TW202146524A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The invention relates to a liquid crystal alignment including a polymer (A) and a solvent (B). The polymer (A) includes a first polymer (A1) and a second polymer (A2). The first polymer (A1) is formed by reaction of a first mixture including a tetracarboxylic dianhydride component (a1) and a diamine component (b1). The diamine component (b1) includes at least one diamine compound (b1-1) represented as formula (I). The second polymer (A2) is formed by reaction of a first mixture including a tetracarboxylic dianhydride component (a2) and a diamine component (b2). The diamine component (b2) includes at least one diamine compound (b2-1) represented as formula (II). The invention further relates to a liquid crystal alignment film formed of the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film.

Description

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

The present disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element, and in particular, to a liquid crystal alignment agent with good environmental resistance and less image sticking, a liquid crystal alignment film formed from the aforementioned liquid crystal alignment agent, and a liquid crystal alignment film having the aforementioned liquid crystal alignment agent. Alignment film for liquid crystal display elements.

Liquid crystal display elements such as liquid crystal televisions and liquid crystal displays are usually provided with liquid crystal alignment films inside the elements to control the alignment state of the liquid crystals. At present, the most common method of forming a liquid crystal alignment film in the industry is to form a film on the electrode substrate with polyimide and/or polyimide which is imidized, and then rub it (that is, use cotton , nylon, polyester and other fabrics rub the surface of the film in a single direction) to obtain a liquid crystal alignment film.

In the alignment process of the liquid crystal alignment film, the method that is easier to produce in the industry is to rub the surface of the film. However, with the increasing demand for high efficiency, high definition, and large-scale liquid crystal display elements, during the rubbing treatment, the surface of the liquid crystal alignment film is damaged, flying dust, mechanical force and static electricity. The influence of force and various problems such as unevenness on the alignment treatment surface also become more prominent.

As a method of replacing the rubbing treatment, a photo-alignment method using polarized ultraviolet irradiation to impart alignment energy to a liquid crystal is known. The liquid crystal alignment treatment of the photo-alignment method may include substances using photoisomerization reaction, substances using photocrosslinking reaction, substances using photolysis reaction, and the like in the reaction mechanism. Furthermore, Japanese Patent Laid-Open No. 9-297313 proposes that the photo-alignment method uses a polyimide film having an alicyclic structure such as cyclobutane in its main chain. When polyimide is used as an alignment film for photo-alignment, since the heat resistance of the alignment film is higher than that of other types of alignment films, the applicability of this alignment film is expected.

The photo-alignment method is a method that does not require rubbing alignment treatment. It not only has the advantages of simple process in industry, but also has the advantages of lateral electric field effect technology (In-Plane-Switching; IPS) driving method and boundary electric field switching wide viewing angle technology (Fringe Field Switching technology). In the liquid crystal display element of the FFS) driving mode, compared with the liquid crystal alignment film obtained by the rubbing treatment method, when the liquid crystal alignment film obtained by the above-mentioned photo-alignment method is used, the contrast and viewing angle characteristics of the liquid crystal display element are expected to be improved. The alignment method is a promising liquid crystal alignment treatment method attracting attention.

However, when the liquid crystal alignment film obtained by the photo-alignment method is applied to a liquid crystal display element, there are still problems such as poor environmental resistance and easy generation of image sticking. As can be seen from the above, in order to meet the requirements of the current photo-alignment IPS type liquid crystal display manufacturers, it is the goal of those skilled in the art to provide a liquid crystal alignment agent that can form a liquid crystal display element with good environmental resistance and less image sticking.

Due to the special composition and/or ratio of the liquid crystal alignment agent, the liquid crystal alignment film prepared by the present invention has the advantages of good environmental resistance and/or less image afterimage when the liquid crystal alignment film is applied to a liquid crystal display element.

式(I) 式(I)中，R¹ 至R¹⁰ 為相同或不同之氫原子或一價有機基，其中R¹ 至R¹⁰ 中至少含兩個伯胺基； 該第二聚合物(A2)由第二混合物反應而製得，該第二混合物包含四羧酸二酐組份(a2)及二胺組份(b2)，其中該二胺組份(b2)包含至少一種如式(II)所示之二胺化合物(b2-1)：

式(II) 式(II)中，E₁ 及E₅ 各自獨立地代表單鍵或碳數為1至5之亞烷基；E₂ 及E₄ 各自獨立地代表碳數為1至5之亞烷基；E₃ 代表碳數為1至6之亞烷基、或亞環烷基；B₁ 及B₅ 各自獨立地代表單鍵、－O－、－NH－、－NCH₃ －、－C(=O)－、－C(=O)O－、－C(=O)NCH₃ －、－OC(=O)－、－NHC(=O)－或－N(CH₃ )C(=O)－；a代表0或1；且D₁ 具有式(II-1)所示之結構：

式(II-1) 式(II-1)中，R為碳數為1至20之直鏈、分支或環狀的一價羥基，*代表連結基。Therefore, the present invention provides a liquid crystal alignment agent, comprising: a polymer (A); and a solvent (B); wherein the polymer (A) comprises a first polymer (A1) and a second polymer (A2), the The first polymer (A1) is prepared by reacting a first mixture, the first mixture comprising a tetracarboxylic dianhydride component (a1) and a diamine component (b1), wherein the diamine component (b1) comprises At least one diamine compound (b1-1) represented by formula (I):

Formula (I) In formula (I), R ¹ to R ¹⁰ are the same or different hydrogen atoms or monovalent organic groups, wherein R ¹ to R ¹⁰ contain at least two primary amino groups; the second polymer (A2 ) is prepared by the reaction of a second mixture, the second mixture comprising a tetracarboxylic dianhydride component (a2) and a diamine component (b2), wherein the diamine component (b2) comprises at least one such as formula (II) ) represented by the diamine compound (b2-1):

Formula (II) In formula (II), E ₁ and E ₅ each independently represent a single bond or an alkylene group with 1 to 5 carbon atoms; E ₂ and E ₄ each independently represent a sub-group with 1 to 5 carbon atoms Alkyl; E ₃ represents an alkylene group having 1 to 6 carbon atoms, or a cycloalkylene group; B ₁ and B ₅ each independently represent a single bond, -O-, -NH-, -NCH ₃ -, -C (=O)-, -C(=O)O-, -C(=O)NCH ₃ -, -OC(=O)-, -NHC(=O)- or -N(CH ₃ )C(= O)-; a represents 0 or 1; and D ₁ has the structure shown in formula (II-1):

Formula (II-1) In formula (II-1), R is a linear, branched or cyclic monovalent hydroxyl group having 1 to 20 carbon atoms, and * represents a linking group.

The present invention further provides a liquid crystal alignment film, which is formed by the aforementioned liquid crystal alignment agent.

The present invention further provides a liquid crystal display element comprising the aforementioned liquid crystal alignment film.

式(I) 式(I)中，R¹ 至R¹⁰ 為相同或不同之氫原子或一價有機基，其中R¹ 至R¹⁰ 至少含兩個伯胺基； 該第二聚合物(A2)由第二混合物反應而製得，該第二混合物包含四羧酸二酐組份(a2)及二胺組份(b2)，其中該二胺組份(b2)包含至少一種如式(II)所示之二胺化合物(b2-1)：

式(II) 式(II)中，E₁ 及E₅ 各自獨立地代表單鍵或碳數為1至5之亞烷基；E₂ 及E₄ 各自獨立地代表碳數為1至5之亞烷基；E₃ 代表碳數為1至6之亞烷基、或亞環烷基；B₁ 及B₅ 各自獨立地代表單鍵、－O－、－NH－、－NCH₃ －、－C(=O)－、－C(=O)O－、－C(=O)NCH₃ －、－OC(=O)－、－NHC(=O)－或－N(CH₃ )C(=O)－；a代表0或1；且D₁ 具有式(II-1)所示之結構：

式(II-1) 式(II-1)中，R為碳數為1至20之直鏈、分支或環狀的一價羥基，*代表連結基。第一聚合物 (A1) The present invention provides a liquid crystal alignment agent, comprising: a polymer (A); and a solvent (B); wherein the polymer (A) comprises a first polymer (A1) and a second polymer (A2), the first The polymer (A1) is prepared by reacting a first mixture, the first mixture comprises a tetracarboxylic dianhydride component (a1) and a diamine component (b1), wherein the diamine component (b1) comprises at least one Diamine compound (b1-1) represented by formula (I):

