surface and the sealant to contact the film surface, and then the injection hole was sealed. The above-mentioned liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. Hereinafter, a liquid crystal composition having a positive dielectric anisotropy is also referred to as a positive type liquid crystal, and a liquid crystal composition having a negative dielectric anisotropy is also referred to as a negative type liquid crystal. The above-mentioned liquid crystal composition may also contain fluorine atoms, hydroxyl groups, amino groups, groups containing fluorine atoms (for example: trifluoromethyl), cyano atoms, alkyl groups, alkoxy groups, alkenyl groups, isothiocyanate Liquid crystal compounds of radicals, heterocycles, cycloalkanes, cycloalkenes, steroid skeletons, benzene rings, or naphthalene rings may also contain compounds with more than two rigid sites (mesogen skeletons) exhibiting liquid crystallinity in the molecule (for example: Rigid two biphenyl structures, or biphenyl compounds formed by linking terphenyl structures with alkyl groups). The liquid crystal composition may also be a liquid crystal composition in a nematic phase, a liquid crystal composition in a smectic phase, or a liquid crystal composition in a cholesteric phase. In addition, in the above-mentioned liquid crystal composition, an additive may be further added from the viewpoint of making the alignment of the liquid crystal better. Such additives include: photopolymerizable monomers such as compounds having the following polymerizable groups; optically active compounds (for example: S-811 manufactured by Merck Co., Ltd.); antioxidants; ultraviolet absorbers; pigment; defoamer; polymerization initiator; or polymerization inhibitor, etc. Examples of positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, and MLC-7081 manufactured by Merck & Co., Ltd. Negative liquid crystal, such as MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, or MLC-7029 manufactured by Merck wait. In addition, in the PSA mode, MLC-3023 manufactured by Merck & Co., Ltd. is exemplified as a liquid crystal containing a compound having a polymerizable group.

Also, the second method is a method called ODF (One Drop Fill) method. On one of the two substrates on which the liquid crystal alignment film has been formed, apply, for example, a UV-curable sealant on predetermined positions, and then drop liquid crystal composition on several predetermined positions on the surface of the liquid crystal alignment film. Then, with the liquid crystal alignment film facing the other substrate, the liquid crystal composition is pushed out on the entire surface of the substrate to make it contact with the film surface. Then, the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant. When using either method, it is more heated until the liquid crystal composition used becomes the temperature of the isotropic phase, and then slowly cooled to room temperature to remove the flow alignment when filling the liquid crystal is ideal. In addition, when rubbing the coating film, two substrates are arranged facing each other so that the rubbing directions of the respective coating films form a predetermined angle with each other, for example, perpendicularly or antiparallel. As the sealing agent, for example, an epoxy resin containing alumina balls as a hardener and a spacer can be used. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred.

The liquid crystal alignment agent of the present invention is also suitable for use in a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal comprising a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The composition is a liquid crystal display element (PSA type liquid crystal display element) produced by polymerizing a polymerizable compound by at least one of active energy ray irradiation and heating while applying a voltage between electrodes. The liquid crystal alignment agent of the present invention is also suitable for use in a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. Liquid crystal alignment film, a liquid crystal display element (SC-PVA mode type liquid crystal display element) manufactured through the step of applying voltage between electrodes.

<Step (4-2): In the case of a PSA type liquid crystal display element> Except injecting or dripping the liquid crystal composition containing a polymerizable compound, it is the same as (4) above. A polymerizable compound, for example, a polymerizable compound having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule.

<Procedure (4-3): In case of SC-PVA mode type liquid crystal display element> It is also possible to employ a method of producing a liquid crystal display element through a step of irradiating ultraviolet rays described later in the same manner as in (4) above. According to this method, a liquid crystal display element with excellent response speed can be obtained with a small amount of light irradiation as in the case of manufacturing the above-mentioned PSA type liquid crystal display element. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups in the molecule, and its content is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of all polymer components, more preferably 1 ~20 parts by mass. In addition, the polymer used in the liquid crystal alignment agent may also have the above-mentioned polymerizable group. Such a polymer is, for example, a polymer obtained by reacting a diamine component containing a diamine having the above-mentioned photopolymerizable group at the end.

