KR20140055967A - Liquid crystal aligning agent for psa mode liquid crystal display device, liquid crystal alignment film for psa mode liquid crystal display device, and the psa mode liquid crystal display device and manufacturing method thereof - Google Patents

Abstract

A PSA mode liquid crystal display device difficult to generate an afterimage can be obtained while showing a high voltage holding ratio even after a liquid crystal cell is irradiated with light. A polymer (A1) having a polymerizable unsaturated bond is contained in a liquid crystal aligning agent for the PSA mode liquid crystal display device. It is preferable that a group including the polymerizable unsaturated bond which the polymer (A1) has is at least one selected from the group consisting of a group represented by the formula (f1), a group represented by the formula (f2), and a group represented by the formula (f3).

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment agent for a liquid crystal display element, a liquid crystal alignment layer for a liquid crystal display element, a liquid crystal alignment element for a liquid crystal display element, and a method of manufacturing the liquid crystal display element. CRYSTAL DISPLAY DEVICE, AND THE PSA MODE LIQUID CRYSTAL DISPLAY DEVICE AND MANUFACTURING METHOD THEREOF}

The present invention relates to a liquid crystal aligning agent and a liquid crystal alignment film for a PSA mode liquid crystal display, and a PSA mode liquid crystal display device and a method of manufacturing the same. More particularly, the present invention relates to a technique for improving the voltage maintenance characteristics of a PSA mode liquid crystal display .

Conventionally, various driving methods having different electrode structures and physical properties of liquid crystal molecules used have been developed as liquid crystal display elements. For example, TN type, STN type, VA type, in-plane switching type (IPS Type liquid crystal display devices are known. These liquid crystal display devices have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of the liquid crystal alignment film, for example, polyamic acid, polyamic acid ester, polyimide, polyester, and polyorganosiloxane are known.

Recently, in a liquid crystal display device, a PSA (Polymer Sustained Alignment) mode has been proposed as a new driving mode for controlling the orientation of liquid crystal molecules. The PSA mode is a mode in which a photopolymerizable compound is incorporated into a liquid crystal material and the liquid crystal cell is irradiated with light while a voltage is applied between a pair of electrodes sandwiching the liquid crystal layer, And controlling the molecular orientation of the liquid crystal molecules by polymerization. According to this technique, there is an advantage that the viewing angle can be enlarged and high-speed response can be achieved.

On the other hand, in the PSA mode, when the light irradiation amount is insufficient, the unreacted photopolymerizable compound remains in the liquid crystal layer, and image burn-in (after-image) tends to occur due to the unreacted substance. Further, if the light irradiation amount is increased for the complete reaction of the photopolymerizable compound, the quality of the liquid crystal molecules or the liquid crystal alignment film is lowered, and the display quality of the panel may be lowered. In order to solve such a problem, various techniques for reducing the amount of the photopolymerizable compound remaining in the liquid crystal layer without increasing the light irradiation amount have been proposed (see, for example, Patent Document 1). This patent document 1 discloses that a liquid crystal compound having a terphenyl ring structure (hereinafter also referred to as "terphenyl liquid crystal") is contained in the liquid crystal layer.

In recent years, further rapid response of PSA type liquid crystal panels has been investigated. As a technique for solving this problem, monofunctional liquid crystalline compounds each having one of an alkenyl group and a fluoroalkenyl group (hereinafter referred to as " alkenyl- (For example, refer to Patent Documents 2 to 4).

International Publication No. 2009/050869 Japanese Patent Application Laid-Open No. 2010-285499 Japanese Patent Application Laid-Open No. 9-104644 Japanese Patent Application Laid-Open No. 6-108053

However, even when the terphenyl-based liquid crystal is introduced into the liquid crystal layer, the number of unreacted photopolymerizable compounds remaining after light irradiation is still large, and there is still room for further improvement in terms of afterimage characteristics. In addition, in the liquid crystal display device using the alkenyl-based liquid crystal, the response speed can be increased. On the other hand, when the light irradiation to the liquid crystal cell is performed, the voltage holding ratio is lower than that of the liquid crystal cell in which the alkenyl- It is becoming clear that it grows. From the viewpoint of further improving the display quality of the liquid crystal display element, it is required to suppress the decrease of the voltage holding ratio by light irradiation as much as possible.

The present invention has been made in view of the above problems and provides a liquid crystal aligning agent capable of exhibiting a high voltage holding ratio even after light irradiation to a liquid crystal cell and capable of obtaining a PSA mode liquid crystal display element in which after- The purpose.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to achieve the above-mentioned problems of the prior art. As a result, they have found that by forming a liquid crystal alignment film using a liquid crystal aligning agent containing a specific polymer in the process of manufacturing a PSA mode liquid crystal display element, The present inventors have found that the problems can be solved and accomplished the present invention. Specifically, a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a manufacturing method thereof for PSA mode liquid crystal display elements described below are provided by the present invention.

In one aspect, the present invention provides a liquid crystal aligning agent for a PSA mode liquid crystal display element containing a polymer (A1) having a polymerizable unsaturated bond.

The liquid crystal aligning agent of the present invention contains a polymer (A1) having a polymerizable unsaturated bond as a polymer component. By forming the liquid crystal alignment film of the PSA mode liquid crystal display element with such a liquid crystal aligning agent, it is possible to exhibit a high voltage retention rate even after the liquid crystal cell is irradiated with light in the process of manufacturing the PSA mode liquid crystal display element, A liquid crystal display element can be obtained. In particular, by using the liquid crystal aligning agent of the present invention for the production of a liquid crystal display element containing a monofunctional liquid crystal compound having any one of an alkenyl group and a fluoroalkenyl group in a liquid crystal layer, a high voltage retention ratio It is possible to more suitably obtain the effect of being able to be expressed and the effect that the afterimage is less likely to occur.

According to another aspect of the present invention, there is provided a liquid crystal display device comprising a first step of coating a liquid crystal aligning agent of the present invention on a conductive film of a pair of substrates each having a conductive film and then heating the same to form a coated film, A second step of arranging a pair of substrates on which a pair of substrates are formed so as to face each other with a liquid crystal layer containing a liquid crystal compound interposed therebetween to construct a liquid crystal cell; And a third step of irradiating the liquid crystal cell with light in a state where the liquid crystal cell is irradiated with light.

In another aspect, the present invention provides a liquid crystal alignment film for a PSA mode liquid crystal display element formed using the liquid crystal aligning agent of the present invention, and a PSA mode liquid crystal display element comprising the liquid crystal alignment film.

1 is a view showing electrode patterns of a transparent electrode film used in Examples and Comparative Examples.
2 is a view showing an electrode pattern of a transparent electrode film used in Examples and Comparative Examples.
3 is a view showing an electrode pattern of a transparent electrode film used in Examples and Comparative Examples.

(Mode for carrying out the invention)

Hereinafter, each component contained in the liquid crystal aligning agent for PSA mode liquid crystal display elements of the present invention, and other components arbitrarily blended as required will be described.

≪ Polymer (A1) >

The liquid crystal aligning agent of the present invention contains a polymer (A1) having a polymerizable unsaturated bond as a polymer component. The structure of the polymerizable unsaturated bond is not particularly limited, but preferable examples thereof include a group represented by the following formula (f1), a group represented by the following formula (f2), a group represented by the following formula (f3) You can:

(Formula (f1) of, R ^1, R ⁴ and R ⁶ are, each independently, a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 5 carbon atoms of 1 to 5 carbon atoms; formula (f2) of, R ² is, A hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent group having -O- between at least one carbon-carbon bond of the hydrocarbon group, and * in the formulas (f1) to (f3) Indicating a combined hand).

Examples of the alkyl group having 1 to 5 carbon atoms for R ¹ , R ⁴ and R ⁶ in the formula (f1) include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. It may be in powder form. Examples of the substituted alkyl group having 1 to 5 carbon atoms include groups in which at least one hydrogen atom of the above-exemplified alkyl group is substituted with, for example, a halogen atom (fluorine, chlorine, bromine, iodine, etc.) . R ¹ , R ⁴ and R ⁶ are preferably a hydrogen atom or an alkyl group or substituted alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ² of the formula (f2) include a monovalent chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, A cyclohexyl group, a phenyl group, a tolyl group, a xylyl group, a benzyl group, a biphenyl group, a 4,4'-bicyclohexyl group, a 4-cyclohexyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, A hexylphenyl group, an ethylphenyl group, a propylphenyl group, and a pentylphenyl group.

The group containing the polymerizable unsaturated bond of the polymer (A1) is preferably at least one selected from the group consisting of the group represented by the formula (f1), the group represented by the formula (f2) and the group represented by the formula (f3) , More preferably at least one selected from the group consisting of the group represented by the formula (f1) and the group represented by the formula (f2).

Examples of the main skeleton of the polymer (A1) include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, poly (styrene-phenylmaleimide ) Derivatives, poly (meth) acrylate derivatives, and the like. The polymer (A1) is preferably at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane. And more preferably at least one member selected from the group consisting of polyamic acid, polyimide and polyorganosiloxane. Hereinafter, the polyamic acid, the polyamic acid ester, the polyimide and the polyorganosiloxane as the polymer (A1) of the present invention will be described in detail.

[Polyamic acid (A1)]

In the present invention, the polyamic acid as the polymer (A1) has a polymerizable unsaturated bond and preferably has the polymerizable unsaturated bond in the side chain. A polyamic acid having such a polymerizable unsaturated bond (hereinafter also referred to as " polyamic acid (A1) ") can be synthesized by reacting, for example, tetracarboxylic acid dianhydride with a diamine having a polymerizable unsaturated bond.

[Tetracarboxylic acid dianhydride]

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid (A1) in the present invention include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, and the like. . Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6,8-2 anhydride, 4,9-dioxotricyclo [5.3.1.0 ^2,6 ] undecane- , 5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride and the like;

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride and the like;

Tetracarboxylic acid dianhydride described in JP-A-2010-97188, and the like can be used. The tetracarboxylic acid dianhydride may be used singly or in combination of two or more.

As the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid, it is preferable to contain an alicyclic tetracarboxylic dianhydride, and 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4 -Cyclobutane tetracarboxylic acid dianhydride, and the like. The content (total amount) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride is preferably in the range of , Preferably 60 mol% or more, and more preferably 80 mol% or more.