Formula (I) In formula (I), R ¹ to R ¹⁰ are the same or different hydrogen atoms or monovalent organic groups, wherein R ¹ to R ¹⁰ contain at least two primary amino groups; the second polymer (A2) Prepared by the reaction of a second mixture, the second mixture comprising a tetracarboxylic dianhydride component (a2) and a diamine component (b2), wherein the diamine component (b2) comprises at least one such as formula (II) The shown diamine compound (b2-1):

Formula (II) In formula (II), E ₁ and E ₅ each independently represent a single bond or an alkylene group with 1 to 5 carbon atoms; E ₂ and E ₄ each independently represent a sub-group with 1 to 5 carbon atoms Alkyl; E ₃ represents an alkylene group having 1 to 6 carbon atoms, or a cycloalkylene group; B ₁ and B ₅ each independently represent a single bond, -O-, -NH-, -NCH ₃ -, -C (=O)-, -C(=O)O-, -C(=O)NCH ₃ -, -OC(=O)-, -NHC(=O)- or -N(CH ₃ )C(= O)-; a represents 0 or 1; and D ₁ has the structure shown in formula (II-1):

Formula (II-1) In formula (II-1), R is a linear, branched or cyclic monovalent hydroxyl group having 1 to 20 carbon atoms, and * represents a linking group. First polymer (A1)

The first polymer (A1) of the present invention is obtained by reacting the first mixture. Specifically, the first polymer (A1) can be selected from a polyimide polymer, a polyimide polymer, a polyimide-based block copolymer or any combination of the above polymers. Wherein, the polyimide block copolymer is selected from the group consisting of polyimide block copolymer, polyimide block copolymer, polyimide-polyimide block copolymer or Any combination of the above polymers.

The first mixture includes a tetracarboxylic dianhydride component (a1) and a diamine component (b1), wherein a preferred specific example of the tetracarboxylic dianhydride component (a1) is (1) aliphatic tetracarboxylic acid di Anhydride compounds, (2) alicyclic tetracarboxylic dianhydride compounds, (3) aromatic tetracarboxylic dianhydride compounds, or (4) tetracarboxylic acids represented by formulae (a1-1) to (a1-6) Acid dianhydride compounds, etc.

The (1) aliphatic tetracarboxylic dianhydride compound of the present invention includes, but is not limited to, aliphatic tetracarboxylic dianhydride compounds such as ethane tetracarboxylic dianhydride or butane tetracarboxylic dianhydride.

(2) Alicyclic tetracarboxylic dianhydride compounds of the present invention include but are not limited to 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane Tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyl tetracarboxylic dianhydride, cis-3,7-dibutyl cycloheptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride or bicyclo[2.2.2]-octane - Alicyclic tetracarboxylic dianhydride compounds such as 7-ene-2,3,5,6-tetracarboxylic dianhydride.

Specific examples of the (3) aromatic tetracarboxylic dianhydride compound of the present invention may include, but are not limited to, 3,4-dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, benzene homo Tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3' ,4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3'- 4,4'-diphenylethane tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetra Phenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4, 4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 2,3,3',4'-diphenyl sulfide Tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylene dianhydride, 4 ,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylene diphthalic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride Anhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride , bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro trimellitate) trimellitate), 1,8-octanediol-bis(anhydrotrimellitate), 2,2-bis(4-hydroxyphenyl)propane-bis(anhydrotrimellitate), 2 ,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxy-3-furyl)- Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-methyl-5-(tetrahydro-2,5-dione pendant oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-ethyl-5 -(Tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b - Hexahydro-7-methyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1 ,3,3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]- furfur Furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxy-3-furyl)- Naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-ethyl-5-(tetrahydro-2,5-dione pendant oxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5,8-dimethyl Alkyl-5-(tetrahydro-2,5-dioxy-3-furyl)-naphtho[1,2-c]-furan-1,3-dione, 5-(2,5-dione pendant oxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, etc.

式(a1-1)

式(a1-2)

式(a1-3)

式(a1-4)

式(a1-5)

式(a1-6)(4) according to the present invention has tetracarboxylic dianhydride compounds represented by formulae (a1-1) to (a1-6), which are described in detail below.

Formula (a1-1)

Formula (a1-2)

Formula (a1-3)

Formula (a1-4)

Formula (a1-5)

Formula (a1-6)

式(a1-5-1)

式(a1-5-2)

式(a1-5-3)In formula (a1-5), A ₁ represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; A ₂ and A ₃ may be the same or different, and may respectively represent a hydrogen atom or an alkyl group. Preferably, the tetracarboxylic dianhydride compound represented by the formula (a1-5) can be selected from the compounds represented by the following formulae (a1-5-1) to (a1-5-3).

Formula (a1-5-1)

Formula (a1-5-2)

Formula (a1-5-3)

式(a1-6-1)In formula (a1-6), A ₄ represents a divalent group containing an aromatic ring; A ₅ and A ₆ may be the same or different, and represent a hydrogen atom or an alkyl group, respectively. Preferably, the tetracarboxylic dianhydride compound represented by the formula (a1-6) can be selected from the compounds represented by the following formula (a1-6-1).

Formula (a1-6-1)

In the tetracarboxylic dianhydride component (a1), the above-mentioned tetracarboxylic dianhydride compounds may be used alone or in combination of two or more.

Based on 100 mol of the diamine component (b1), the used amount of the tetracarboxylic dianhydride component (a1) is in the range of 20 mol to 200 mol; preferably 30 mol to 120 mol .

式(I) 式(I)中，R¹ 至R¹⁰ 為相同或不同之氫原子或一價有機基，其中R¹ 至R¹⁰ 中至少含兩個伯胺基。The diamine component (b1) of the first mixture comprises at least one diamine compound (b1-1) represented by formula (I):

Formula (I) In formula (I), R ¹ to R ¹⁰ are the same or different hydrogen atoms or monovalent organic groups, wherein R ¹ to R ¹⁰ contain at least two primary amino groups.

In one embodiment, two and only two of ^{R 1} to R ^{10 are primary amino groups.}

式(I-1)

式(I-2)Specific examples of the diamine compound (b1-1) include the following formula (I-1), in which ^{two primary amino groups in R 1} to R ¹⁰ are linked to different benzene rings; or the following formula (I-1) -2), wherein ^{two primary amine groups in R 1} to R ¹⁰ are linked to the same benzene ring.

Formula (I-1)

Formula (I-2)

The remaining R ¹ to R ¹⁰ are the same or different hydrogen atoms or monovalent organic groups, and the monovalent organic groups may include alkyl groups, alkenyl groups, cycloalkyl groups, phenyl groups, biphenyl groups with carbon numbers of 1 to 20 group, terphenyl, fluorine atom and combinations thereof. Among the diamine compounds (b1-1), 4,4'-diaminodiphenyl is preferred from the viewpoints of reactivity with tetracarboxylic dianhydride and liquid crystal alignment when forming a liquid crystal alignment film. amine, 2,4-diaminodiphenylamine, more preferably 2,4-diaminodiphenylamine.

Based on the total usage amount of the diamine component (b1) is 100 moles, the usage amount of the diamine compound (b1-1) is 3 moles to 50 moles, preferably 5 moles to 50 moles, then More preferably, 5 moles to 45 moles.

If the diamine component (b1) does not contain the diamine compound (b1-1), the obtained liquid crystal display element has the defect of poor environmental resistance.

The diamine component (b1) may further comprise other diamine compounds (b1-2).

Other diamine compounds (b1-2) may include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminobutane Pentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diamino Decane, 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1 ,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-Diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 2,6-diaminopyridine, 1,2- Bis(3-aminopropoxy)ethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo[6.2.1.0 ^2,7 ]-undecane Carbenedimethyldiamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-Diaminodiphenylene, 4,4'-Diaminobenzylaniline, 4,4'-Diaminodiphenyl ether, 3,4'-Diaminodiphenyl Ether, 1,5-diaminonaphthalene, 5-amino-1-(4'-aminophenyl)-1,3,3-trimethylhydroindene, 6-amino-1-(4' -Aminophenyl)-1,3,3-trimethylhydroindene, hexahydro-4,7-methylhydroindenyl dimethylenediamine, 3,3'-diaminodiphenylmethane ketone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-( 4-Aminophenoxy)phenyl] bismuth, 1,4-bis(4-aminophenoxy)cyclohexane, 1,5-bis(4-aminophenoxymethylene)adamantane , 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9 ,9-bis(4-aminophenyl)-10-hydroanthracene, 9,10-bis(4-aminophenyl) anthracene [9,10-bis(4-aminophenyl) anthracene], 2,7- Diamino fluoride, 9,9-bis(4-aminophenyl) fluoride, 4,4'-methylene-bis(2-chloroaniline), 4,4'-(p-phenylene isoidene Propyl)dianiline, 4,4'-(m-phenylene isopropylidene)dianiline, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy) Phenyl]hexafluoropropane, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 5-[4-( 4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene{5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene}, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane{1,1-bis[4-(4-aminophenoxy)phenyl] -4-(4-ethyl phenyl)cyclohexane} or other diamine compounds represented by the following formulae (3-1) to (3-31).