<Step (4-4): Step of irradiating ultraviolet rays> The liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates obtained in the above (4-2) or (4-3). The voltage applied here can be, for example, a DC or AC voltage of 5-50V. Also, as the light to be irradiated, for example, ultraviolet rays and visible rays including light with a wavelength of 150 to 800 nm can be used, but ultraviolet light including light with a wavelength of 300 to 400 nm is preferable. As a light source for irradiating 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 irradiation is preferably 1,000-200,000 J/m ² , more preferably 1,000-100,000 J/m ² .

In addition, if necessary, a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. The polarizing plate attached to the outer surface of the liquid crystal cell can be exemplified: a polarizing film made of a polarizing film called "H film" obtained by sandwiching a cellulose acetate protective film while stretching and aligning polyvinyl alcohol to absorb iodine. Polarizing plate composed of plate or H film itself.

The liquid crystal display device of the present invention can be effectively used in various devices, such as clocks, portable game machines, word processors, notebook personal computers, navigation systems, video cameras, PDAs, digital cameras, mobile phones, smart phones, various Various display devices such as monitors, LCD TVs, and information displays. [Example]

[化36]

[化37]

Hereinafter, the present invention will be specifically described with examples and the like, but the present invention is not limited to these examples. In addition, the abbreviations of compounds and solvents are as follows. (Organic solvent) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: Ethylene glycol monobutyl ether (diamine) DA-1~DA-7: Each is the following structural formula (DA-1 )~(DA-7) Compounds (tetracarboxylic acid derivatives) CA-1~CA-3: Each is a compound (diisocyanate) represented by the following structural formulas (CA-1)~(CA-3) DI- 1: 4,4'-diphenylmethane diisocyanate (diol) EG-1: Polyethylene Glycol 400 (manufactured by Tokyo Chemical Industry Co., Ltd.) (an organic compound in which R in the formula (EG) is a hydrogen atom and n is 5 or more diol) EG-2: Polyethylene Glycol 600 (manufactured by Tokyo Chemical Industry Co., Ltd.) (a diol having an organic group in which R in the formula (EG) is a hydrogen atom and n is 5 or more) EG-3: Ethylene Glycol ( Tokyo Chemical Industry Co., Ltd. (manufactured by Tokyo Chemical Industry Co., Ltd.) (diol having an organic group in which R in the formula (EG) is a hydrogen atom and n is 1) EG-4: Diethylene Glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) (having R is a hydrogen atom and n is a diol with an organic group of 2) EG-5: Tetraethylene Glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) (a diol with an organic group in which R is a hydrogen atom and n is 4 in the formula (EG) ) (blocking agent) Boc ₂ O: di-tert-butyl dicarbonate (additive) AD-1~AD-3: each is a compound represented by the following structural formula (AD-1)~(AD-3) [Chemical 35 ]

[chem 36]

[chem 37]

＜Viscosity＞ In the synthesis example, the viscosity of the polymer solution is determined by using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL, a conical rotor TE-1 (1°34', R24), and a temperature of 25°C. condition determination. ＜Determination of imidization rate of polyimide＞ The imidization rate of the polyimide in the synthesis example was measured in the following manner. 30 mg of polyimide powder was charged into an NMR (nuclear magnetic resonance) sample tube (NMR standard test tube, φ5 (manufactured by Kusano Science Co., Ltd.)), and deuterated dimethyl sulfide (DMSO-d6, 0.05% by mass TMS (four Methylsilane) mixture) (0.53mL), apply ultrasound to dissolve it completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring machine (JNW-ECA500) (manufactured by JEDC). The imidization rate is determined by taking the proton from the structure that does not change before and after imidization as the standard proton, using the peak cumulative value of this proton and the NH from the amino acid that appears around 9.5ppm~10.0ppm The cumulative value of the proton peak of the base can be calculated according to the following formula. Imidization rate (%)＝(1-α・x/y)×100 In the above formula, x is the cumulative value of the proton peak from the NH group of amide acid, y is the cumulative value of the peak proton of the reference proton, and α is the case of polyamide acid (imidization rate is 0%) , the number ratio of the reference proton relative to the NH group proton of amide acid.