[Diamine]

The diamine used for synthesizing the polyamic acid in the present invention preferably contains a diamine having a polymerizable unsaturated bond (hereinafter also referred to as "specific diamine"). The specific diamine is not particularly limited as long as it has a polymerizable unsaturated bond and two primary amino groups. Examples of the diamine having a group represented by the formula (f1) include a compound represented by each of the following formulas (E1-1) to (E1-3); As the diamine having a group represented by the formula (f2), a compound represented by the following formula (E1-5) or the like; As the diamine having a group represented by the formula (f3), a compound represented by the following formula (E1-4) or the like; Preferred embodiments include:

(Formula (E1-1) of, R ^1, R ⁴ and R ⁶ are, each independently, a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 5 carbon atoms of 1 to 5 carbon atoms; X ^1, Y ¹ and Z ¹ A ¹ and g ¹ are each independently an integer of 0 to 12, and b ¹ , c ¹ , d ¹ , e ¹ , f ¹ and e ² are each independently a phenylene group, a cyclohexylene group or an oxygen atom; h ¹ , k ¹ and l ¹ are each independently 0 or 1, provided that a ^{1 to} l ¹ are combinations in which oxygen atoms are adjacent to each other, "-CO-O-" and a carbonyl group adjacent to each other And " -CO-O- " and the oxygen atom are not in mutually adjacent combinations);

(In the formula (E1-2), two R ¹ , R ⁴ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms, and X ² and Y ² are B ²¹ , b ²² , c ² , d ² , e ² , g and g are each independently a phenylene group or a cyclohexylene group; a ²¹ , a ²² and f ² are each independently an integer of 0 to 12; ^2, h ^2, k ²¹ and k ²² each independently 0 or 1; ^{stage, a 21, a 22, b} 21, b 22, c 2, d 2, e 2, f 2, g 2, h ² , k ²¹ and k ²² may be a combination in which oxygen atoms are adjacent to each other, a combination in which "-CO-O-" and a carbonyl group are adjacent to each other and a combination in which oxygen atoms are adjacent to each other with "-CO- Lt; / RTI >

(Wherein R ¹ , R ⁴ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom, alkyl group of 1 to 12 or the "- (CH _{2) n} -OH" and (where, n is an integer of 1~4); a ³ and c is ^3, are each an integer from 1 to 12 independently, b is 2, ³ Or 3, d ³ is an integer of 0 to 12, e ³ , f ³ and k ³ are each independently 0 or 1, provided that a plurality of R ¹ , R ⁴ , R ⁶ , a ³ and k ³ Each independently have the above definition; when d ³ = 0, e ³ = f ³ = 0);

X ⁴ , Y ⁴ and Z ⁴ are each independently a phenylene group, a cyclohexylene group or an oxygen atom; a ⁴ and g ⁴ each independently represent an integer of 0 to 12, and, b ^4, c ^{4, 4} d, ⁴ e, ⁴ f, ⁴ h and i ⁴ are each independently 0 or 1; stage, a ⁴ ~i ⁴ are combined with each other by the oxygen atoms adjacent to each other, Quot; -CO-O- " and a carbonyl group adjacent to each other and a combination in which -CO-O- and oxygen atoms are not adjacent to each other);

(Wherein (E1-5), R ⁵ is a hydrogen atom or a methyl group, W ^5, X ^5, Y ⁵ and Z ⁵ are, each independently, a phenylene group, a cyclohexylene group, an oxygen atom or a carbon number of 1 to 12 alkanediyl group gt; f ⁵ is an integer of 0~12, ⁵ a, ⁵ b, ⁵ c, ⁵ d, ⁵ e, ⁵ g, and h ⁵ are each independently 0 or 1; stage, a ^{5 to} h ⁵ represent a combination in which oxygen atoms are adjacent to each other, a combination in which "-CO-O-" and a carbonyl group are adjacent to each other, and "-CO-O-" and a combination in which oxygen atoms are not adjacent to each other ).

In the formula (E1-1), from the viewpoint that the good image retention characteristic, as k ¹ = ^1, it is preferable that R ⁴ and R ⁶ is a hydrogen atom. From the viewpoint of improving the high-speed responsiveness of the liquid crystal display element, it is preferable that k ¹ = 0.

The formula ¹ a ~l in the (E1-1) ¹ is a combination between the oxygen atom adjacent to each other, "-CO-O-" and carbonyl groups and combinations, "-CO-O-" which neighbor each other, And oxygen atoms are not adjacent to each other. Specifically, when a ¹ = 0, at least one of b ¹ and k ¹ is zero. When g ¹ = 0, at least two of f ¹ , h ¹ and l ¹ are 0, or f ¹ = 0 and h ¹ = l ¹ = 1. When c ¹ = d ¹ = e ¹ = 0, at least one of b ¹ and f ¹ is zero. X ¹ , Y ¹ and Z ¹ are not a combination in which oxygen atoms are adjacent to each other or a combination in which oxygen atoms and carbonyl groups are adjacent to each other. At least two of h ¹ , k ¹ and l ¹ are 0 when a ¹ -g ¹ are both 0, or k ¹ = 0 and h ¹ = l ¹ = 1.

In the formula ^{(E1-2), a 21, a} 22, b 21, b 22, c 2, d 2, e 2, f 2, g 2, h 2, k 21 and k ²² is, between the oxygen atom Quot; -CO-O- " and a carbonyl group adjacent to each other and a combination in which " -CO-O- " and oxygen atoms are not adjacent to each other. Specifically, when a ²¹ = 0, at least one of b ²¹ and k ²¹ is 0, and when a ²² = 0, at least one of b ²² and k ²² is zero. f ² = a 0 when, e ^2, g ² and h, or at least two of the ² 0, ² or e = 0 and g ² = h ² = 1.

Examples of the alkyl group having 1 to 12 carbon atoms for R ³ in the formula (E1-3) include an alkyl group having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, A dodecyl group, and the like. They may be linear or branched.

In the formula (E1-4), a ⁴ ~i ⁴ are combined with each other by the oxygen atoms adjacent to each other, "-CO-O-" and carbonyl groups and combinations, "-CO-O-" which neighbor each other, And oxygen atoms are not adjacent to each other. Specifically, when g ⁴ = 0, at least two of f ⁴ , h ⁴ and i ⁴ are 0, or f ⁴ = 0 and h ⁴ = i ⁴ = 1. When c ⁴ = d ⁴ = e ⁴ = 0, at least one of b ⁴ and f ⁴ is zero. X ⁴ , Y ⁴ and Z ⁴ are not a combination in which oxygen atoms are adjacent to each other or a combination in which oxygen atoms and carbonyl groups are adjacent to each other. and at least two of b ⁴ , h ⁴ and i ⁴ are 0 when c ^{4 to} g ⁴ are both 0 or b ⁴ = 0 and h ⁴ = i ⁴ = 1.

Further, the formula (E1-5) as the W ^5, X ^5, Y ^5, and Al having 1 to 12 carbon atoms in the alkanediyl group Z ⁵ in, for example, methylene group, ethylene group, propane-1,3- A butane-1,4-diyl group, a butane-1,3-diyl group, a pentane-1,5-diyl group, a heptane-1,7-diyl group, , 8-diyl group, decane-1,10-diyl group, dodecane-1,12-diyl group and the like.

In the above formula (E1-5), a combination in which oxygen atoms are adjacent to each other, a combination in which -CO-O- and a carbonyl group are adjacent to each other, and a combination in which oxygen atoms are adjacent to each other and -CO- . Specifically, the f ⁵ = 0 when, e ^{5, 5} g, and h of ⁵ or at least two are each 0, ^5, or e = 0 and g ⁵ = h ⁵ = 1. W ⁵ , X ⁵ , Y ⁵ and Z ⁵ are not a combination in which oxygen atoms are adjacent to each other or a combination in which oxygen atoms and carbonyl groups are adjacent to each other.

Specific examples of the compound represented by each of the above formulas (E1-1) to (E1-5) include compounds represented by the above formula (E1-1), for example, compounds represented by the following formulas (E1-1-1) to E1-1-9); Examples of the compound represented by the formula (E1-2) include compounds represented by each of the following formulas (E1-2-1) to (E1-2-5); Examples of the compound represented by the formula (E1-3) include compounds represented by each of the following formulas (E1-3-1) to (E1-3-5); Examples of the compound represented by the formula (E1-4) include compounds represented by each of the following formulas (E1-4-1) to (E1-4-5); Examples of the compound represented by the formula (E1-5) include compounds represented by the following formulas (E1-5-1) to (E1-5-6), respectively; Respectively.

The above specific diamine is preferably a compound having a polymerizable unsaturated bond and having a group represented by the formula (f1) or the formula (f2) above, and the formula (E1-1) to (E1- 5) is more preferably at least one selected from the group consisting of the compound represented by the formula (E1-1) and the compound represented by the formula (E1-4). When the group represented by the formula (f1) is used, the group is preferably contained as a part of the acryloyl group or the methacryloyl group from the viewpoint of improving the afterimage characteristic, and it is preferable that the group has a high- It is preferable that the alkenyl group is an alkenyl group.

As the diamine for synthesizing the polyamic acid (A1) in the present invention, the above-mentioned specific diamine may be used singly, but a diamine other than the specific diamine (hereinafter also referred to as " other diamine " May be used.

Examples of the other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like; As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'- Diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'- Phenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9- ) Phenyl hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- (p-phenylenediisopropylidene) (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-bis (4-aminophenoxy) benzene, Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole,

N, N'-bis (4-aminophenyl) benzidine, N, N'- Aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5- diaminobenzoic acid, dodecaneoxy- Oxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy- 2,5-diaminobenzene, pentadecaneoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecanoxy-2, 5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy- 2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid ranostanyl, (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, Bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1 (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, Heptylcyclohexane, 1,1-bis (4 - ((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1-bis (4 - ((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 1- (3,5-diaminobenzoyloxy) cholestane represented by the following formula (D-1): < EMI ID =

^Wherein X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and n is 0 or 1, provided that a and b are not 0 at the same time.

And the like;

As the diaminoorganosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be used. In addition, the diamine described in JP-A-2010-97188 can be used have.