式(3-1) 於式(3-1)中，Z₁ 代表

、

、

、

、

或

，且Z₂ 代表含甾基團、三氟甲基、氟基、碳數為2至30之烷基或衍生自吡啶、嘧啶、三嗪、哌啶及哌嗪等含氮原子環狀結構的一價基團。Formula (3-1) is as follows:

Formula (3-1) In formula (3-1), Z ₁ represents

,

,

,

,

or

, and Z ₂ represents a steroid group, a trifluoromethyl group, a fluoro group, an alkyl group with a carbon number of 2 to 30, or a nitrogen atom-containing cyclic structure derived from pyridine, pyrimidine, triazine, piperidine and piperazine. monovalent group.

式(3-1-1)

式(3-1-2)

式(3-1-3)

式(3-1-4)

式(3-1-5)

式(3-1-6)Other diamine compounds represented by the above formula (3-1) are preferably 2,4-diaminophenyl ethyl formate, 3,5-diaminophenyl carboxylic acid Ethyl ester (3,5-diaminophenyl ethyl formate), 2,4-diaminophenyl propyl formate (2,4-diaminophenyl propyl formate), 3,5-diaminophenyl propyl formate (3,5-diaminophenyl propyl formate) -diaminophenyl propyl formate), 1-dodecoxy-2,4-diamino-benzene (1-dodecoxy-2,4-diamino-benzene), 1-hexadecoxy-2,4-diamine 1-hexadecoxy-2,4-diaminobenzene, 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene) or the following formula (3-1-1 ) to other diamine compounds represented by formula (3-1-6).

Formula (3-1-1)

Formula (3-1-2)

Formula (3-1-3)

Formula (3-1-4)

Formula (3-1-5)

Formula (3-1-6)

式(3-2) 於式(3-2)中，Z₃ 代表

、

、

、

、

或

，Z₄ 及Z₅ 代表伸脂肪族環、伸芳香族環或伸雜環基團，且Z₆ 代表碳數為3至18之烷基、碳數為3至18之烷氧基、碳數為1至5之氟烷基、碳數為1至5之氟烷氧基、氰基或鹵素原子。Formula (3-2) is as follows:

Formula (3-2) In formula (3-2), Z ₃ represents

,

,

,

,

or

, Z ₄ and Z ₅ represent aliphatic ring extension, aromatic ring extension or heterocyclic extension group, and Z ₆ represents an alkyl group with a carbon number of 3 to 18, an alkoxy group with a carbon number of 3 to 18, a carbon number is a fluoroalkyl group of 1 to 5, a fluoroalkoxy group having a carbon number of 1 to 5, a cyano group or a halogen atom.

式(3-2-1)

式(3-2-2)

式(3-2-3)

式(3-2-4)

式(3-2-5)

式(3-2-6)

式(3-2-7)

式(3-2-8)

式(3-2-9)

式(3-2-10)

式(3-2-11)

式(3-2-12)

式(3-2-13) 於式(3-2-10)至式(3-2-13)中，s可代表3至12的整數。The other diamine compounds represented by the above formula (3-2) can preferably be the diamine compounds represented by the following formulas (3-2-1) to (3-2-13):

Formula (3-2-1)

Formula (3-2-2)

Formula (3-2-3)

Formula (3-2-4)

Formula (3-2-5)

Formula (3-2-6)

Formula (3-2-7)

Formula (3-2-8)

Formula (3-2-9)

Formula (3-2-10)

Formula (3-2-11)

Formula (3-2-12)

Formula (3-2-13) In Formula (3-2-10) to Formula (3-2-13), s may represent an integer of 3 to 12.

式(3-3) 於式(3-3)中，Z₇ 代表氫原子、碳數為1至5的醯基、碳數為1至5的烷基、碳數為1至5的烷氧基或鹵素。P1代表1至3的整數。當P1大於1時，複數個Z₇ 可為相同或不同。Formula (3-3) is as follows:

Formula (3-3) In formula (3-3), Z ₇ represents a hydrogen atom, an acyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms base or halogen. P1 represents an integer from 1 to 3. When P1 is greater than 1, the plurality of Z ₇ may be the same or different.

The diamine compound shown in the above formula (3-3) is preferably selected from (1) P1 is p-diamine benzene, m-diamine benzene, o-diamine benzene or 2,5-diamine toluene, etc. ; (2) P1 is 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4' -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3 '-Dichloro-4,4'-diaminobiphenyl, 2,2',5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4, 4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, etc.; (3) P1 is 1 ,4-bis(4'-aminophenyl)benzene, etc., more preferably selected from p-diaminebenzene, 2,5-diaminetoluene, 4,4'-diaminobiphenyl, 3,3 '-dimethoxy-4,4'-diaminobiphenyl or 1,4-bis(4'-aminophenyl)benzene.

式(3-4) 於上式(3-4)中，P2代表1至5的整數。式(3-4)所示之結構較佳係選自於4,4'-二胺基二苯基硫醚。Formula (3-4) is as follows:

Formula (3-4) In the above formula (3-4), P2 represents an integer of 1 to 5. The structure represented by the formula (3-4) is preferably selected from 4,4'-diaminodiphenyl sulfide.

式(3-5) 於式(3-5)中，Z₈ 及Z₁₀ 可為相同或不同，且分別代表二價有機基團，Z₉ 代表衍生自吡啶、嘧啶、三嗪、哌啶及哌嗪等含氮原子環狀結構的二價基團。Equation (3-5) is as follows:

Formula (3-5) In formula (3-5), Z ₈ and Z ₁₀ may be the same or different, and respectively represent a divalent organic group, Z ₉ represents derived from pyridine, pyrimidine, triazine, piperidine and Piperazine and other divalent groups of nitrogen-containing cyclic structures.

式(3-6) 於式(3-6)中，Z₁₁ 、Z₁₂ 、Z₁₃ 及Z₁₄ 分別可為相同或不同，且可代表碳數為1至12的烴基。P3代表1至3的整數，且P4代表1至20的整數。Equation (3-6) is as follows:

Formula (3-6) In Formula (3-6), Z ₁₁ , Z ₁₂ , Z ₁₃ and Z ₁₄ may be the same or different, respectively, and may represent a hydrocarbon group having 1 to 12 carbons. P3 represents an integer of 1 to 3, and P4 represents an integer of 1 to 20.

式(3-7) 於式(3-7)中，Z₁₅ 代表

或伸環己烷基，Z₁₆ 代表

，Z₁₇ 代表伸苯基或伸環己烷基，且Z₁₈ 代表氫原子或庚基。

Formula (3-7) In formula (3-7), Z ₁₅ represents

or cyclohexylene, Z ₁₆ represents

, Z ₁₇ represents a phenylene group or a cyclohexylene group, and Z ₁₈ represents a hydrogen atom or a heptyl group.

式(3-7-1)

式(3-7-1)The diamine compound represented by the above formula (3-7) is preferably selected from the diamine compounds represented by the following formula (3-7-1) and (3-7-2).

Formula (3-7-1)

Formula (3-7-1)

式(3-8)

式(3-9)

式(3-10)

式(3-11)

式(3-12)

式(3-13)

式(3-14)

式(3-15)

式(3-16)

式(3-17)

式(3-18)

式(3-19)

式(3-20)

式(3-21)

式(3-22)

式(3-23)

式(3-24)

式(3-25)

式(3-26)

式(3-27)

式(3-28)

式(3-29)

式(3-30)

式(3-31) 於式(3-16)至式(3-19)中，Z₁₉ 較佳係碳數為1至10之烷基或碳數為1至10之烷氧基。於式(3-20)至式(3-24)中，Z₂₀ 較佳為氫原子、碳數為1至10之烷基或碳數為1至10之烷氧基。Other diamine compounds represented by formula (3-8) to formula (3-31) are as follows:

Formula (3-8)

Formula (3-9)

Formula (3-10)

Formula (3-11)

Formula (3-12)

Formula (3-13)

Formula (3-14)

Formula (3-15)

Formula (3-16)

Formula (3-17)

Formula (3-18)

Formula (3-19)

Formula (3-20)

Formula (3-21)

Formula (3-22)

Formula (3-23)

Formula (3-24)

Formula (3-25)

Formula (3-26)

Formula (3-27)

Formula (3-28)

Formula (3-29)

Formula (3-30)

Formula (3-31) In formulas (3-16) to (3-19), Z _{19 is} preferably an alkyl group having 1 to 10 carbons or an alkoxy group having 1 to 10 carbons. In formulas (3-20) to (3-24), Z _{20 is} preferably a hydrogen atom, an alkyl group having 1 to 10 carbons, or an alkoxy group having 1 to 10 carbons.