[Synthesis of Polymer] (Synthesis Example 1) DA-1 (8.02g, 28.0mmol) and NMP (58.8g) were measured in a 100mL eggplant-shaped flask with a stirring device and a nitrogen gas introduction tube, and nitrogen gas was introduced. Stir to dissolve. This diamine solution was stirred under water cooling and CA-1 (5.11g, 26.0mmol) and NMP (37.4g) were added simultaneously, and stirred for 2 hours under a nitrogen atmosphere to obtain a polymer (polymer-1) solution ( Viscosity: 182mPa・s). (Synthesis Examples 2 to 5) Using the diamines and tetracarboxylic acid derivatives shown in Table 1 below, the same procedures as in Synthesis Example 1 were used to obtain the polymers shown in Table 1 below (Polymer-2 )~(Polymer-5) solution. In Table 1, the numerical value described below the compound name represents the mass of each compound used in the synthesis. [Table 1]

(Synthesis Example 6) Measure DA-2 (6.84g, 28.0mmol) and NMP (61.6g) into a 100mL eggplant-shaped flask equipped with a stirring device and a nitrogen gas introduction tube, and stir while feeding nitrogen gas to dissolve them. Stirring this diamine solution under water cooling, CA-2 (4.52g, 20.2mmol) and NMP (21.7g) were added, and it stirred at 40 degreeC under nitrogen atmosphere for 2 hours. Furthermore, DI-1 (1.40g, 5.60mmol) and NMP (10.3g) were added and stirred at 23°C for 2 hours under a nitrogen atmosphere to obtain a solution of the polymer (polymer-6) (viscosity: 242mPa·s) . (Synthesis Example 7) DA-5 (8.04g, 40.2mmol), DA-6 (4.36g, 10.9mmol), DA-7 (12.2g , 21.9mmol) and NMP (98.4g), were stirred while feeding nitrogen gas, and dissolved. Stirring this diamine solution under water cooling, CA-3 (9.40g, 47.5mmol) and NMP (37.6g) were added, and it stirred at 50 degreeC in nitrogen atmosphere for 2 hours. Then CA-1 (4.65g, 23.7mmol) and NMP (18.6g) were added, and stirred at 23°C for 2 hours under nitrogen atmosphere to obtain a solution of polyamic acid (PAA-I) (viscosity: 1230mPa·s). Measure the solution (100g) of the polyamic acid (PAA-I) obtained above in a 200mL Erlenmeyer flask equipped with a stirring bar, add Boc2O (1.24g, _5.68mmol ), and stir at 40°C for 15 hours to obtain Solution of blocked polyamic acid (PAA-I-1). Take the above solution (100g) of (PAA-I-1) in a 200mL Erlenmeyer flask equipped with a stirring bar, add NMP (66.7g), acetic anhydride (14.2g) and pyridine (4.70g), and stir at room temperature After 30 minutes, the reaction was carried out at 60° C. for 4 hours. This reaction solution was poured into methanol (650 g), and the obtained precipitate was separated and filtered. After washing this precipitate with methanol, it dried under reduced pressure at 80 degreeC, and obtained the powder of polyimide (imidization rate: 90%). Furthermore, the polyimide powder (9.60 g) was measured in a 100 mL Erlenmeyer flask equipped with a stirring bar, NMP (70.4 g) was added, and stirred at 70° C. for 24 hours to dissolve it to obtain polyimide (Polymer-7) solution (viscosity: 76mPa·s).

(Synthesis Example 8) Measure EG-1 (4.80 g, 12.0 mmol) and NMP (7.20 g) in a 100 mL eggplant-shaped flask equipped with a stirring device and a nitrogen gas introduction tube, and stir while feeding nitrogen gas to dissolve them. While stirring this solution under water cooling, DI-1 (2.97 g, 11.9 mmol) and NMP (4.50 g) were added, and stirred for 2 hours under a nitrogen atmosphere. After the reaction, NMP (58.3 g) was added to obtain a solution of the polymer (Polymer-8) (viscosity: 12 mPa·s). (Synthesis Examples 9~12) Use the diisocyanate and diol shown in Table 2 below, and implement the same procedure as in Synthesis Example 8, to obtain the polymers (polymer-9) shown in Table 2 below~ (Polymer-12) solution. In Table 2, the numerical value described below the compound name represents the mass of each compound used in the synthesis. [Table 2]

[Preparation of liquid crystal alignment agent] (Example 1) In a 50mL Erlenmeyer flask equipped with a stirring bar, measure 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. g), NMP (0.59g), GBL (9.30g) and BCS (4.00g) were added and stirred at room temperature for 2 hours to obtain liquid crystal alignment agent (1).