Examples of the divalent group represented by "-X ^I - (R ^I -X ^II ) _n -" in the above formula (D-1) include an alkanediyl group having 1 to 3 carbon atoms, * -O-, Or * -OC ₂ H ₄ -O- (provided that a bonding hand having "*" attached thereto is bonded to a diaminophenyl group).

Specific examples of the group "-C _c H _{2c +1} " include a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an n-pentyl group, n-heptadecyl, n-heptadecyl, n-octadecyl, n-hexadecyl, n-hexadecyl, An n-nonadecyl group, and an n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-4).

As other diamines, one of these compounds may be used alone or two or more of them may be used in combination.

In the synthesis of the polyamic acid (A1), the amount of the specific diamine to be used is preferably from 0.1 to 50 mol%, more preferably from 1 to 30 mol%, based on the total amount of the diamine used in the synthesis , And still more preferably from 5 to 30 mol%.

[Molecular Weight Regulator]

In the synthesis of the polyamic acid, the endmodified polymer may be synthesized by using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and the diamine as described above. By using such a polymer having a terminal modification type, the coating property (printing property) of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention.

Examples of the molecular weight regulator include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds. Specific examples thereof include acid anhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, and n-decylsuccinic anhydride; As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and the like; As the monoisocyanate compound, for example, phenyl isocyanate, naphthyl isocyanate and the like; Respectively.

The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and diamine to be used.

<Synthesis of polyamic acid>

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid in the present invention is such that the ratio of the acid anhydride group of the tetracarboxylic acid dianhydride to the equivalent of 0.2 to 2 equivalents , More preferably from 0.3 to 1.2 equivalents. The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 캜 to 150 캜, more preferably 0 to 100 캜. The reaction time is preferably 0.5 to 24 hours, more preferably 2 to 10 hours.

As the organic solvent to be used for the reaction, the polyamic acid (A1) to be synthesized may be dissolved. Specific examples thereof include N-methyl-2-pyrrolidone, N-ethyl- , N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone,? -Butyrolactone, tetramethylurea, hexamethylphosphoric triamide Non-protonic polar solvents such as N-methylpyrrolidone; phenol-based solvents such as m-cresol, xylenol, phenol, and halogenated phenol; And the like. These organic solvents may be used singly or in combination of two or more.

As the organic solvent used in the reaction, a poor solvent of the polyamic acid (A1) may be used in combination within a range in which the polyamic acid (A1) is not precipitated. Examples of such a poor solvent include alcohols such as methanol, ethanol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol and ethylene glycol monomethyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; But are not limited to, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, isoamyl propionate, Ester; Diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, Ethylene 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, tetrahydrofuran, diisopentyl ether Ether; Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene and o-dichlorobenzene; And hydrocarbons such as hexane, heptane, octane, benzene, toluene and xylene. These poor solvents may be used singly or in combination of two or more.

When a poor solvent of the polyamic acid (A1) is used as the organic solvent to be used in the reaction, the use ratio thereof is preferably 50% by weight or less based on the total amount of the organic solvent used in the synthesis, Is not more than 40% by weight, and more preferably not more than 30% by weight.

The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is from 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution.

As described above, a reaction solution obtained by dissolving the polyamic acid (A1) is obtained. The reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent. Alternatively, the polyamic acid (A1) contained in the reaction solution may be isolated and then supplied to the preparation of a liquid crystal aligning agent, Or may be provided for the preparation of a liquid crystal aligning agent. When the polyamic acid (A1) is subjected to dehydration cyclization to form polyimide, the reaction solution may be directly supplied to the dehydration ring-closing reaction. Alternatively, the polyamic acid (A1) contained in the reaction solution may be isolated, Or may be subjected to a dehydration cyclization reaction after the isolated polyamic acid (A1) is purified. The polyamic acid (A1) can be isolated and purified by a known method.

&Lt; Polyamic acid ester (A1) >

The polyamic acid ester as the polymer (A1) in the present invention has a polymerizable unsaturated bond. The polyamic acid ester (hereinafter also referred to as &quot; polyamic acid ester (A1) &quot;) having such a polymerizable unsaturated bond may be obtained by, for example, [I] reacting a polyamic acid (A1) A method of reacting a tetracarboxylic acid diester with a diamine, [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine, and have.

Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; Phenols such as phenol and cresol, and the like. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like, and the epoxy group-containing compound For example, propylene oxide. The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring opening the tetracarboxylic acid dianhydride exemplified in the synthesis of the above polyamic acid by using the above-mentioned alcohols. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester thus obtained with a suitable chlorinating agent such as thionyl chloride. As the diamines used in the methods [II] and [III], diamines and the like exemplified for the synthesis of the polyamic acid (A1) can be used. The polyamic acid ester (A1) may have only an amide ester structure, or may be a partial esterified entity in which the amide structure and the amide ester structure coexist.

&Lt; Polyimide (A1) >

In the present invention, the polyimide as the polymer (A1) has a polymerizable unsaturated bond. The polyimide having such a polymerizable unsaturated bond (hereinafter also referred to as &quot; polyimide (A1) &quot;) can be obtained, for example, by imidizing the polyamic acid (A1) synthesized as described above by dehydration ring closure.

The polyimide (A1) may be a completely imidized product obtained by dehydrating and ring closure of all of the arboric acid structure of the polyamic acid (A1), which is a precursor thereof, and dehydrating and cyclizing only a part of the arboric acid structure, It may be a partially imide cargo. The polyimide (A1) of the present invention preferably has an imidization ratio of 40% or more, more preferably 50 to 99%. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. A part of the imide ring may be an isoimide ring.

The dehydration ring-closure of the polyamic acid (A1) can be carried out by heating the polyamic acid (A1) or by dissolving the polyamic acid (A1) in an organic solvent, adding a dehydrating agent and a dehydrating ring- . &Lt; / RTI &gt; Of these, the latter method is preferable.

In the method of adding the dehydrating agent and the dehydrating ring-closing catalyst to the solution of the polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as N-methylpiperidine, pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of the polyamic acid (A1). The reaction temperature of the dehydration cyclization reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 0.5 to 20 hours, more preferably 1.0 to 8 hours.

In this way, a reaction solution containing the polyimide (A1) is obtained. This reaction solution may be provided as it is in the preparation of the liquid crystal aligning agent as it is or may be added to the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. After the polyimide (A1) The polyimide (A1) may be provided in the preparation or may be provided in the preparation of the liquid crystal aligning agent after purified polyimide (A1). These purification operations can be carried out according to a known method.

The polyamic acid (A1), the polyamic acid ester (A1) and the polyimide (A1) obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s, And more preferably a solution viscosity of 15 to 500 mPa · s. The solution viscosity (mPa 占 퐏) of the polymer was determined by using a solution of these polymers (for example,? -Butyrolactone, N-methyl-2-pyrrolidone and the like) % Of the polymer solution at 25 占 폚 using an E-type rotational viscometer.

The polyamic acid (A1), the polyamic acid ester (A1) and the polyimide (A1) preferably have a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 500 to 300,000, More preferably 200,000.

[Polyorganosiloxane (A1)]

In the present invention, the polyorganosiloxane as the polymer (A1) has a polymerizable unsaturated bond. The polyorganosiloxane having such a polymerizable unsaturated bond (hereinafter also referred to as &quot; polyorganosiloxane (A1) &quot;) can be synthesized by appropriately combining organic chemical methods. As an example thereof,

(I) a method of hydrolyzing and condensing a hydrolyzable silane compound (s1) having a polymerizable unsaturated bond or a mixture of the silane compound (s1) and another silane compound;

(II) a hydrolyzable silane compound (s2) having an epoxy group, or a polymer obtained by hydrolysis and condensation of a mixture of the silane compound (s2) and another silane compound (hereinafter also referred to as "epoxy group-containing polyorganosiloxane" ) And a carboxylic acid (c1) having a polymerizable unsaturated bond;

(III) a method in which the silane compound (s1) or a mixture of the silane compound (s1) and another silane compound is heated in an alcohol solvent under an oxalic acid catalyst;

And the like.

[Silane compound (s1)]

The silane compound (s1) is a hydrolyzable silane compound having a polymerizable unsaturated bond, and specific examples thereof include 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxy (Meth) acryloxypropyltriethoxysilane, 2- (meth) acryloxyethyltrichlorosilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (Meth) acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Silane, vinyltriethoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, and the like. As the silane compound (s1), one kind or a mixture of two or more kinds of them can be used. Further, in the present specification, "(meth) acryloxy" means acryloxy and methacryloxy.

[Silane compound (s2)]

The silane compound (s2) is a hydrolyzable silane compound having an epoxy group, and specific examples thereof include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- Glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxypropyldimethoxysilane, Glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethylmethyldimethoxysilane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxy Ethyldimethylmethoxysilane, 2-glycidyloxyethyldimethylethoxysilane, 4-glycidyloxybutyltrimethoxysilane, 4-glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyl Dimethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 4-glycidyloxybutyldimethylmethane (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-ethylhexyltrimethoxysilane, - (3,4-epoxycyclohexyl) propyltrimethoxysilane, and 3- (3,4-epoxycyclohexyl) propyltriethoxysilane. As the silane compound (s2), one kind or a mixture of two or more kinds of them can be used.

Examples of other silane compounds (hereinafter, also referred to as silane compounds (s3)) that can be optionally used in the above methods (I) to (III) include methyltrichlorosilane, methyltrimethoxysilane , Methyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethyl Silane, ethoxytrimethylsilane, tetramethoxysilane, tetraethoxysilane, octadecyltrichlorosilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and the like. Can. As the other silane compound (s3), one kind or a mixture of two or more kinds of them may be used.

The silane compound used in the synthesis of the polyorganosiloxane (A1) according to the above-mentioned method (I) is such that the silane compound (s1) is contained in an amount of 1 to 80 mol% based on the total amount of the silane compound , More preferably from 5 to 50 mol%. The silane compound used in the synthesis preferably contains a silane compound (s2) in order to facilitate introduction of a structure such as a vertically aligning group to be described later into the side chain of the polymer. The use ratio of the silane compound (s2) is preferably 20 to 90 mol%, more preferably 50 to 80 mol%, based on the total amount of the silane compound used in the synthesis. The content of the other silane compound (s3) is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total amount of the silane compound used in the synthesis.