Other diamine compounds (b1-2) may preferably include but are not limited to 1,2-diaminoethane, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether, 5-[4-(4-n-pentylcyclohexyl)cyclohexyl]phenylmethylene-1,3-diaminobenzene, 1, 3-bis(3-aminophenoxy)benzene, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-(4-ethylphenyl)cyclohexane, 2 ,4-Diaminophenyl ethyl carboxylate, p-diamine benzene, m-diamine benzene, o-diamine benzene, formula (3-1-1), formula (3-1-2), formula ( 3-1-5), formula (3-2-1), formula (3-2-11), formula (3-7-1), formula (3-25) or formula (3-28) compound.

The aforementioned other diamine compounds (b1-2) may be used alone or in combination.

Based on the total usage amount of the diamine component (b1) is 100 moles, the usage amount of the other diamine compounds (b1-2) is 80 moles to 99 moles, preferably 85 moles to 99 moles, then More preferably, 90 moles to 99 moles. Preparation method of first polymer (A1)

The preparation of the polyamic acid polymer of the present invention can be carried out by a general method. Preferably, the preparation method of the polyamic acid polymer described above comprises the following steps: adding a tetracarboxylic dianhydride component (a1) and a diamine The first mixture of component (b1) is dissolved in a solvent, and the polycondensation reaction is carried out at a temperature of 0°C to 100°C and the reaction is carried out for 1 hour to 24 hours, and then the above reaction solution is subjected to vacuum distillation with an evaporator The polyamide acid polymer can be obtained in the following way, or the above-mentioned reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and then the aforesaid precipitate is dried by drying under reduced pressure to obtain the polyamide Amino acid polymers.

The solvent used in the polycondensation reaction may be the same as or different from the solvent used in the liquid crystal aligning agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactant and the product. Preferably, the solvent includes but is not limited to (1) aprotic polar solvents, such as: N-methyl-2-pyrrolidinone (N-methyl-2-pyrrolidinone; NMP), N,N-dimethylacetamide , aprotic polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethyl urea or hexamethylphosphoric triamine; (2) phenolic solvents, For example: phenolic solvents such as m-cresol, xylenol, phenol or halogenated phenols. The amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the mixture.

In particular, in the polycondensation reaction, an appropriate amount of poor solvent can be used in combination with the solvent, wherein the poor solvent will not cause the precipitation of the polyamic acid polymer. The poor solvent can be used alone or in combination, and it includes but is not limited to (1) alcohols, such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol Alcohols such as alcohol or triethylene glycol; (2) ketones, such as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; (3) esters, such as: Esters of methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate or ethylene glycol ethyl ether acetate; (4) ethers, such as diethyl ether, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether ethers such as base ethers; (5) halogenated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichloromethane Halogenated hydrocarbons such as benzene; (6) Hydrocarbons, such as: tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene and other hydrocarbons or any combination of the above solvents. The usage amount of the lean solvent is preferably 0 to 60 parts by weight, more preferably 0 to 50 parts by weight, based on 100 parts by weight of the diamine component (b1).

The preparation of the polyimide polymer of the present invention can be performed by a general method. Preferably, the preparation method of the polyimide polymer firstly dissolves the first mixture in the solution, wherein the first mixture contains tetracarboxylic dianhydride The component (a1) and the diamine component (b1) are subjected to a polymerization reaction to form a polyamic acid polymer. Next, in the presence of a dehydrating agent and a catalyst, further heating is performed, and a dehydration ring-closure reaction is carried out, so that the aramidic acid functional group in the polyamic acid polymer is converted into an amide-imide functional group (that is, an amide-imide functional group) through the dehydration ring-closure reaction. amination) to obtain a polyimide polymer.

The solvent used in the dehydration ring-closure reaction can be the same as the solvent in the liquid crystal alignment agent described below, so it will not be repeated. The amount of the solvent used in the dehydration ring-closure reaction is preferably 200 to 2000 parts by weight, more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamide polymer.

In order to obtain a better degree of imidization of the polyamic acid polymer, the operating temperature of the dehydration ring-closure reaction is preferably 40°C to 200°C, more preferably 40°C to 150°C. If the operating temperature of the dehydration ring-closure reaction is lower than 40°C, the imidization reaction is incomplete, and the degree of imidization of the polyamic acid polymer is reduced. However, if the operating temperature of the dehydration ring-closure reaction is higher than 200°C, the weight-average molecular weight of the obtained polyimide polymer is relatively low.

The dehydrating agent used in the dehydration ring-closure reaction can be selected from acid anhydride compounds, such as acid anhydride compounds such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The dehydrating agent is used in an amount of 0.01 mol to 20 mol based on 1 mol of the polyamide polymer. The catalyst used in the dehydration ring-closure reaction can be selected from (1) pyridine compounds, such as: pyridine compounds such as pyridine, collidine or lutidine; (2) tertiary amine compounds, such as: Tertiary amine compounds such as triethylamine. The used amount of the dehydrating agent is 1 mol, and the used amount of the catalyst is 0.5 mol to 10 mol.

Preferred specific examples of the polyimide-based block copolymer of the present invention are polyimide block copolymer, polyimide block copolymer, polyimide-polyimide block Copolymers, or any combination thereof.

The polyimide-based block copolymer of the present invention can be prepared by a general method. Preferably, in the preparation method of the polyimide-based block copolymer, the starting material is first dissolved in a solvent, and the A polycondensation reaction, wherein the starting material comprises the above-mentioned at least one polyimide polymer and/or the above-mentioned at least one polyimide polymer, and may further comprise a tetracarboxylic dianhydride component (a1) and the diamine component (b1).

The tetracarboxylic dianhydride component (a1) and the diamine component (b1) in the aforementioned starting materials are the same as the tetracarboxylic dianhydride component (a1) and the diamine component (a1) used in the above-mentioned preparation of the polyamic acid polymer. The amine component (b1) is the same, and the solvent used in the polycondensation reaction can be the same as the solvent in the liquid crystal alignment agent described below, which will not be repeated here.

The amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the aforementioned starting materials. The operating temperature of the polycondensation reaction is preferably 0°C to 200°C, and more preferably 0°C to 100°C.

Preferably, the starting materials include but are not limited to (1) two kinds of polyamide polymers with different end groups and different structures; (2) two kinds of polyimides with different end groups and different structures polymers; (3) polyamide polymers and polyimide polymers with different terminal groups and structures; (4) polyamide polymers, tetracarboxylic dianhydride compounds and diamine compounds, Wherein, at least one of the tetracarboxylic dianhydride compound and the diamine compound has a different structure from the tetracarboxylic dianhydride component (a1) and the diamine component (b1) used to form the polyamic acid polymer ; (5) Polyimide polymer, tetracarboxylic dianhydride compound and diamine compound, wherein at least one of the tetracarboxylic dianhydride compound and diamine compound is used for forming the polyimide polymer The structures of the tetracarboxylic dianhydride component (a1) and the diamine component (b1) are different; (6) polyamide acid polymer, polyimide polymer, tetracarboxylic dianhydride compound and diamine A compound, wherein at least one of a tetracarboxylic dianhydride compound and a diamine and the tetracarboxylic dianhydride component (a1) and the diamine component used to form a polyamic acid polymer or a polyimide polymer (b1) The structures are different; (7) Two kinds of polyimide polymers, tetracarboxylic dianhydride compounds and diamine compounds with different structures; (8) Two kinds of polyimide polymers with different structures , tetracarboxylic dianhydride compounds and diamine compounds; (9) two kinds of end groups are acid anhydride groups and have different structures of polyamide polymers and diamine compounds; (10) two kinds of end groups are amine groups and have different structures Dissimilar polyimide polymers and tetracarboxylic dianhydride compounds; (11) Two kinds of end groups are acid anhydride groups and structurally different polyimide polymers and diamine compounds; (12) Two kinds of end groups Polyimide polymers and tetracarboxylic dianhydride compounds with amine groups and different structures.