(Examples 2 to 12, Comparative Examples 1 to 12) The types and amounts of the polymer solution, solvent, and additive to be used were changed as shown in the following table 3, and the same operations as in Example 1 were performed except that The liquid crystal alignment agents (2)-(24) were obtained. In addition, among the additives in Table 3, AD-1 to AD-3 were each added as a solution containing 10% by mass of NMP. Add additives (AD-1~AD-3, EG-1~EG-2) before adding NMP, GBL and BCS. [table 3] Liquid crystal alignment agent polymer NMP GBL BCS additive Example 1 (1) Polymer-1 5.83g Polymer-8 0.28g 0.59g 9.30g 4.00g - Example 2 (2) Polymer-1 5.83g Polymer-8 0.56g 0.31g 9.30g 4.00g - Example 3 (3) Polymer-1 5.83g Polymer-9 0.28g 0.59g 9.30g 4.00g - Example 4 (4) Polymer-1 5.83g Polymer-9 0.28g 0.31g 9.30g 4.00g - Example 5 (5) Polymer-2 5.83g Polymer-9 0.56g 0.31g 9.30g 4.00g - Example 6 (6) Polymer-3 5.83g Polymer-9 0.56g 0.31g 9.30g 4.00g - Example 7 (7) Polymer-4 5.83g Polymer-9 0.56g 0.31g 9.30g 4.00g - Example 8 (8) Polymer-5 5.83g Polymer-9 0.56g 0.31g 9.34g 4.00g - Example 9 (9) Polymer-5 5.50g Polymer-9 0.53g 0.30g 9.34g 4.00g AD-1 0.33g Example 10 (10) Polymer-5 5.50g Polymer-9 0.53g 0.30g 9.34g 4.00g AD-2 0.33g Example 11 (11) Polymer-5 5.50g Polymer-9 0.53g 0.30g 9.34g 4.00g AD-3 0.33g Example 12 (12) Polymer-6 5.83g Polymer-9 0.56g 0.31g 9.30g 4.00g - Comparative example 1 (13) Polymer-1 5.83g - 0.87g 9.30g 4.00g - Comparative example 2 (14) Polymer-2 5.83g - 0.87g 9.30g 4.00g - Comparative example 3 (15) Polymer-3 5.83g - 0.87g 9.30g 4.00g - Comparative example 4 (16) Polymer-4 5.83g - 0.87g 9.30g 4.00g - Comparative Example 5 (17) Polymer-5 5.83g - 0.87g 9.30g 4.00g - Comparative Example 6 (18) Polymer-6 5.83g - 0.87g 9.30g 4.00g - Comparative Example 7 (19) Polymer-7 5.83g - 0.87g 9.30g 4.00g - Comparative Example 8 (20) Polymer-1 5.83g Polymer-10 0.56g 0.87g 9.30g 4.00g - Comparative Example 9 (twenty one) Polymer-1 5.83g Polymer-11 0.56g 0.87g 9.30g 4.00g - Comparative Example 10 (twenty two) Polymer-1 5.83g Polymer-12 0.56g 0.87g 9.30g 4.00g - Comparative Example 11 (twenty three) Polymer-1 5.83g - 0.81g 9.30g 4.00g EG-1 0.06g Comparative Example 12 (twenty four) Polymer-1 5.83g - 0.81g 9.30g 4.00g EG-2 0.06g

[Production of liquid crystal display elements] Fabrication of liquid crystal cells with the configuration of fringe field switching (Fringe Field Switching: FFS) mode liquid crystal display elements. First prepare the substrate with electrodes. The substrate is a glass substrate with a size of 35mm×40mm and a thickness of 0.7mm. Form an ITO electrode with a full-surface pattern on the substrate as the counter electrode of the first layer, and form a film by CVD (chemical vapor deposition) method as the second layer on the counter electrode of the first layer SiN (silicon nitride) film. For the SiN film of the second layer, a film with a thickness of 500nm that functions as an interlayer insulating film is used. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning the ITO film as the third layer is arranged, and two pixels of the first pixel and the second pixel are formed, each pixel The size is 10mm in length and 5mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the SiN film of the second layer.

The pixel electrode on the third layer, the central part is bent at an inner angle of 160°, and the electrode elements with a width of 3 μm are spaced in parallel at intervals of 6 μm. It has a comb-tooth shape arranged in many places, and one pixel is used to connect multiple electrode elements. The line of the Ministry is the boundary, with the first and second districts.