The silane compound used in the synthesis of the polyorganosiloxane (A1) by the method (II) preferably contains the silane compound (s2) in an amount of 10 to 100 mol% based on the total amount of the silane compound , More preferably 20 to 100 mol%. The content of the other silane compound (s3) is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total amount of the silane compound used in the synthesis.

The silane compound used in the synthesis of the polyorganosiloxane (A1) by the method (III) preferably contains the silane compound (s1) in an amount of 1 to 80 mol% based on the total amount of the silane compound , More preferably 5 to 50 mol%. The use ratio of the silane compound (s2) is preferably 20 mol% or less, more preferably 10 mol% or less, based on the total amount of the silane compound used in the synthesis. The content of the other silane compound (s3) is preferably 99 mol% or less, more preferably 95 mol% or less, based on the total amount of the silane compound used in the synthesis.

The hydrolysis / condensation reaction of the silane compound in the formulas (I) and (II) can be carried out by reacting one or more of the above-mentioned silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent . In the hydrolysis-condensation reaction, the use ratio of water is preferably 0.5 to 100 moles, more preferably 1 to 30 moles, per 1 mole of the silane compound (total amount).

Examples of the catalyst that can be used in the hydrolysis / condensation reaction include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Specific examples of these catalysts include acids such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid and the like as acids; As the alkali metal compound, for example, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like; Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole: triethylamine, tri-n-propylamine, tri- Tertiary organic amines such as butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and quaternary organic amines such as tetramethylammonium hydroxide; Respectively.

Among these catalysts, an alkali metal compound or an organic base is preferable among these catalysts in that side reactions such as ring-opening of the epoxy group can be suppressed, the rate of hydrolysis and condensation can be increased, Organic bases are preferred. The organic base is preferably a tertiary organic amine or a quaternary organic amine.

The amount of the organic base to be used differs depending on the kind of the organic base, the reaction conditions such as the temperature, and the like, and is appropriately set. For example, the amount is preferably 0.01 to 3 moles per mole of the total silane compound, more preferably 0.05 It is ~ 1 baud.

Examples of the organic solvent that can be used in the above hydrolysis-condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Specific examples thereof include, for example, toluene, xylene and the like as hydrocarbons; As the ketone, for example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and the like; As the ester, for example, ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; As the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; As the alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like; Respectively. Of these, it is preferable to use a water-insoluble organic solvent. These organic solvents may be used singly or in combination of two or more.

The use ratio of the organic solvent in the hydrolysis and condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound used in the reaction.

The above hydrolysis-condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing the solution with an organic base and water, and heating the mixture with, for example, an oil bath. In the hydrolysis-condensation reaction, the heating temperature is preferably 130 ° C or lower, more preferably 40 to 100 ° C. The heating time is preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During the heating, the mixed solution may be stirred or refluxed. After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this cleaning, cleaning is preferably performed by using water containing a small amount of a salt (for example, an aqueous solution of ammonium nitrate of about 0.2 wt%) from the standpoint of facilitating the cleaning operation. The washing is carried out until the water layer after the washing becomes neutral. Thereafter, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain the objective polyorganosiloxane , A polyorganosiloxane having a polymerizable unsaturated bond in the case of the above method (I), and a polyorganosiloxane having an epoxy group in the case of the above method (II) (hereinafter also referred to as "epoxy group-containing polyorganosiloxane" ), Respectively.

In the above method (II), the epoxy group-containing polyorganosiloxane obtained by the hydrolysis-condensation reaction is reacted with a carboxylic acid (c1) having a polymerizable unsaturated bond. As a result, the polyorganosiloxane (A1) having a polymerizable unsaturated bond can be obtained. The carbonic acid used in this reaction may be a carbonic acid (c1) alone or a mixture of a carboxylic acid (c1) and a carboxylic acid (c1) having a group capable of giving a vertical orientation to the coating film (hereinafter also referred to as a &quot; liquid crystal aligning group & c2), and other carbonic acid (c3) may be used.

When the polyorganosiloxane obtained by the hydrolysis-condensation reaction of the silane compound in the method (I) has an epoxy group, the epoxy group of the polyorganosiloxane and the carboxylic acid (c2) having a liquid crystal aligning group By reacting, the liquid crystal alignability can be imparted to the polyorganosiloxane. In the reaction of the polyorganosiloxane having an epoxy group and the polymerizable unsaturated bond in the method (I) with the carboxylic acid, the reaction between the carboxylic acid (c2) and the carboxylic acid (c1) and the carboxylic acid May be used.

[Carbonic acid (c1)]

The remaining structure of the carboxylic acid (c1) is not particularly limited as long as it has a polymerizable unsaturated bond and a carboxyl group. Specifically, for example, a compound represented by each of the following formulas (C1-1) to (C1-3) as a carboxylic acid having a group represented by the above formula (f1); As the carbonic acid having a group represented by the formula (f2), a compound represented by the following formula (C1-5); As the carbonic acid having a group represented by the formula (f3), a compound represented by the following formula (E1-4); Each can be:

(Wherein R ¹ , R ⁴ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms; X ⁶ , Y ⁶ and Z ⁶ are, each independently, a phenylene group, cyclohexylene group, or an oxygen atom; a and ⁶ and g ⁶ are each independently an integer of 0~12, ⁶ b, ⁶ c, ⁶ d, ⁶ e, and f ⁶ k ⁶ is independently 0 or 1, provided that a ^{6 to} g ⁶ and k ⁶ are combinations in which oxygen atoms are adjacent to each other, a combination in which "-CO-O-" and a carbonyl group are adjacent to each other, Quot; -CO-O- &quot; and the oxygen atom are not adjacent to each other);

(Wherein R ¹ , R ⁴ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms, X ⁷ and Y ⁷ are each a hydrogen atom, , each independently, a phenylene group or cyclohexylene group and; a ^71, a ⁷² and a ⁷ f are each independently an integer of 0~12, b ^71, b ^72, c ^{7, 7} d, ⁷ e, k ⁷¹ and k ⁷² each independently 0 or 1; stage, a ^71, a ^72, b ^71, b ^72, c ^7, d ^7, e ^7, f ^7, k ⁷¹ and k ⁷² is, between the oxygen atom Quot; -CO-O- &quot; and a carbonyl group adjacent to each other and a combination in which -CO-O- and oxygen atoms are not adjacent to each other);

(Wherein R ¹ , R ⁴ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms, R ⁸ is a hydrogen atom, An alkyl group having 1 to 12 carbon atoms or "- (CH ₂ ) _n -OH" (wherein n is an integer of 1 to 4), a ⁸ , c ⁸ and d ⁸ are each independently an integer of 1 to 12, ⁸ is 2 or 3 and k ⁸ is 0 or 1, provided that a plurality of R ¹ , R ⁴ , R ⁶ , a ⁸ and k ⁸ each independently have the above definition;

X ⁹ , Y ⁹ and Z ⁹ each independently represent a phenylene group, a cyclohexylene group or an oxygen atom; a ⁹ and g ⁹ each independently represent an integer of 0 to 10; And each of b ⁹ , c ⁹ , d ⁹ , e ⁹ and f ⁹ is independently 0 or 1, with the proviso that a ^{9 to} g ⁹ represent a combination in which oxygen atoms are adjacent to each other, "-CO-O- Quot; and a carbonyl group adjacent to each other, and &quot; -CO-O- &quot; and oxygen atoms are not adjacent to each other);

(Wherein R ¹⁰ is a hydrogen atom or a methyl group; W ¹⁰ , X ¹⁰ , Y ¹⁰ and Z ¹⁰ each independently represent a phenylene group, a cyclohexylene group, an oxygen atom, A ¹⁰ , b ¹⁰ , c ¹⁰ , d ¹⁰ and e ¹⁰ are each independently 0 or 1, provided that when e ¹⁰ is 1, f ¹⁰ is an integer of 0 to 12, f ¹⁰ is an integer of 1 or more).

As a specific example of the alkyl group having 1 to 12 carbon atoms represented by R ⁸ in the formula (C1-3), the description of R ³ in the formula (E1-3) can be applied. Further, the formula (C1-5) of ¹⁰ W, X ^10, Y ¹⁰ and Z ¹⁰ group having 1 to 12 carbon atoms in the alkanediyl group Specific examples of the formula (E1-5) of the W ^5, X ^5, Y ⁵ And Z ⁵ can be applied.

In the formula (C1-1), from the viewpoint of improving the afterimage characteristic, it is preferable that k ⁶ = 1 and R ⁴ and R ⁶ are hydrogen atoms. From the viewpoint of improving the high-speed responsiveness of the liquid crystal display element, it is preferable that k ⁶ = 0.

In the formula (C1-1) a ⁶ ~g ⁶ and k is ^6, in combination with each other to the oxygen atom adjacent to each other, "-CO-O-" and carbonyl groups and combinations, "-CO- neighboring each other O- &quot; and the oxygen atom are not adjacent to each other. Specifically, when a ⁶ = 0, at least one of b ⁶ and k ⁶ is zero. a = 0 when ⁶ g, f ⁶ = 0. c is ^{6 = d 6 = e 6 =} 0 when at least one of b and ⁶ f ⁶ is zero. X ⁶ , Y ⁶ and Z ⁶ are not a combination in which oxygen atoms are adjacent to each other or a combination in which oxygen atoms and carbonyl groups are adjacent to each other. When a ^{6 to} g ⁶ are both 0, k ⁶ is an integer of 1 or more.

In the formula (C1-2), a ⁷¹ , a ⁷² , b ⁷¹ , b ⁷² , c ⁷ , d ⁷ , e ⁷ , f ⁷ , k ⁷¹ and k ⁷² are combinations in which oxygen atoms are adjacent to each other, It is assumed that the combination of "-CO-O-" and a carbonyl group adjacent to each other and the combination of "-CO-O-" and oxygen atoms are not adjacent to each other. Concretely, when a ⁷¹ = 0, at least one of b ⁷¹ and k ⁷¹ is 0, and when a ⁷² = 0, at least one of b ⁷² and k ⁷² is zero. When f ⁷ = 0, e ⁷ = 0.