Within the scope of not affecting the efficacy of the present invention, preferably, the aforementioned polyimide polymer, the aforementioned polyimide polymer, and the aforementioned polyimide-based block copolymer may be the end of which the molecular weight is adjusted first. Modified polymers. By using the terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method for preparing the aforementioned terminal-modified polymer can be prepared by adding a monofunctional compound while the polyamide acid polymer undergoes a polycondensation reaction, and the monofunctional compound includes but is not limited to (1) a monobasic acid anhydride, such as : Monobasic acid anhydride such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride or n-hexadecyl succinic anhydride; ( 2) Monoamine compounds, such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine Monoamine compounds such as alkylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine or n-eicosylamine; (3) Monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

The weight average molecular weight of the first polymer (A1) of the present invention in terms of polystyrene measured by gel permeation chromatography is 10,000 to 100,000, preferably 10,000 to 90,000, and more preferably 10,000 to 75,000. Second polymer (A2)

The second polymer (A2) of the present invention is obtained by reacting the second mixture. Specifically, the second polymer (A2) can be selected from a polyimide polymer, a polyimide polymer, a polyimide-based block copolymer or any combination of the above polymers. Wherein, the polyimide block copolymer is selected from the group consisting of polyimide block copolymer, polyimide block copolymer, polyimide-polyimide block copolymer or Any combination of the above polymers.

式(III) 式(III)中，R₁ 至R₄ 各自獨立地代表氫原子、鹵素原子、碳數為1至6的烷基、碳數為2至6的烯基、碳數為2至6的炔基、含有氟原子且碳數為1至6的一價有機基團或苯基，R₁ 至R₄ 為相同或不相同，且R₁ 、R₂ 、R₃ 及R₄ 之至少一者不為氫原子。The second mixture includes a tetracarboxylic dianhydride component (a2) and a diamine component (b2), wherein the tetracarboxylic dianhydride component (a2) includes at least one tetracarboxylic dianhydride represented by formula (III) Compound (a2-1):

Formula (III) In formula (III), R ₁ to R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a group having 2 to 6 carbon atoms. alkynyl group of 6, monovalent organic group containing fluorine atom and carbon number of 1 to 6 or phenyl group, R ₁ to R ₄ are the same or different, and at least one of _{R 1} , R ₂ , R ₃ and R ₄ One is not a hydrogen atom.

In the case that R ₁ , R ₂ , R ₃ and R ₄ have a steric barrier structure, the liquid crystal alignment of the liquid crystal alignment agent will be poor. Therefore, R ₁ , R ₂ , R ₃ and R _{4 are} preferably hydrogen atoms, methyl groups or ethyl groups, and among them, methyl groups are more preferred.

式(III-1)

式(III-2)

式(III-3)

式(III-4)

式(III-5)

式(III-6)

式(III-7)

式(III-8)Specific examples of the tetracarboxylic dianhydride compound (a2-1) having the structure represented by the formula (III) can be, for example, the compounds represented by the following formulae (III-1) to (III-8). For liquid crystal alignment, formula (III-1) is preferred.

Formula (III-1)

Formula (III-2)

Formula (III-3)

Formula (III-4)

Formula (III-5)

Formula (III-6)

Formula (III-7)

Formula (III-8)

The above-mentioned tetracarboxylic dianhydride compound (a2-1) may be used alone or in combination of two or more.

Based on the total usage amount of the tetracarboxylic dianhydride component (a2) is 100 moles, the usage amount of the tetracarboxylic dianhydride compound (a2-1) is 30 moles to 100 moles, preferably 40 moles to 100 moles 100 moles, but 50 moles to 100 moles is better.

When the usage-amount of the tetracarboxylic dianhydride compound (a2-1) falls within the above-mentioned range, the resulting liquid crystal display element is less likely to have image sticking.

The tetracarboxylic dianhydride component (a2) may further comprise other tetracarboxylic dianhydride compounds (a2-2), and the types of the other tetracarboxylic dianhydride compounds (a2-2) may be the same as the aforementioned first polymer The tetracarboxylic dianhydride component (a1) in (A1) is the same as listed, so it will not be repeated here.

The total usage amount based on the tetracarboxylic dianhydride component (a2) is 100 mol, and the usage amount of the other tetracarboxylic dianhydride compounds (a2-2) is 0 mol to 70 mol, preferably 0 mol to 60 mol, but preferably 0 to 50 mol.

式(II) 式(II)中，E₁ 及E₅ 各自獨立地代表單鍵或碳數為1至5之亞烷基。以密封劑中之官能基的反應性而言，較佳為單鍵或亞甲烷基。E₂ 及E₄ 各自獨立地代表碳數為1至5之亞烷基，較佳為亞甲烷基或亞乙烷基。The diamine component (b2) contains at least one diamine compound (b2-1) represented by formula (II):

Formula (II) In formula (II), E ₁ and E ₅ each independently represent a single bond or an alkylene group having 1 to 5 carbons. In terms of the reactivity of the functional group in the sealant, a single bond or a methylene group is preferred. E ₂ and E ₄ each independently represent an alkylene group having 1 to 5 carbon atoms, preferably a methylene group or an ethylene group.

E ₃ represents an alkylene group having 1 to 6 carbon atoms, or a cycloalkylene group. In terms of the reactivity of the functional group in the sealant, a methylene group or an ethylene group is preferred. a stands for 0 or 1.

B ₁ and B ₂ each independently represent a single bond, -O-, -NH-, -NCH ₃ -, -C(=O)-, -C(=O)O-, -C(=O)NCH ₃ -, -OC(=O)-, -NHC(=O)- or -N(CH ₃ )C(=O)-. In terms of the liquid crystal alignment of the obtained liquid crystal aligning agent, a single bond or -O- is preferable.

式(II-1) 式(II-1)中，R為碳數為1至20之直鏈、分支或環狀的一價羥基。D ₁ has the structure shown in formula (II-1):

Formula (II-1) In formula (II-1), R is a linear, branched or cyclic monovalent hydroxyl group having 1 to 20 carbon atoms.

In terms of the convenience of raw material acquisition, R is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexane, n-octyl, benzyl , n-hexadecyl or 9-fluorenylmethyl, more preferably tert-butyl or 9-fluorenylmethyl.

Examples of D ₁ include, for example, tert-butoxycarbonyl, 9-fluorenylmethoxycarbonyl, dimethoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, benzyloxycarbonyl, hexyloxycarbonyl or octyloxycarbonyl. Among them, a thermally dissociable group such as tert-butoxycarbonyl or 9-fluorenylmethoxycarbonyl is preferably used. If D ₁ is a thermally dissociable group, the resulting liquid crystal display element is not prone to image sticking.

式(II-2) 式(II-3)

式(II-4) 式(II-5)

式(II-6) 式(II-7)

式(II-8) 式(II-9)

式(II-10) 式(II-11)

式(II-12) 式(II-13)

式(II-14) 式(II-15)

式(II-16) 式(II-17)

式(II-18) 式(II-19)

式(II-20) 式(II-21)

式(II-22) 式(II-23)

式(II-24) 式(II-25)

式(II-26) 式(II-27)

式(II-28) 式(II-29)

式(II-30) 式(II-31)

式(II-32) 式(II-33)

式(II-34) 式(II-35)

式(II-36) 式(II-37)

式(II-38) 式(II-39)

式(II-40) 式(II-41)

式(II-42) 式(II-43)

式(II-44) 式(II-45)

式(II-46) 式(II-47) 式(II-2)至式(II-47)中，Me為甲基、Et為乙基、iPr為異丙基、Bn為苄基、Boc為叔丁氧羰基。Examples of the diamine compound (b2-1) represented by the formula (II) include those represented by the following formulae (II-2) to (II-47):

Formula (II-2) Formula (II-3)

Formula (II-4) Formula (II-5)

Formula (II-6) Formula (II-7)

Formula (II-8) Formula (II-9)

Formula (II-10) Formula (II-11)

Formula (II-12) Formula (II-13)

Formula (II-14) Formula (II-15)

Formula (II-16) Formula (II-17)

Formula (II-18) Formula (II-19)

Formula (II-20) Formula (II-21)

Formula (II-22) Formula (II-23)

Formula (II-24) Formula (II-25)

Formula (II-26) Formula (II-27)

Formula (II-28) Formula (II-29)

Formula (II-30) Formula (II-31)

Formula (II-32) Formula (II-33)

Formula (II-34) Formula (II-35)

Formula (II-36) Formula (II-37)

Formula (II-38) Formula (II-39)

Formula (II-40) Formula (II-41)

Formula (II-42) Formula (II-43)

Formula (II-44) Formula (II-45)

Formula (II-46) Formula (II-47) In formula (II-2) to formula (II-47), Me is methyl, Et is ethyl, iPr is isopropyl, Bn is benzyl, and Boc is tert-butoxycarbonyl.