Comparing the first area and the second area of each pixel, the formation directions of the electrode elements constituting the pixel electrodes are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as the reference, the first region of the pixel is formed in such a way that the electrode elements of the pixel electrode form an angle (clockwise) of +10°, and the second region of the pixel is formed The electrode elements of the pixel electrodes are formed at an angle of -10° (counterclockwise). That is, in the first area and the second area of each pixel, the direction of the rotation of the liquid crystal in the substrate surface (in-plane switching) caused by the voltage application between the pixel electrode and the counter electrode, Departments become opposite directions to each other.

Then filter the liquid crystal alignment agent obtained above with a filter with a pore size of 1.0 μm, and apply it on the surface of the substrate with electrodes (the first glass substrate) prepared above and the surface of the ITO film formed on the back by the spin coating method. The surface of the glass substrate (second glass substrate) of the columnar spacer of 4 μm. Then, it was dried on a hot plate at 80°C for 2 minutes, and then calcined in a hot air circulation oven at 230°C for 30 minutes to obtain a substrate with a liquid crystal alignment film with a film thickness of 60 nm. After rubbing the surface of the substrate with the liquid crystal alignment film with a yarn cloth (YA-20R manufactured by Yoshikawa Chemical Co., Ltd.) (roller diameter: 120mm, roll speed: 1000rpm, moving speed: 20mm/sec, push-in length: 0.4mm), Ultrasonic irradiation was carried out in pure water for 1 minute and washed, and then the water droplets were removed by blowing air, and then dried at 80°C for 15 minutes to obtain a substrate with a liquid crystal alignment film. The obtained 2 substrates with liquid crystal alignment film were used as a group, and a sealant (XN-1500T manufactured by Mitsui Chemicals Co., Ltd.) was printed on the substrate in the form of retaining the liquid crystal injection port, and the other substrate was connected with the liquid crystal alignment film surface. Facing, the rubbing direction becomes antiparallel to fit. Afterwards, heat treatment was carried out at 150°C for 60 minutes to harden the sealant and produce void cells with a cell gap of 4 μm. Liquid crystal MLC-7026 (manufactured by Merck & Co., Ltd.) was injected into this ghost cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS type liquid crystal display element. After that, the obtained liquid crystal display element was heated at 120° C. for 1 hour, and left overnight at 23° C. for evaluation.

[Evaluation of afterimage characteristics due to long-term AC drive] For the FFS-driven liquid crystal cell manufactured above, an AC voltage of ±5.8V was applied at a frequency of 60Hz for 120 hours in a constant temperature environment of 60°C. Thereafter, the pixel electrode and the counter electrode of the liquid crystal cell were short-circuited, and left at room temperature for one day in this state. For the above-mentioned liquid crystal cell, calculate the deviation between the alignment direction of the liquid crystal in the first area of the pixel and the alignment direction of the liquid crystal in the second area in the state of no voltage applied, and define it as the angle Δθ. Specifically, a liquid crystal cell is placed between two polarizers arranged so that the polarization axes are perpendicular to each other, the backlight is turned on, and the arrangement angle of the liquid crystal cell is adjusted so that the transmitted light intensity in the first area of the pixel becomes the minimum, and then the The rotation angle (Δθ) required to rotate the liquid crystal cell so that the intensity of transmitted light in the second area of the pixel is minimized. Regarding the afterimage characteristic caused by long-term AC drive, the smaller the value of the rotation angle, the better it can be said. Specifically, when the rotation angle was 0.15 degrees or less, it was rated as "O", when it exceeded 0.15 degrees and 0.25 degrees or less, it was rated as "Δ", and when it exceeded 0.25 degrees, it was rated as "×". The results are shown in Table 4.