In the formula (C1-4), a ^{9 to} g ⁹ are combinations in which oxygen atoms are adjacent to each other, a combination in which "-CO-O-" and a carbonyl group are adjacent to each other and "-CO- And oxygen atoms are not adjacent to each other. Specifically, when f ⁹ = 1, g ⁹ is an integer of 1 or more. When f ⁹ = 0, the carboxyl group in the formula is bonded with a phenylene group, a cyclohexylene group or an alkanediyl group. c is ^{9 = d 9 = e 9 =} 0 when, b ^9, and at least one of f ⁹ is zero. X ⁹ , Y ⁹ and Z ⁹ are not a combination in which oxygen atoms are adjacent to each other or a combination in which oxygen atoms and carbonyl groups are adjacent to each other. When c ^{9 to} g ⁹ are all 0, b ⁹ = 0.

Specific examples of the compound represented by each of the above formulas (C1-1) to (C1-5) include compounds represented by the above formula (C1-1), for example, compounds represented by the following formulas (C1-1-1) to C1-1-10); Examples of the compound represented by the formula (C1-2) include compounds represented by the following formulas (C1-2-1) to (C1-2-5); Examples of the compound represented by the formula (C1-3) include compounds represented by each of the following formulas (C1-3-1) to (C1-3-5); Examples of the compound represented by the formula (C1-4) include compounds represented by each of the following formulas (C1-4-1) to (C1-4-5); Examples of the compound represented by the formula (C1-5) include compounds represented by each of the following formulas (C1-5-1) to (C1-5-5); Respectively.

Among them, the above-mentioned carbonic acid (c1) is preferably a group containing a polymerizable unsaturated bond and having a group represented by the formula (f1) or a group represented by the formula (f2) More preferably a compound having an appearing group. When the group represented by the formula (f1) is used, the group is preferably contained as a part of the acryloyl group or the methacryloyl group from the viewpoint of improving the afterimage characteristic, and it is preferable that the group has a high- It is preferable that the alkenyl group is an alkenyl group. The above-mentioned carbonic acid (c1) can be used singly or in combination of two or more kinds.

[Carbonic acid (c2)]

The remaining structure of the carboxylic acid (c2) is not particularly limited as long as it has a liquid crystal aligning group and a carboxyl group. Examples of the liquid crystal aligning group include an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, an alkoxy group having 4 to 40 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, .

Specific examples of the carboxylic acid (c2) having such a liquid crystal aligning group include long chain fatty acids such as caproic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid and stearic acid; Benzoic acid having a long chain alkyl group such as 4-n-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid and 4-stearylbenzoic acid; 4-n-octyloxybenzoic acid, 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, Benzoic acid having a long chain alkoxy group; Cholestanyloxybenzoic acid, cholestenyloxybenzoic acid, cholestenyloxybenzoic acid, lanostanyloxybenzoic acid, cholestanyloxycarbonylbenzoic acid, cholestenyloxycarbonylbenzoic acid, lanostanyloxycarbonylbenzoic acid, succinic acid-5? Benzoic acid having a steroid skeleton such as succinic acid -5? -Cholesten-3-yl, succinic acid-5? -Lanosan-3-yl; Benzoic acid, 4- (4-pentyl-cyclohexyl) benzoic acid, 4- (4-pentyl-cyclohexyl) Heptyl-bicyclohexyl-4-carbonic acid, 4'-pentyl-biphenyl-4-carboxylic acid, 4'-hexyl-biphenyl- 4-carboxylic acid, 4- (4-pentyl-bicyclohexyl-4-yl) benzoic acid, 4- (4-hexyl- (4'-cyanobiphenyl-4-yloxy) hexanoic acid, 11- (4-cyclohexylphenoxy) undecanoic acid, etc. Benzoic acid containing a polycyclic structure; Carbonic acid containing a fluoroalkyl group such as 6,6,6-trifluorohexanoic acid and 4- (4,4,4-trifluorobutyl) benzoic acid; And the like. The above-mentioned carboxylic acid (c2) may be used singly or in combination of two or more kinds.

The other carbonic acid (c3) is a carbonic acid other than the carbonic acid (c1) and the carbonic acid (c2), and specific examples thereof include formic acid, acetic acid, propionic acid, benzoic acid and methylbenzoic acid .

In the above method (I), the carbonic acid to be reacted with the polyorganosiloxane having a polymerizable unsaturated bond and an epoxy group is preferably a carboxylic acid having a carbon number of not more than 0.7 mol per 1 mol of the epoxy group of the polyorganosiloxane , More preferably from 0.1 to 0.6 mol. The proportion of the carboxylic acid (c1) to be used is preferably 0.5 mol or less, more preferably 0.3 mol or less, per 1 mol of the epoxy group of the polyorganosiloxane. The proportion of the carboxylic acid (c3) to be used is preferably 0.3 mol or less, more preferably 0.2 mol or less, per 1 mol of the epoxy group of the polyorganosiloxane.

In the method (II), the carbonic acid to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.02 to 0.7 mol per 1 mol of the epoxy group of the polyorganosiloxane, , And more preferably 0.1 to 0.5 mol. The use ratio of the carboxylic acid (c2) is preferably 0.6 mol or less, more preferably 0.2 to 0.6 mol, per 1 mol of the epoxy group of the polyorganosiloxane. The proportion of the carboxylic acid (c3) to be used is preferably 0.3 mol or less, more preferably 0.2 mol or less, per 1 mol of the epoxy group of the polyorganosiloxane.

The polyorganosiloxane (A1) in the present invention preferably has an epoxy equivalent of 5,000 g / mol or less, more preferably 500 to 3,000 g / mol. The total use ratio of the carbonic acid (c1), (c2) and (c3) is preferably 0.8 mol or less with respect to 1 mol of the epoxy group of the polyorganosiloxane to be reacted with the carboxylic acid.

The reaction between the epoxy group of the polyorganosiloxane and the carboxylic acid can be preferably carried out in the presence of a catalyst and an organic solvent. As the catalyst used in the reaction, for example, known compounds such as so-called curing accelerators for promoting the reaction of organic bases and epoxy compounds can be used.

The organic base includes, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene; Quaternary organic amines such as tetramethylammonium hydroxide; And the like. As the organic base, a tertiary organic amine or a quaternary organic amine is preferable.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine; Imidazole compounds such as 2-methylimidazole; Organic phosphorus compounds such as diphenylphosphine; Quaternary phosphonium salts such as benzyltriphenylphosphonium chloride; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7; Organometallic compounds such as zinc octylate, and tin octylate; Quaternary ammonium salts such as tetraethylammonium bromide; Boron compounds such as boron trifluoride; Metal halide compounds such as zinc chloride and stannic chloride; And the like. In addition to these, known ones as latent curing accelerators can be used.

The catalyst may be used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyorganosiloxane to be reacted with the carboxylic acid .

Examples of the organic solvent that can be used in the reaction between the polyorganosiloxane and the carboxylic acid include hydrocarbon compounds, ethers, esters, ketones, amides, and alcohols. Of these, ethers, esters and ketones are preferable in view of the solubility of the raw materials and the products and the ease of purification of the products. Specific examples of the particularly preferable solvents include 2-butanone, 2-hexanone, methylisobutylketone, Butyl acetate, and the like. The organic solvent is preferably used in such a ratio that the solid concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) is 0.1 wt% or more, preferably 5 to 50 wt% Is more preferable.

The reaction temperature is preferably 0 to 200 캜, more preferably 50 to 150 캜. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours. Further, after completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. After washing with water, the organic solvent layer is dried, if necessary, with a suitable drying agent, and then the solvent is removed to obtain the objective polyorganosiloxane.

On the other hand, in the case of the above method (III), oxalic acid is added in advance to the alcohol to prepare an alcohol solution of oxalic acid, and the solution is mixed with the silane compound (the silane compound (s1), the silane compound (s2) (s3) are mixed and heated to obtain a solution containing the objective polyorganosiloxane.

Examples of the alcohol used in the reaction include methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and the like. .

The use ratio of the alcohol in the reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound used in the reaction. The amount of oxalic acid to be used in the reaction is preferably 0.2 to 2 mol per 1 mol of the total alkoxy groups of the silane compound. The heating temperature is preferably 50 to 180 DEG C, and the heating time may be, for example, several tens of minutes to several tens of hours.

Thus, a reaction solution containing a polyorganosiloxane (A1) having a polymerizable unsaturated bond is obtained by the above method (III). The reaction solution may be directly supplied to the preparation of a liquid crystal aligning agent, or may be provided in the preparation of a liquid crystal aligning agent after concentration or dilution of the reaction solution, if necessary. When the polyorganosiloxane (A1) obtained by the above reaction has an epoxy group, the polyorganosiloxane may further be reacted with the carboxylic acid (c2) having the liquid crystal aligning group. By this reaction, it is possible to further introduce a liquid crystal aligning group into the polyorganosiloxane.

The specific polyorganosiloxane to be contained in the liquid crystal aligning agent of the present invention preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 500 to 100,000, more preferably 1,000 to 30,000 Do.

The content of the polymer (A1) is preferably 1% by weight or more, more preferably 3% by weight or more, of the total amount of the polymer contained in the liquid crystal aligning agent from the viewpoint of satisfactorily obtaining the effect of the present invention By weight, more preferably 5% by weight or more. The proportion of the polymerizable unsaturated bond to the total amount of the polymer component in the liquid crystal aligning agent is preferably 0 to 15 mmol / g as a whole, more preferably 0.5 to 10 mmol / g desirable.

<Other components>

The liquid crystal aligning agent of the present invention may contain other components as required. Such other components include, for example, other polymers other than the polymer (A1), a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), and a functional silane compound.

[Other Polymers]

The other polymer may be used for improving solution characteristics and electrical properties. Such other polymer is a polymer having no polymerizable unsaturated bond and specifically includes, for example, polyamic acid, polyimide, polyamic ester, polyester, polyamide, polyorganosiloxane, cellulose derivative, polyacetal derivative, A polymer having a main skeleton composed of a polystyrene derivative, a poly (styrene-phenylmaleimide) derivative, a poly (meth) acrylate derivative or the like and having no polymerizable unsaturated bond in its side chain. The other polymer is preferably at least one member selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane, and is preferably selected from the group consisting of polyamic acid, polyimide and polyorganosiloxane Is more preferable.