Based on the total usage amount of the diamine component (b2) is 100 moles, the usage amount of the diamine compound (b2-1) is 3 moles to 50 moles, preferably 5 moles to 50 moles, then More preferably, 5 moles to 45 moles.

If the diamine component (b2) does not contain the diamine compound (b2-1), the obtained liquid crystal display element has the defect that image sticking is likely to occur.

The diamine component (b2) may further comprise other diamine compounds (b2-2), and the types of the other diamine compounds (b2-2) may be the same as the diamine components in the aforementioned first polymer (A1). The other diamine compounds (b1-2) of (b1) are the same as those listed, so they will not be repeated here.

Based on the total usage amount of the diamine component (b2) is 100 moles, the usage amount of the other diamine compounds (b2-2) is 50 moles to 97 moles, preferably 50 moles to 95 moles, then More preferably, 55 moles to 95 moles. Process for the preparation of the second polymer (A2)

The preparation method of the second polymer (A2) of the present invention is the same as the preparation method of the aforementioned first polymer (A1), except that the second polymer (A2) uses the aforementioned tetracarboxylic dianhydride component ( a2) is prepared by reacting with the diamine component (b2), so the preparation method of the second polymer (A2) will not be repeated here.

The weight average molecular weight of the second polymer (A2) of the present invention in terms of polystyrene measured by gel permeation chromatography is 10,000 to 90,000, preferably 12,000 to 75,000, and more preferably 15,000 to 60,000.

Based on the total usage amount of the polymer (A) being 100 parts by weight, the usage amount of the first polymer (A1) is 30 parts by weight to 90 parts by weight, preferably 40 parts by weight to 90 parts by weight; and the second polymer The usage amount of (A2) is 5 parts by weight to 70 parts by weight, preferably 10 parts by weight to 70 parts by weight, more preferably 10 parts by weight to 60 parts by weight.

When the usage-amount of the 1st polymer (A1) and the usage-amount of a 2nd polymer (A2) are in the said range, the environment resistance of the formed liquid crystal display element is good. Solvent (B)

The solvent used in the liquid crystal aligning agent of the present invention is not particularly limited, as long as it can dissolve the polymer (A) and other optional components, and does not react with them, preferably the same as the aforementioned synthetic polyamide acid. As for the solvent to be used, the poor solvent used in the synthesis of the aforementioned polyamic acid may also be used in combination.

Specific examples of the solvent (B) include, but are not limited to, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, γ-butyrolactone, 4-hydroxy-4- Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol Ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetic acid Esters, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate or N,N-dimethylformamide or N,N-dimethylacetamide (N,N-dimethyl acetamide) and the like.

The solvent (B) may be used alone or in combination of two or more.

Based on 100 parts by weight of the polymer (A), the amount of the solvent (B) used is 800 to 4000 parts by weight, preferably 900 to 3500 parts by weight, and more preferably 1000 to 3000 parts by weight . Additives (C)

The liquid crystal alignment agent of the present invention may optionally contain an additive (C) within the scope of not affecting the efficacy of the present invention, and the additive (C) may be an epoxy compound or a silane compound having a functional group. The function of the additive (C) is to improve the adhesion of the liquid crystal alignment film to the surface of the substrate. The additives (C) may be used alone or in combination of two or more.

The aforementioned epoxy compounds may include but are not limited to 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, Glycerol Diglycidyl Ether, 2,2-Dibromoneopentyl Diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-di Toluenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-di Aminodiphenylmethane, N,N-glycidyl-p-glycidoxyaniline, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N,N-diepoxypropyl)aminopropyltrimethoxysilane, etc.

The epoxy compound is generally used in an amount of 40 parts by weight or less, and preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the polymer (A).

The above-mentioned silane compounds with functional groups may include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, Aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyl 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane Silane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine Triamine, 10-trimethoxysilyl-1,4,7-triazdecane, 10-triethoxysilyl-1,4,7-triazdecane, 9-trimethoxysilyl- 3,6-Diaznonyl acetate, 9-triethoxysilyl-3,6-diaznonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N -Bis(ethylene oxide)-3-aminopropyltrimethoxysilane, N-bis(ethylene oxide)-3-aminopropyltriethoxysilane, etc.

Based on 100 parts by weight of the polymer (A), the amount of the silane compound used is generally 10 parts by weight or less, and preferably 0.5 parts by weight to 10 parts by weight.

The additive (C) may be used in an amount of 0.5 to 50 parts by weight, and preferably 1 to 45 parts by weight, based on 100 parts by weight of the polymer (A). Preparation method of liquid crystal alignment agent

The preparation method of the liquid crystal alignment agent of the present invention is not particularly limited, and a general mixing method can be used, for example, firstly mixing the first polymer (A1) and the first polymer (A2) to form the polymer (A), and then mixing The polymer (A) is added with the solvent (B) and the additive (C) at a temperature of 0°C to 200°C, and the stirring device is continuously stirred until dissolved. Preferably, the polymer (A) and the additive (C) are added to the solvent (B) at a temperature of 20°C to 60°C. Method for forming liquid crystal alignment film

The present invention further provides a liquid crystal alignment film, which is formed by the aforementioned liquid crystal alignment agent. In one embodiment, the liquid crystal alignment agent can be coated on the substrate, and subjected to pre-baking, post-baking and photo-alignment treatment to form the liquid crystal alignment film.

The substrate coated by the liquid crystal alignment agent of the present invention is selected from transparent materials, wherein the transparent materials include but are not limited to alkali-free glass, soda lime glass, hard glass (Pyles glass), quartz glass for liquid crystal display devices , polyethylene terephthalate, polybutylene terephthalate, polyether terephthalate, polycarbonate, etc., preferably using ITO electrodes for liquid crystal driving that have been formed on the substrate to simplify the process. Furthermore, for a reflective liquid crystal display having only a single-sided substrate, the substrate may be made of an opaque material such as silicon wafer, and the electrodes in this case may be formed of a material that reflects light such as aluminum. The coating method of the liquid crystal aligning agent of the present invention can be, for example, a spin coating method, a printing method, an inkjet method, or the like.

The liquid crystal aligning agent of the present invention can choose any temperature and time to carry out the drying and baking processes after coating. In general, in order to sufficiently remove the contained organic solvent, drying at 50°C to 120°C for 1 minute to 10 minutes is required. After that, bake at 150°C to 300°C for 5 minutes to 120 minutes. The thickness of the coating film after baking is not particularly limited, but an excessively thin coating film will cause the deterioration of the reliability of the liquid crystal display, so the above coating film thickness is preferably 5 nm to 300 nm, and 10 nm to 200 nm. is better.

Although the liquid crystal alignment agent of the present invention can be subjected to the conventional rubbing alignment treatment, the effect is better when the photo alignment treatment method is used.

A specific example of the photo-alignment treatment method can be, for example, irradiating the surface of the above-mentioned coating film with radiation polarized in a specific direction, and then performing heat treatment at a temperature of 150°C to 250°C as appropriate to impart the above-mentioned coating film liquid crystal. Alignment energy. Among them, ultraviolet rays or visible light with wavelengths of 100 nm to 800 nm can be used as the above-mentioned radiation, and ultraviolet rays with wavelengths of 100 nm to 400 nm are preferable, and those with wavelengths of 200 nm to 400 nm are more preferable. Furthermore, in order to improve the liquid crystal alignment, the coated substrate may be irradiated with radiation while the coated substrate is heated at 150°C to 250°C. The irradiation dose of the aforementioned radiation is preferably 1 mJ/cm ² to 10,000 mJ/cm ² , more preferably 100 mJ/cm 2 to 5,000 mJ/cm ² . The liquid crystal alignment film prepared in the above manner can stably align the liquid crystal molecules in a certain direction.

The liquid crystal alignment agent of the present invention is subjected to pre-baking treatment, post-baking treatment and photo-alignment treatment to form a liquid crystal alignment film, and the pretilt angle of the liquid crystal alignment film is 0° to 3°. Manufacturing method of liquid crystal display element

The present invention further provides a liquid crystal display element comprising the aforementioned liquid crystal alignment film.

The manufacturing method of the liquid crystal display element is well known to those skilled in the art, therefore, the following description is only briefly made.

Referring to FIG. 1, a preferred embodiment of the liquid crystal display element 100 of the present invention includes a first unit 110, a second unit 120 and a liquid crystal unit 130, wherein the second unit 120 and the first unit 110 are spaced opposite to each other, and the liquid crystal unit 130 is disposed in the first unit 130. between the first unit 110 and the second unit 120 .

The first unit 110 includes a first substrate 112, an electrode 114 and a first liquid crystal alignment film 116, wherein the electrode 114 is formed on the surface of the first substrate 112 in a patterned manner, and the first liquid crystal alignment film 116 is formed on the electrode 114's surface.