[Evaluation of film strength] The liquid crystal alignment agent filtered through a filter with a pore size of 1.0 μm was spin-coated on the ITO surface of the glass substrate with ITO electrodes attached to the entire surface, and dried on a hot plate at 80° C. for 2 minutes. Afterwards, it was calcined in a hot air circulation oven at 230° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film with a film thickness of 60 nm. This liquid crystal alignment film was rubbed with a yarn cloth (roller diameter: 120mm, roll rotation speed: 1000rpm, moving speed: 20mm/sec, pushing length: 0.6mm). The haze value of this board|substrate was measured with the HZ-V3 haze meter manufactured by Suga Testing Instrument Co., Ltd. The smaller the haze value, it can be said that the film is not scraped, that is, the film strength is high. When the haze value was 0.1 or less, it was rated as "o", when it exceeded 0.1 and 0.2 or less, it was rated as "△", and when it exceeded 0.2, it was rated as "x". The results are shown in Table 4. [Table 4]

[Evaluation of flicker that occurs during drive] The FFS method liquid crystal display element prepared above was placed between two polarizers arranged so that the polarization axes were perpendicular to each other, and the backlight was turned on with no voltage applied (light source: LED , Luminosity: 20000cd/m ² ), adjust the configuration angle of the liquid crystal cell to minimize the brightness of the transmitted light. Then, the VT curve (voltage-transmittance curve) was measured while applying an AC voltage with a frequency of 30 Hz to the liquid crystal cell, and the AC voltage at which the relative transmittance became 23% was calculated and defined as the driving voltage. In the flicker measurement, temporarily turn off the backlight that has been turned on, and then turn on the backlight after 72 hours in the dark, and at the same time that the backlight starts to turn on, apply an AC voltage with a frequency of 30 Hz with a relative transmittance of 23%, and make the liquid crystal cell Drive for 60 minutes and track the flicker amplitude. For the flicker amplitude, the data collection/data acquisition switching unit 34970A (manufactured by Agilent Technologies) connected via a photodiode and an IV conversion amplifier reads the transmitted light passing through the backlight of the two polarizers and the liquid crystal cell between them. The value calculated using the following formula based on this data is defined as the flicker level. Flicker level (%)={flicker amplitude/(2×z)}×100 In the above formula, z is an AC voltage with a frequency of 30Hz and a relative transmittance of 23% read by the data collection/data acquisition switching unit 34970A Brightness value when driving. The evaluation of the above-mentioned flicker was carried out under the temperature condition that the temperature of the liquid crystal cell was 40°C, and the value after 30 minutes had elapsed from the time when the backlight was turned on and the application of the AC voltage was started was defined as the flicker level (%). The results are shown in Table 5. The smaller the flicker level, the better the flicker characteristics. [table 5] Liquid crystal alignment agent Flicker level (%) Example 8 (8) 6.2% Example 9 (9) 3.8% Example 10 (10) 3.0% Example 11 (11) 3.4%

By using the liquid crystal alignment agent of the embodiment of the present invention, a liquid crystal display element with good liquid crystal alignment (that is, excellent AC image sticking characteristics) can be obtained In addition, the liquid crystal alignment agent described in the examples of the present invention has good film hardness, so scraping of the film is less likely to occur during rubbing treatment. Furthermore, the liquid crystal alignment agent added with a cross-linking compound as an additive exhibits good blinking properties.

In addition, the entire content of the Japanese patent application No. 2021-004434 filed on January 14, 2021, the scope of claims, drawings, and abstract, and the Japanese patent application filed on October 28, 2021 are cited here. The entire content of the specification, patent application scope, drawings and abstract of Case No. 2021-176483 is cited as the disclosure of the specification of the present invention.

Claims (21)

A polymer composition, characterized by: containing the following (A) component and (B) component, (A) component: is selected from a polyimide precursor having a repeating unit represented by the following formula (a) and is the Polymer (A) of at least one of the group consisting of polyimides of imides of polyimide precursors, (B) component: has a repeating unit represented by the following formula (1) and does not have The repeating unit represented by the formula (a) and the polyurethane of its imidized structure,

X represents a 4-valent organic group, Y represents a 2-valent organic group derived from diamine, each of the two Rs independently represents a hydrogen atom or a 1-valent organic group, and each of the 2 Zs independently represents a hydrogen atom or a 1-valent organic group;

A1 is _a divalent organic group derived from diisocyanate; A2 is a divalent organic group formed by removing hydrogen atoms contained in _two hydroxyl groups from an organic diol; at least _one of A1 and A2 has the following _formula (EG) represents a divalent organic group;

n is an integer of 5 or more; R represents a hydrogen atom or a methyl group. The polymer composition according to claim 1, wherein, in the above formula (EG), n is an integer of 5-40. The polymer composition according to any one of claim items 1 to 2, wherein, Y in the formula (a) is derived from a diamine represented by the following formula (O), having an amide bond or a urea bond Amine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Phenyl ketone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, Diamine represented by formula (d _o ), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and the group "-N(D)-" (D Indicates divalent organic groups of diamines in the group consisting of diamines that are detached by heating and replaced by hydrogen atom protecting groups);