The polyamic acid not having a polymerizable unsaturated bond can be synthesized, for example, by reacting the tetracarboxylic acid dianhydride with the above other diamine. The polyamic acid ester having no polymerizable unsaturated bond can be obtained by, for example, a method of esterifying a polyamic acid having no polymerizable unsaturated bond, a method of reacting tetracarboxylic acid diester dichloride with the above other diamine, And then reacting the acid diester with the other diamine. The polyimide having no polymerizable unsaturated bond can be synthesized, for example, by dehydration ring closure of a polyamic acid having no polymerizable unsaturated bond. The polyorganosiloxane having no polymerizable unsaturated bond is obtained by hydrolyzing and condensing at least one monomer selected from the group consisting of the silane compound (s2) and the silane compound (s3), for example, With at least one member selected from the group consisting of a carboxylic acid (c2) and a carboxylic acid (c3) according to the following reaction formula.

When the above other polymer is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 99% by weight or less based on the total amount of the polymer contained in the liquid crystal aligning agent from the viewpoint of not impairing the effect of the present invention, More preferably 96% by weight or less, and still more preferably 0.1 to 90% by weight.

The liquid crystal aligning agent of the present invention comprises the polymer (A1) as an essential component, but preferable embodiments thereof include a polymer component comprising (I) only a polyorganosiloxane (A1); (II) an embodiment comprising at least one member selected from the group consisting of a polyamic acid (A1) and a polyimide (A1); (III) a mode comprising at least one member selected from the group consisting of polyorganosiloxane (A1), polyamic acid (A1) and polyimide (A1); (IV) a mode in which the polyorganosiloxane (A1) and the other polymer are at least one selected from the group consisting of a polyamic acid and a polyimide having no polymerizable unsaturated bond; (V) a polyorganosiloxane comprising at least one member selected from the group consisting of a polyamic acid (A1) and a polyimide (A1) and other polymer, and the other polymer is a polyorganosiloxane having no polymerizable unsaturated bond, At least one member selected from the group consisting of polyamic acid and polyimide; And the like. The mixing ratio of the polyorganosiloxane, polyamic acid and polyimide in each mode can be arbitrarily set depending on the application of the liquid crystal display element to be used and the like.

Among these, from the viewpoint of improving the afterimage characteristic of the liquid crystal display element (in particular, difficulty of occurrence of afterimage accompanying application of an AC voltage, hereinafter also referred to as &quot; AC afterimage characteristic &quot;), . The ratio of the polyorganosiloxane (A1) to the polyamic acid and the polyimide (total) in the aspects of the above (III) and (IV) is preferably 100 parts by weight or more based on 100 parts by weight of the total amount of the polyamic acid and the polyimide, The amount of the polyorganosiloxane (A1) is preferably 1 to 50 parts by weight, more preferably 2 to 35 parts by weight, and still more preferably 3 to 25 parts by weight.

Further, in the present invention, by forming a liquid crystal alignment film of a PSA mode liquid crystal display element using a liquid crystal aligning agent containing the polymer (A1), the reaction of the photopolymerizable compound contained in the liquid crystal layer during the light irradiation to the liquid crystal cell It can be assured from the side of the liquid crystal alignment film, and as a result, it is deduced that the effect of the present invention can be obtained.

[Epoxy Compound]

The epoxy compound can be used to improve the adhesion to the substrate surface and electric characteristics in the liquid crystal alignment film. Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol di Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromonopentyl N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, and the like. When these epoxy compounds are added to the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the printability of a liquid crystal aligning agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-tri Methoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like, Can.

When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio thereof is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight per 100 parts by weight of the total amount of the polymers.

In addition to the above-exemplified compounds, compounds having at least one oxetanyl group in the molecule, an antioxidant, and the like may be used as the other components.

<Solvent>

The liquid crystal aligning agent of the present invention is constituted by dissolving a polymer component and optionally other optional components, if necessary, in an organic solvent.

Examples of the solvent used in the preparation of the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, Propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethyleneglycol ethyl ether acetate, diethylene glycol diisopropyl ether, diethylene glycol diisopropyl ether, Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Tate, and in deep and the like pyrene glycol monomethyl ether (DPM), di-isobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate. These may be used alone or in combination of two or more.

The solid concentration of the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., Is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and preferably heated to form a coating film which is a liquid crystal alignment film or a liquid crystal alignment film. At this time, when the solid concentration is less than 1% by weight, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, and it becomes difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent is increased and the coating property is poor.

A particularly preferable range of the solid concentration is different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, it is particularly preferable that the solid concentration is in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable to set the solid concentration in the range of 3 to 9% by weight and the solution viscosity in the range of 12 to 50 mPa · s accordingly. In the case of the inkjet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and the solution viscosity is in the range of 3 to 15 mPa · s. The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚.

<Liquid Crystal Alignment Film and Liquid Crystal Display Device>

The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent prepared as described above and is used as a liquid crystal alignment film of a PSA mode liquid crystal display device. Further, the PSA mode liquid crystal display element of the present invention comprises the liquid crystal alignment film. (I) to (iii) below;

(i) a first step of applying the liquid crystal aligning agent of the present invention onto a conductive film of a pair of substrates each having a conductive film, and then heating the liquid crystal aligning agent to form a coated film,

(Ii) a second step of constructing a liquid crystal cell by disposing a pair of substrates on which the coating film is formed, with the coating film facing each other through a liquid crystal layer containing a liquid crystal compound,

(Iii) a third step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates. Hereinafter, each of these steps will be described in detail.

[First Step: Formation of Coating Film]

Examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the conductive film, is preferable to use a transparent conductive film is, for example, tin oxide (SnO ₂₎ made of a NESA film (US PPG Company registered trademark), indium oxide-tin oxide consisting of (In ₂ O ₃ -SnO ₂₎ ITO film or the like can be used. The conductive film is preferably a patterned conductive film divided into a plurality of regions. With such a conductive film, it is possible to change the direction of the pretilt angle of the liquid crystal molecules in each region by applying different voltages in each region when a voltage is applied between the conductive films, thereby making it possible to widen the viewing angle characteristic.

The method of applying the liquid crystal aligning agent of the present invention on the surface of the pair of substrates on which the transparent conductive film is formed can be preferably performed by an offset printing method, a spin coating method, a roll coating method, or an inkjet printing method. In the application of the liquid crystal aligning agent, a functional silane compound, a functional titanium compound or the like is added to the surface of the substrate surface on which the coating film is to be formed, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film It is also possible to carry out the pre-treatment for applying the coating.

After the liquid crystal aligning agent is applied to the substrate, preheating (prebaking) is preferably performed for the purpose of preventing the liquid flow of the applied liquid crystal aligning agent and the like. The prebaking temperature is preferably 30 to 200 캜, more preferably 40 to 150 캜, particularly preferably 40 to 100 캜. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, the solvent is completely removed, and a firing (post-baking) process is carried out in order to thermally modify the structure of the acid in the polymer as required. The post-baking temperature is preferably 80 to 300 占 폚, and more preferably 120 to 250 占 폚. The post baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 占 퐉, and more preferably 0.005 to 0.5 占 퐉.

After the application of the liquid crystal aligning agent, the organic solvent is removed by heating, whereby a coating film to be an alignment film is formed. At this time, when the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imide ring structure and an arboric acid structure, And the coating film may be further imidized.

The coating film thus formed may be provided to the second step as it is, or may be provided to the second step after rubbing treatment on the coating film surface as necessary. This rubbing treatment can be carried out by rubbing the coated film surface in a predetermined direction with a roll of cloth made of fibers such as nylon, rayon or cotton.

[Second Step: Construction of Liquid Crystal Cell]

Two liquid crystal alignment layers are formed as described above, and a liquid crystal layer containing a liquid crystal compound and a photopolymerizable compound is disposed between two substrates arranged opposite to each other to produce a liquid crystal cell. To produce a liquid crystal cell, for example, the following two methods can be mentioned. The first method is a conventionally known method (vacuum injection method). First, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealant. A liquid crystal compound and a photopolymerizable compound are injected and filled in the cell gap, and then the injection port is sealed to manufacture a liquid crystal cell. The second method is a method called ODF (One Drop Fill) method. For example, an ultraviolet curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and a liquid crystal compound and a photopolymerizable compound After the mixture with the compound was dropped, the other substrate was bonded so as to face the liquid crystal alignment film, and the liquid crystalline compound was spread over the entire surface of the substrate. Subsequently, ultraviolet light was irradiated to the entire surface of the substrate to form a sealant Thereby curing the liquid crystal cell.

Regardless of the method, the liquid crystal cell manufactured as described above is heated to a temperature at which the liquid crystalline compound used takes an isotropic phase, and then gradually cooled to room temperature to remove the flow orientation at the time of filling the liquid crystal good.

As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used.

As the liquid crystalline compound, a nematic liquid crystal having a negative dielectric anisotropy can be preferably used. For example, a dicyanobenzene-based liquid crystal, a pyridazine-based liquid crystal, a hepta base-based liquid crystal, Liquid crystal, phenylcyclohexane-based liquid crystal, terphenyl-based liquid crystal, and the like. As the liquid crystal compound, an alkenyl-based liquid crystal which is a monofunctional liquid crystal compound having one of an alkenyl group and a fluoroalkenyl group can be used as the liquid crystal compound in order to speed up the response speed of the PSA mode liquid crystal display element It is preferable to use them in combination. As such alkenyl-based liquid crystals, conventionally known ones can be used, and examples thereof include compounds represented by the following formulas (L1-1) to (L1-9).

As the photopolymerizable compound, a compound having a functional group capable of radical polymerization such as acryloyl group, methacryloyl group, vinyl group and the like can be used. From the viewpoint of reactivity, it is preferable to use a polyfunctional compound having an acryloyl group or a methacryloyl group among them. From the viewpoint of maintaining the orientation properties of the liquid crystal molecules stably, as the photopolymerizable compound, it is preferable to use, as the liquid crystal skeleton, a compound having at least two rings in total of at least any one of cyclohexane ring and benzene ring. As the photopolymerizable compound, conventionally known ones can be used. The compounding ratio of the photopolymerizable compound is preferably 0.1 to 0.5 wt% with respect to the total amount of the liquid crystalline compound to be used. The thickness of the liquid crystal layer is preferably 1 to 5 mu m.