The second unit 120 includes a second substrate 122 and a second liquid crystal alignment film 126 , wherein the second liquid crystal alignment film 126 is formed on the surface of the second substrate 122 .

The first substrate 112 and the second substrate 122 are selected from transparent materials, etc., wherein the transparent materials include but are not limited to alkali-free glass, soda lime glass, hard glass (Pyles glass), quartz glass for liquid crystal display devices , polyethylene terephthalate, polybutylene terephthalate, polyether terephthalate, polycarbonate, etc. The material of the electrode 114 is _{a transparent electrode selected from tin oxide (SnO 2} ), indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc.; or a metal electrode such as chromium.

The first liquid crystal alignment film 116 and the second liquid crystal alignment film 126 are respectively the above-mentioned liquid crystal alignment films, and their functions are to make the liquid crystal cell 130 form a pretilt angle, and the liquid crystal cell 130 can be driven by the parallel electric field generated by the electrode 114 .

The liquid crystals used in the liquid crystal unit 130 can be used alone or in combination, and the liquid crystals include, but are not limited to, diaminobenzene liquid crystals, pyridazine liquid crystals, Schiff base liquid crystals, and azo-based liquid crystals. (azoxy) liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal , biphenylcyclohexane (biphenylcyclohexane) liquid crystal, pyrimidine (pyrimidine) liquid crystal, dioxane (dioxane) liquid crystal, bicyclooctane (bicyclooctane) liquid crystal, cubane (cubane) liquid crystal, etc. Add cholesteryl liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate, etc., or use the trade names "C-15" and "CB-15" A chiral agent (manufactured by Merck & Co., Ltd.) or the like, or a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate.

The liquid crystal display element produced by the liquid crystal alignment agent of the present invention is suitable for various types of nematic liquid crystals, such as liquid crystal display elements of TN, STN, TFT, VA, IPS and the like. In addition, depending on the selected liquid crystal, it can also be used for liquid crystal display elements with different inductive properties or anti-inductive properties. Among the above-mentioned liquid crystal display elements, it is particularly suitable for an IPS type liquid crystal display element.

The following examples are used to illustrate the present invention in detail, but it is not intended that the present invention is limited to the contents disclosed by these examples. Synthetic Polymer (A1) Synthesis Example A1-1

A nitrogen inlet, a stirrer, a condenser and a thermometer are set on a four-necked conical flask with a volume of 500 ml, and nitrogen is introduced. Then, 0.0015 mol of 4,4'-diaminodiphenylamine (b1-1-1), 0.0235 mol of p-diamine benzene (b1-2-1), 0.025 mol of 2, 2'-dimethyl-4,4'-diaminobiphenyl (b1-2-2) and 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and stirred at room temperature until dissolved . Next, 0.005 mol of 2,3,5-tricarboxycyclopentylacetic dianhydride (a1-1) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction, the reaction solution was poured into 1500 ml of water to precipitate the polymer, the obtained polymer was filtered, and the steps of washing and filtering with methanol were repeated three times. After that, the product was placed in a vacuum oven and dried at a temperature of 60° C. to obtain the polymer (A1-1), the formula of which is shown in Table 1. Synthesis Examples A1-1 to A1-8 and Synthesis Comparative Examples A1'-1 to A1'-3

表1中： a1-1 2,3,5-三羧基環戊基醋酸二酐 a1-2 1,2,3,4-環丁烷四羧酸二酐 a1-3 苯均四羧酸二酐 b1-1-1 4,4'-二胺基二苯基胺 b1-1-2 2,4-二胺基二苯基胺 b1-2-1 對-二胺苯 b1-2-2 2,2'-二甲基-4,4'-二胺基聯苯 b1-2-3 4,4'-亞甲基雙(環己基胺) b1-2-4 1,4-二胺基環己烷 b1-2-5 2,6-二胺基吡啶 b1-2-6

合成聚合物 (A2) 合成例 A2-1 至 A2-11 及合成比較例 A2'-1 至 A2'-3 Synthesis Examples A1-1 to A1-8 and Synthesis Comparative Examples A1'-1 to A1'-3 used the same preparation method as the preparation method of the polymer (A1-1) of Synthesis Example A1-1, except that the synthesis Examples A1-1 to A1-8 and Synthetic Comparative Examples A1'-1 to A1'-3 change the types and amounts of raw materials in the polymer, and the formulations are shown in Table 1, which will not be repeated here. Table 1:

in FIG. 1: a1-1 2,3,5-Tricarboxycyclopentylacetic dianhydride a1-2 1,2,3,4-Cyclobutanetetracarboxylic dianhydride a1-3 pyromellitic dianhydride b1-1-1 4,4'-Diaminodiphenylamine b1-1-2 2,4-Diaminodiphenylamine b1-2-1 p-diamine benzene b1-2-2 2,2'-Dimethyl-4,4'-diaminobiphenyl b1-2-3 4,4'-Methylenebis(cyclohexylamine) b1-2-4 1,4-Diaminocyclohexane b1-2-5 2,6-Diaminopyridine b1-2-6

Synthetic Polymer (A2) Synthesis Examples A2-1 to A2-11 and Synthesis Comparative Examples A2'-1 to A2'-3

表2中： a2-1-1 式(III-1) a2-1-2 式(III-2) a2-1-3 式(III-3) a2-1-4 式(III-5) a2-1-5 式(III-8) a2-2-1 2,3,5-三羧基環戊基醋酸二酐 a2-2-2 1,2,3,4-環丁烷四羧酸二酐 a2-2-3 苯均四羧酸二酐 b2-1-1

b2-1-2

b2-1-3

b2-1-4

b2-1-5

b2-1-6

b2-1-7

b2-1-8

b2-2-1 對-二胺苯 b2-2-2 2,2'-二甲基-4,4'-二胺基聯苯 b2-2-3 4,4'-亞甲基雙(環己基胺) b2-2-4 1,4-二胺基環己烷 b2-2-5

b2-2-6

實施例 1 製備液晶配向劑 Synthesis Examples A2-1 to A2-11 and Synthesis Comparative Examples A2'-1 to A2'-3 used the same preparation method as the preparation method of the polymer (A1-1) of Synthesis Example A1-1, except that the synthesis Examples A2-1 to A2-11 and synthesis comparative examples A2'-1 to A2'-3 change the types and usage amounts of raw materials in the polymer, and the formulations thereof are shown in Table 2, which will not be repeated here. Table 2:

In Table 2: a2-1-1 Formula (III-1) a2-1-2 Formula (III-2) a2-1-3 Formula (III-3) a2-1-4 Formula (III-5) a2-1-5 Formula (III-8) a2-2-1 2,3,5-Tricarboxycyclopentylacetic dianhydride a2-2-2 1,2,3,4-Cyclobutanetetracarboxylic dianhydride a2-2-3 pyromellitic dianhydride b2-1-1

b2-1-2

b2-1-3

b2-1-4

b2-1-5

b2-1-6

b2-1-7

b2-1-8

b2-2-1 p-diamine benzene b2-2-2 2,2'-Dimethyl-4,4'-diaminobiphenyl b2-2-3 4,4'-Methylenebis(cyclohexylamine) b2-2-4 1,4-Diaminocyclohexane b2-2-5

b2-2-6

Example 1 Preparation of liquid crystal alignment agent

30 parts by weight of the polymer (A1-1) of Synthesis Example A1-1, 70 parts by weight of the polymer (A2-1) of Synthesis Example A2-1, and 800 parts by weight of NMP were weighed and stirred at room temperature After mixing, the liquid crystal alignment agent of Example 1 can be obtained. Preparation of liquid crystal alignment film and liquid crystal display element

The liquid crystal alignment agent prepared above was spin-coated on a glass substrate, wherein pixel electrodes were formed on the glass substrate, wherein the pixel electrodes had a pair of ITO electrodes (electrode width: 10 μm, electrode spacing: 10 μm). μm, electrode height: 50 nm) IPS driving electrodes, the pair of ITO electrodes have a comb-like shape respectively, and the comb-tooth-like parts of each other are arranged in a manner of being separated and engaged. After that, the glass substrate coated with the liquid crystal alignment agent was dried on a hot plate at 80°C for 5 minutes, and then baked in a hot air circulation oven at 250°C for 60 minutes to form a coating film with a thickness of 100 nm.

Through a polarizing plate, ultraviolet rays with a wavelength of 254 nm are irradiated on the surface of the coating film to prepare a substrate with a liquid crystal alignment film. Next, similarly, a coating film was formed on a counter substrate, which was a glass substrate without electrodes formed but having columnar spacers having a height of 4 μm, and an alignment treatment was applied.