Ar represents a divalent benzene ring, a biphenyl structure, or a naphthalene ring; two Ars can be the same or different, and any hydrogen atom of the above-mentioned benzene ring, biphenyl structure, or naphthalene ring can also be substituted by a monovalent group; p is 0 or an integer of 1; Q ₂ represents -(CH ₂ ) _n -(n is an integer of 2 to 18), or at least a part of the -CH ₂ - of the -(CH ₂ ) _n - is covered by -O-, -C( =O)- or -OC(=O)- any one of the substituents;

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

. The polymer composition according to claim 4 or 5, wherein, the aromatic diisocyanate other than the diisocyanate (DI _EG ) is in the diisocyanate structure (O=C=NRN=C=O), and R does not have the above Aromatic diisocyanate represented by the formula (EG) having a divalent organic group having at least one benzene ring and an organic group with 6 to 30 carbon atoms, and an aliphatic diisocyanate other than the diisocyanate (DI _EG ) having a diisocyanate structure (O=C=NRN=C=O), R is an aliphatic bismuth having an aliphatic group and not having a divalent organic group represented by the above formula (EG) and an organic group having 4 to 30 carbon atoms of an aromatic group. isocyanate. The polymer composition according to any one of claims 1 to 6, wherein the organic diol in the formula (1) is a diol containing a divalent organic group represented by the formula (EG). Such as the polymer composition of claim 7, wherein the diol containing the divalent organic group represented by (EG) is a diol with hydrogen atoms bonded to both ends of the divalent organic group represented by the formula (EG). alcohol. The polymer composition according to any one of claims 1 to 8, wherein X in (a) is a quaternary organic group derived from acyclic aliphatic tetracarboxylic dianhydride or derivatives thereof, derived from aliphatic A tetravalent organic group derived from a cyclic tetracarboxylic dianhydride or a derivative thereof, or a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or a derivative thereof. The polymer composition according to any one of claims 1 to 9, wherein X in (a) is a 4-valent organic group derived from tetracarboxylic dianhydride or derivatives thereof represented by formula (t);

_In the formula, X1 is selected from the structures of the following formulas (X1-1)~(X1-25), and * represents an atomic bond;

In the formulas (X1-1)~(X1-4), R1~ _R21 each independently represent a hydrogen atom, a halogen atom, an alkyl group with ₁ ~6 carbons, an alkenyl group with 2~6 carbons, or an alkenyl group with 2 carbons. ~6 alkynyl groups, monovalent organic groups with 1 to 6 carbon atoms containing fluorine atoms, or phenyl groups, * represents atomic bonds; in formulas (X1-24)~(X1-25), j and k are 0 or An integer of 1, A ₁ and A ₂ each independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amido, and a plurality of A ₂ may be the same or different. The polymer composition according to any one of claims 1 to 10, wherein 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 polymer composition according to any one of claims 1 to 11, wherein the polymer (A) is a terminal-capped polymer. The polymer composition according to any one of claims 1 to 12, wherein 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 polymer composition according to any one of claims 1 to 13, further containing a compound selected from crosslinking compounds, functional silane compounds, metal chelate compounds, hardening accelerators, surfactants, antioxidants, and sensitizers , preservatives, and at least one additive component in the group consisting of compounds for adjusting the dielectric constant and resistance of the resin film. The polymer composition according to any one of claims 1 to 14, further comprising at least one crosslink selected from the group consisting of crosslinkable compound (c-1) and crosslinkable compound (c-2) sexual compounds, The crosslinkable compound (c-1) has at least one substituent selected from epoxy group, isocyanate group, oxetanyl group, cyclocarbonate group, blocked isocyanate group, hydroxyl group and alkoxy group, This crosslinkable compound (c-2) has a polymerizable unsaturated group. The polymer composition as claimed in item 15, wherein the crosslinking compound is a compound represented by any one of the following formulas (CL-1)~(CL-12);

. A liquid crystal alignment agent consisting of 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 alignment film formed using the liquid crystal alignment 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): Step (1): Coating the liquid crystal alignment agent according to claim 17 on the substrate, Step (2): calcining the coated liquid crystal alignment agent to obtain a film, Step (3): performing alignment treatment on the film obtained in step (2).