[Third step: light irradiation step]

After the formation of the liquid crystal cell, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage to be applied here may be DC or AC of 5 to 50 V, for example. As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays including light having a wavelength of 300 to 400 nm are preferable. As the light source of the irradiation light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp and an excimer laser can be used. The ultraviolet ray in the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with, for example, a filter diffraction grating or the like. The irradiation dose of light is preferably 1,000 J / m 2 or more and less than 200,000 J / m 2, and more preferably 1,000 to 100,000 J / m 2.

Then, the PSA mode liquid crystal display device can be obtained by bonding the polarizing plate to the outer surface of the liquid crystal cell after light irradiation. Examples of the polarizing plate used herein include a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state, a polarizing plate sandwiched by a cellulose acetate protective film, or a polarizing plate made of H film itself.

The PSA mode liquid crystal display device of the present invention can be effectively applied to various apparatuses and can be applied to various devices such as a clock, a portable game, a word processor, a notebook PC, a car navigation system, a camcorder, a PDA, A telephone, a smart phone, various monitors, a liquid crystal television, and an information display.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

The weight average molecular weight, the epoxy equivalent, the solution viscosity of each polymer solution, and the imidation rate of polyimide of each polymer in each synthesis example were measured by the following methods.

[Weight average molecular weight of polymer]

The weight average molecular weight Mw of the polymer is a polystyrene reduced value measured by gel permeation chromatography under the following conditions.

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

[Epoxy equivalent]

The epoxy equivalent is a value measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

[Solution viscosity of polymer solution]

The solution viscosity [mPa 占 퐏] of the polymer solution was measured at 25 占 폚 using an E-type rotational viscometer for a solution prepared by using a predetermined solvent at a polymer concentration of 10% by weight.

[Imidization Rate of Polyimide]

The polyimide solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature. The precipitate was dissolved in deuterated dimethyl sulfoxide and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidization ratio [%] was obtained by the formula shown by the following formula (x).

Imidization rate [%] = {(1-A ¹ ) / (A ² x?)} 100 ... (x)

(In the formula (x), A ¹ is the peak area derived from the proton of the NH group appearing near the chemical shift of 10 ppm, A ² is the peak area derived from the other proton, and α is the peak area derived from the proton The number of protons other than one proton in the NH group)

&Lt; Synthesis of Polymer &

[Synthesis Example P1: Synthesis of polyimide as Polymer (A1)] [

(1.0 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 150 g (0.3 mole) of 3- (2,4-diaminophenoxy) cholestane as a diamine, 47 g (0.2 mol) of 2- (2,4-diaminophenoxy) ethyl (compound represented by the above formula (E1-1-6)) and 1- (4-aminophenyl) -2,3- 133 g (0.5 mol) of 1,3,3-trimethyl-1H-inden-5-amine were dissolved in 2,200 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C for 6 hours, Was obtained. The solution viscosity measured by taking a small amount of the obtained polyamic acid solution was about 1,400 mPa · s.

Then, 2,800 g of NMP was added to the obtained polyamic acid solution, 79 g of pyridine and 100 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the polyimide (P-1) which is the polymer (A1) was dissolved in about 15% by adding the solvent in the system to the solvent (substitution of pyridine and anhydrous acetic acid used in the dehydration ring- To obtain a solution containing the solution in weight%. The imidization ratio of the obtained polyimide (P-1) was about 51%.

[Synthesis Example P2: synthesis of polyamic acid as polymer (A1)] [

(1.0 mole) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride as tetracarboxylic dianhydride, 52 g (0.1 mole) of 3- (3,5-diaminobenzoyloxy) cholestane as a diamine, 4 (0.2 mol) of (2-propynyloxy) benzene-1,3-diamine (the compound represented by the formula (E1-5-1)) and 2,2'-dimethyl-4,4'- (P-2) which is a polymer (A1) was dissolved in a mixed solvent consisting of 150 g (0.7 mol) of phenyl, 100 g of NMP3 and 760 g of? -Butyrolactone and reacted at 40 占 폚 for 3 hours, % Solution. The solution viscosity of this polyamic acid solution was 170 mPa · s.

[Synthesis Example P3: Polyimide Synthesis as Other Polymer]

(1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 74 g (0.15 mol) of 3- (2,4-diaminophenoxy) cholestane as diamine, 1- 40 g (0.15 mol) of 3,5-diaminobenzoic acid and 110 g (0.7 mol) of 3,5-diaminobenzoic acid were dissolved in NMP 1,800 g, and the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing polyamic acid. The solution viscosity of the obtained polyamic acid solution was measured by collecting a small amount of the polyamic acid solution, which was about 1,300 mPa · s.

Then, 2,200 g of NMP was added to the obtained polyamic acid solution, 120 g of pyridine and 150 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with a fresh NMP solvent to obtain a solution containing about 15% by weight of the other polymer, polyimide (P-3). The imidization rate of the obtained polyimide (P-3) was about 67%.

[Synthesis Example P4: synthesis of polyamic acid which is another polymer]

(1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride, and 4- (2- (4- (4-pentylcyclohexyl) phenoxy) ethoxy) (0.2 mol) of 1,3-diamine, 40 g (0.2 mol) of 4,4'-diaminodiphenylmethane, and 91 g (0.6 mol) of 2,5-diaminobenzoic acid were added to 2,700 g of NMP and 50 g of γ-butyrolactone And the reaction was carried out at 40 占 폚 for 3 hours to obtain a solution containing 10% by weight of the other polymer, polyamic acid (P-4). The solution viscosity of this polyamic acid solution was 160 mPa · s.

[Synthesis Example S1: synthesis of polyorganosiloxane which is polymer (A1)] [

197 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS) as a hydrolyzable silane compound and 3 g of 3-methacryloxypropyl triethoxysilane were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube 50 g of methoxysilane (GMPTS = GMPTS = 80: 20 (molar ratio)), 500 g of methyl isobutyl ketone as a solvent and 10.0 g of triethylamine as a catalyst were added and mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise over 30 minutes from the dropping funnel, and the mixture was reacted at 80 DEG C for 6 hours under reflux with stirring. After the completion of the reaction, the organic layer was taken out, washed with a 0.2 wt% aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a hydrolyzed condensate having an epoxy group As a transparent liquid.

As a result of ¹ H-NMR analysis of the hydrolysis-condensation product, it was confirmed that a peak belonging to the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm in accordance with theoretical strength, and no side reaction of the epoxy group occurred during the reaction .

Then, the resulting hydrolyzed condensate was reacted with a carbonic acid. First, into a 200-mL three-necked flask, the above-obtained hydrolysis-condensation product having an epoxy group was introduced, and 30.0 g of methyl isobutyl ketone as a solvent and 75.1 g of 4-octyloxybenzoic acid (OCTBA) 30 mol% based on the total amount of the decomposable silane compound and 38 mol% based on the epoxy group of the hydrolyzed condensate) and 36.1 g of 11- (4-cyclohexylphenoxy) undecanoic acid (hydrolyzable silane , And 0.10 g of UCAT 18X (trade name, a curing accelerator of an epoxy compound, manufactured by SAN-A FRON Co., Ltd.) as a catalyst, and the reaction was carried out at 100 ° C for 48 hours with stirring. After completion of the reaction, ethyl acetate was added to the reaction mixture, and the resulting organic layer was washed with water three times, dried over magnesium sulfate, and then the solvent was distilled off to obtain 287.2 g of a polyorganosiloxane (S-1) . The weight average molecular weight Mw of the polyorganosiloxane (S-1) in terms of polystyrene measured by gel permeation chromatography (GPC) was 7,300.

[Synthesis Examples S2 to S4, S6: Synthesis of polyorganosiloxane]

(S-2) to (S-2) as the polymer (A1) were obtained by carrying out the same operations as in Synthesis Example S1 except that the types and amounts of the hydrolyzable silane compound and the carbonic acid were changed as shown in Table 1 below. -3), (S-6) and the other polymer, polyorganosiloxane (S-4). The yields and Mw of these polyorganosiloxanes are shown in Table 1 below.

The abbreviations of the respective compounds in Table 1 are as follows.

(Hydrolyzable silane compound)

ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

GMPTS: 3-methacryloxypropyltrimethoxysilane

TEOS: tetraethoxysilane

ODES: octadecyltriethoxysilane

VTES: vinyltriethoxysilane

(Carbonic acid)

OCTBA: 4-octyloxybenzoic acid

CPUA: 11- (4-Cyclohexylphenoxy) undecanoic acid

PCHBA: 4- (4-pentylcyclohexyl) benzoic acid

ABAMPO: A compound represented by the formula (C1-3-1) (hereinafter referred to as the compound represented by the formula (C1-3-1)): 4- (3- (acryloyloxy) -2,2- )

BMBA: 3,5-bis (methacryloyloxy) benzoic acid (compound represented by the above formula (C1-2-1))

SACY: succinic acid = 5? -Cholestan-3-yl

PCHCHUBA: 11- (4- (4'-Pentylthio (cyclohexane) -4-yl) phenoxy) undecanoic acid (compound represented by the following formula (p1)

VCHCHUA: 11 - ((4'-vinyl- [1,1'-bi (cyclohexane)] -4-yl) oxy) undecanoic acid (compound represented by the formula (C1-1-10)

The &quot; molar ratio &quot; of the hydrolyzable silane compounds in Table 1 indicates the ratio of each silane compound to the sum of the hydrolyzable silane compounds used. The &quot; mole ratio &quot; of the carbonic acid indicates the ratio of each carbonic acid to the sum of the hydrolyzable silane compounds used. In Synthesis Examples S1 to S4 and S6, two kinds of carbonic acid were used, respectively.

[Synthesis Example S5: synthesis of polyorganosiloxane which is polymer (A1)] [

52.8 g of ethanol was added to a four-neck reaction flask equipped with a reflux tube, and 20.0 g of oxalic acid was added in small portions to the ethanol under stirring to prepare an ethanol solution of oxalic acid. Subsequently, this solution was heated to the reflux temperature, and a mixture of 20.8 g of tetraethoxysilane, 4.2 g of octadecyltriethoxysilane and 1.9 g of vinyltriethoxysilane was added dropwise to this refluxing solution. After the completion of the dropwise addition, heating was continued for 5 hours under reflux, then cooled, and 75 g of butyl cellosolve was added to prepare a solution containing polyorganosiloxane (S-5) having a SiO ₂ concentration of 4 wt% did. This solution was analyzed by gas chromatography and no alkoxysilane monomer was detected.