The above-mentioned two substrates are a set, one of which is printed with a sealant, and the other is bonded to the liquid crystal alignment film in a manner that faces the liquid crystal alignment film and the alignment direction is 0°, and then the sealant is hardened to obtain an empty unit cell. This empty cell was injected into liquid crystal MLC-2041 (manufactured by Merck) by a reduced pressure injection method, and the injection port was sealed, which is the liquid crystal display element of Example 1.

The liquid crystal display element of Example 1 was evaluated by the following evaluation method, and Table 3 shows the results. Examples 2 to 15 and Comparative Examples 1 to 8

表3-2：

表4：

表3-1、表3-2及表4中： B-1 N-甲基-2-吡咯烷酮 B-2 乙二醇正丁基醚 B-3 N,N-二甲基乙醯胺 C-1 N,N,N',N'-四環氧丙基-4,4'-二胺基二苯基甲烷 C-2 N,N-環氧丙基-對-環氧丙氧基苯胺 評價方式 耐環境性 Examples 2 to 15 and Comparative Examples 1 to 8 use the same preparation method as the liquid crystal alignment agent of Example 1, except that Examples 2 to 15 and Comparative Examples 1 to 8 change the types and use of raw materials in the liquid crystal alignment agent. The formula and evaluation results are shown in Table 3-1, Table 3-2 and Table 4 respectively, and will not be repeated here. Table 3-1:

Table 3-2:

Table 4:

In Table 3-1, Table 3-2 and Table 4: B-1 N-Methyl-2-pyrrolidone B-2 Ethylene glycol n-butyl ether B-3 N,N-Dimethylacetamide C-1 N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane C-2 N,N-Glycidoxypropyl-p-glycidoxyaniline Evaluation method Environmental resistance

The liquid crystal display elements of Examples 1 to 15 and Comparative Examples 1 to 8 were placed in an environment with a temperature of 65° C. and a relative humidity of 85%, respectively. 6254) The ion densities of the liquid crystal display elements of Examples 1 to 16 and Comparative Examples 1 to 10 were measured, respectively. The test conditions are to apply a voltage of 1.7 volts and a triangular wave of 0.01 Hz at a temperature of 60°C. In the current-voltage waveform, the ion density (pC) can be measured by calculating the peak area in the range of 0 to 1 volt. The lower the ion density, the better the environmental resistance. The evaluation criteria of the ion density are as follows. ◎: Ion density < 20 ○: 20 ≦ Ion density < 40 △: 40 ≦ Ion density < 50 ╳: 50 ≦ Ion density afterimage test

After driving the liquid crystal display elements of Examples 1 to 15 and Comparative Examples 1 to 8 with an AC voltage of 10V for 30 hours, respectively, the measurement was performed using a device in which a polarizer and an analyzer were arranged between the light source and the light quantity detector, and the following formula Calculate the minimum relative transmittance (%). Minimum relative transmittance (%)=(β-B ₀ )/(B ₁₀₀ -B ₀ )×100

In the above formula, B ₀ is blank, and is the transmittance of light under crossed nicols; B ₁₀₀ is blank, and is the transmittance of light under parallel nicols β is the amount of light transmission at which the liquid crystal cell is sandwiched between the polarizer and the analyzer under crossed Nicols and becomes the smallest.

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element, and the smaller the black level, the better the contrast, that is, the better the image sticking property. ◎: Minimum relative transmittance≦0.5% ○: 0.5%＜minimum relative transmittance≦1.0% △: 1.0%＜minimum relative transmittance≦1.5% ╳: Minimum relative transmittance > 1.5%.

The above-mentioned embodiments are only to illustrate the principle and effect of the present invention, but not to limit the present invention. Modifications and changes made to the above embodiments by those skilled in the art still do not violate the spirit of the present invention. The scope of the rights of the present invention should be listed in the scope of the patent application described later.

100: Liquid crystal display element 110: Unit 1 112: The first substrate 114: The first conductive film 116: the first liquid crystal alignment film 120: Unit Two 122: Second substrate 126: The second liquid crystal alignment film 130: Liquid crystal unit

FIG. 1 is a side view of a liquid crystal display element according to an embodiment of the present invention.

100: Liquid crystal display element

110: Unit 1

112: The first substrate

114: The first conductive film

116: the first liquid crystal alignment film

120: Unit Two

122: Second substrate

126: The second liquid crystal alignment film

130: Liquid crystal unit

Claims (12)

A liquid crystal alignment agent, comprising: a polymer (A); and a solvent (B); wherein the polymer (A) comprises a first polymer (A1) and a second polymer (A2), the first polymer ( A1) is prepared by reacting a first mixture, the first mixture comprises a tetracarboxylic dianhydride component (a1) and a diamine component (b1), wherein the diamine component (b1) comprises at least one such as the formula ( The diamine compound (b1-1) shown in I):

Formula (I) In formula (I), R ¹ to R ¹⁰ are the same or different hydrogen atoms or monovalent organic groups, wherein R ¹ to R ¹⁰ contain at least two primary amino groups; the second polymer (A2 ) is prepared by the reaction of a second mixture, the second mixture comprising a tetracarboxylic dianhydride component (a2) and a diamine component (b2), wherein the diamine component (b2) comprises at least one such as formula (II) ) represented by the diamine compound (b2-1):

Formula (II) In formula (II), E ₁ and E ₅ each independently represent a single bond or an alkylene group with 1 to 5 carbon atoms; E ₂ and E ₄ each independently represent a sub-group with 1 to 5 carbon atoms Alkyl; E ₃ represents an alkylene group having 1 to 6 carbon atoms, or a cycloalkylene group; B ₁ and B ₅ each independently represent a single bond, -O-, -NH-, -NCH ₃ -, -C (=O)-, -C(=O)O-, -C(=O)NCH ₃ -, -OC(=O)-, -NHC(=O)- or -N(CH ₃ )C(= O)-; a represents 0 or 1; and D ₁ has the structure shown in formula (II-1):

Formula (II-1) In formula (II-1), R is a linear, branched or cyclic monovalent hydroxyl group having 1 to 20 carbon atoms, and * represents a linking group. The liquid crystal alignment agent of claim 1, wherein in formula (II-1), R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexane, n-octyl, benzyl, n-hexadecyl or 9-fluorenylmethyl. The liquid crystal aligning agent according to claim 1, wherein in formula (II-1), R is tert-butyl group or 9-fluorenylmethyl group. The liquid crystal alignment agent of claim 1, wherein the tetracarboxylic dianhydride component (a2) in the second mixture comprises at least one tetracarboxylic dianhydride compound (a2-1) represented by formula (III):

Formula (III) In formula (III), R ₁ to R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and a group having 2 to 6 carbon atoms. alkynyl group of 6, monovalent organic group containing fluorine atom and carbon number of 1 to 6 or phenyl group, R ₁ to R ₄ are the same or different, and at least one of _{R 1} , R ₂ , R ₃ and R ₄ One is not a hydrogen atom. The liquid crystal aligning agent of claim 1, wherein in the first mixture, based on the total usage amount of the diamine component (b1) is 100 mol, the diamine compound (b1-1) represented by the formula (I) ) is used in an amount ranging from 3 mol to 50 mol. The liquid crystal alignment agent of claim 1, wherein in the second mixture, based on the total usage amount of the diamine component (b2) is 100 mol, the diamine compound (b2-1) represented by the formula (II) ) is used in an amount ranging from 3 mol to 50 mol. The liquid crystal alignment agent according to claim 4, wherein in the second mixture, the total usage amount based on the tetracarboxylic dianhydride component (a2) is 100 moles, and the tetracarboxylic acid represented by the formula (III) The anhydride compound (a2-1) is used in an amount of 30 mol to 100 mol. The liquid crystal alignment agent of claim 1, wherein based on the total usage of the polymer (A) is 100 parts by weight, the usage of the first polymer (A1) is 30 to 95 parts by weight, and the second polymer (A1) is used in an amount of 30 to 95 parts by weight. The polymer (A2) is used in an amount of 5 parts by weight to 70 parts by weight. The liquid crystal alignment agent according to claim 1, wherein the amount of the solvent (B) used is 800 to 3000 parts by weight based on 100 parts by weight of the polymer (A). A liquid crystal alignment film is formed from the liquid crystal alignment agent according to any one of claims 1 to 9. The liquid crystal alignment film of claim 10, wherein the liquid crystal alignment agent is subjected to pre-baking treatment, post-baking treatment and photo-alignment treatment to form the liquid crystal alignment film. A liquid crystal display element comprising the liquid crystal alignment film of claim 11.

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