&Lt; Preparation of liquid crystal composition &

[Preparation of liquid crystal composition LC1]

5 wt% of the liquid crystalline compound represented by the formula (L1-1) and 0.3 wt% of the photopolymerizable compound represented by the following formula (L2-1) were added to 10 g of a nematic liquid crystal (MLC-6608, Were added and mixed to obtain a liquid crystal composition LC1.

[Preparation of liquid crystal composition LC2]

A liquid crystal composition LC2 was prepared in the same manner as the liquid crystal composition LC1 except that the amount of the liquid crystalline compound represented by the formula (L1-1) was changed from 5 wt% to 10 wt%.

&Lt; Example 1 >

[Preparation of liquid crystal aligning agent]

A solution containing polyimide (P-1) and a solution containing polyamic acid (P-2) in a ratio of polyimide (P-1) NMP and butyl cellosolve (BC) were added as an organic solvent to the mixed solution to obtain a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid concentration of 6.0% by weight. This solution was filtered using a filter having a pore diameter of 1 탆 to prepare a liquid crystal aligning agent.

[Production of liquid crystal cell]

Using the liquid crystal aligning agent prepared above, the presence or absence of the pattern of the transparent electrode and the ultraviolet ray irradiation amount (two levels) were changed to produce four liquid crystal cells in total. In addition, various properties were evaluated for the liquid crystal cell produced.

[Production of liquid crystal cell having transparent electrode without pattern]

The liquid crystal aligning agent prepared above was coated on the transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film by using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Sein Insights Co., Ltd.) After the solvent was removed by heating (prebaking) for a minute, the film was heated on a hot plate at 150 ° C for 10 minutes (post baking) to form a coating film having an average film thickness of 600 Å.

The coating film was subjected to a rubbing treatment with a rubbing machine having a roll wrapped with a rayon hot spring at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair pressing indentation length of 0.1 mm. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, and then the substrate was dried in a 100 占 폚 clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film. This rubbing treatment is a weak rubbing treatment for the purpose of controlling the inclination of the liquid crystal and performing the orientation division by a simple and easy method.

Next, one of the pair of substrates was coated with an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 on the outer edge of the surface having the liquid crystal alignment film, and then a pair of substrates were stacked so as to face the liquid crystal alignment film surface Followed by squeezing and curing the adhesive. Subsequently, the liquid crystal composition LC1 prepared above was charged between a pair of substrates from the liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to produce a liquid crystal cell.

The above operation was repeated to produce two liquid crystal cells having transparent electrodes without a pattern. One of them provided the evaluation of the voltage holding ratio as is. For the remaining one liquid crystal cell, an alternating current of 10 V at a frequency of 60 Hz was applied between the conductive films, and the light source was irradiated with ultraviolet light using a metal halide lamp at an irradiation dose of 100,000 J / m & Ultraviolet rays were irradiated. This irradiation dose is a value measured using a photometer which is measured based on a wavelength of 365 nm.

[Evaluation of Voltage Conservation Rate]

For each of the liquid crystal cells prepared above, a voltage of 5 V was applied at 23 캜 for an application time of 60 microseconds and a span of 167 milliseconds, and a voltage maintenance ratio (VHR) after 167 ms after the application was released was measured. The measurement results are shown in Table 2 below. As a measuring apparatus, VHR-1 (manufactured by Toyotecnica Co., Ltd.) was used.

[Production of liquid crystal cell having patterned transparent electrode]

The liquid crystal aligning agent of Example 1 prepared in the above was patterned in a slit shape as shown in Fig. 1, and on each electrode surface of two glass substrates each having ITO electrodes partitioned into a plurality of regions, a liquid crystal alignment film printing machine (Post-baking) on a hot plate at 150 DEG C for 10 minutes to obtain an average (average thickness) Thereby forming a coating film having a thickness of 600 ANGSTROM. This coating film was ultrasonically cleaned in ultrapure water for 1 minute and then dried in a 100 ° C clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film. The pattern of the electrode used is a pattern of the same type as the electrode pattern in the PSA mode.

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the outer edges of each of the pair of substrates having the liquid crystal alignment film, and the adhesive was superimposed on the liquid crystal alignment film so as to face each other. Subsequently, the liquid crystal composition LC1 prepared above was charged between a pair of substrates from the liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to produce a liquid crystal cell.

The above operations were repeated to produce two liquid crystal cells each having a patterned transparent electrode. One of them was provided for evaluation of AC afterimage characteristic as will be described later. The remaining one liquid crystal cell was irradiated with light at an irradiation dose of 100,000 J / m &lt; 2 &gt; in a state in which a voltage was applied between the conductive films by the same method as in the case of manufacturing a liquid crystal display element having a transparent electrode without a pattern, And was provided for the evaluation of the afterimage characteristic.

[Evaluation of AC afterimage characteristics (evaluation of pretilt angle stability)] [

For the liquid crystal cell prepared above, T. J. Scheffer et al., J. Appl. Phys. vol. 48, p. 1783 (1977) and F. Nakano, et al., JPN.J.Appl.Phys. vol. 19, p2013 (1980) "by a rotation determination method using He-Ne laser light. The measurement was performed on the pretilt angle (initial pretilt angle? Ini) before voltage application to the liquid crystal cell and the pretilt angle (pretilt angle? Ac after driving) after driving for 13 hours at AC 9V and room temperature. The pretilt angle change rate? [%] Was calculated by the following equation (y). The case where the pretilt angle change rate? Was less than 3% was evaluated as &quot; good &quot;, and the case where the pretilt angle change rate was less than 3% and less than 5% was evaluated as &quot; defective &quot; The results are shown in Table 2 below.

Pretilt angle change rate? [%] = {(? Ac-? Ini) /? (y)

The &quot; parts by weight &quot; in Table 2 above represents the blending amount of each component relative to 100 parts by weight of the total amount of the liquid crystal aligning agent.

<Examples 2 to 9, 11 and 12 and Comparative Examples 1 and 2>

A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the kind and amount of the polymer used in the preparation of the liquid crystal aligning agent were changed as shown in Table 2 above. The polyorganosiloxanes (S-1) to (S-4) and (S-6) were dissolved in NMP and then supplied to the preparation of a liquid crystal aligning agent. For the polyorganosiloxane (S-5), the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol and then dried under reduced pressure at 40 DEG C for 15 hours, Was dissolved in NMP and supplied to the preparation of a liquid crystal aligning agent. Using these liquid crystal aligning agents, a liquid crystal cell was produced in the same manner as in Example 1, and the liquid crystal cell thus prepared was evaluated. In Examples 6 and 12 and Comparative Example 1, the liquid crystal composition used in the production of the liquid crystal cell was changed from LC1 to LC2. The evaluation results are shown in Table 2 above.

[Evaluation of high-speed response]

&Lt; Example 6A >

The liquid crystal cell having the transparent electrode without the pattern prepared in Example 6 was used to evaluate the high-speed responsiveness of the liquid crystal molecules. After sandwiching the liquid crystal cell prepared above with two polarizing plates arranged in a cross-Nicol state, a visible light lamp was irradiated without applying a voltage, and the luminance of light transmitted through the liquid crystal cell was measured by a photomulti meter , And this value was regarded as a relative transmittance of 0%. Next, the transmittance when an AC voltage of 5 V was applied for 5 seconds between the electrodes of the liquid crystal cell was measured in the same manner as described above, and the relative transmittance was 100%. The time from the relative transmittance of 10% to 90% when the AC voltage of 5 V was applied to each liquid crystal cell was measured, and this time was defined as the response speed. The response speed was evaluated as &quot; good &quot; when the response speed was less than 5 msec, and &quot; the response speed was high &quot; As a result, in the liquid crystal cell of Example 6, the high-speed response was "positive".

&Lt; Example 12A and Comparative Example 1A &

The response speed of the liquid crystal molecules was evaluated in the same manner as in Example 6A except that the liquid crystal cell used was changed from Example 12 to Comparative Example 1. The results are shown in Table 3 below.

&Lt; Example 10 >

[Preparation of liquid crystal aligning agent]

The polyorganosiloxane (S-1) obtained in Synthesis Example S1 was dissolved in NMP, and the solution containing the polyorganosiloxane-containing solution and the polyimide (P-3) as the other polymer obtained in Synthesis Example P3 Solution was mixed so that the polyimide (P-3): polyorganosiloxane (S-1) = 90: 5 as the weight of each solid component. Subsequently, NMP and BC were added, and N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane was added to the polyorganosiloxane (S-1) , A solvent composition of NMP: BC = 50: 50 (weight ratio), and a solid concentration of 6.0 wt%. This solution was filtered using a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent. A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal aligning agent used was changed, and the evaluation was carried out. The evaluation results are shown in Table 2 above.

In Comparative Examples 1 and 2, the decrease of the voltage maintenance rate and the deterioration of the after-image characteristic of AC by ultraviolet irradiation were remarkable. On the other hand, in Examples 1 to 12, a high voltage holding ratio was maintained even after the ultraviolet irradiation, and the AC afterimage characteristic was also good. In particular, in Examples 3, 6, 7, 9, 11, and 12 using at least one of polyamic acid and polyimide and a liquid crystal aligning agent containing polyorganosiloxane (A1) as the polymer, did. From these results, it was found that when a liquid crystal alignment film containing a polymer (A1) is formed by using an alkenyl-based liquid crystal in a PSA mode to achieve a high-speed response of the liquid crystal panel, Can be suppressed and the AC afterimage characteristic can be improved. From the results of Examples 6A and 12A, it was found that a liquid crystal display device with high-speed response can be obtained.

The liquid crystal aligning agents of Examples 1 to 12 were used in the same manner as in Example 1 except that the pattern of the ITO electrode on the glass substrate was changed to the electrode pattern of the fishbone shape as shown in Figs. To prepare a liquid crystal cell, and evaluation was performed. Even in this case, the same effects as those of Examples 1 to 12 were obtained.

1: ITO electrode
2:
3:

Claims (8)

A liquid crystal aligning agent for a PSA mode liquid crystal display element, which contains a polymer (A1) having a polymerizable unsaturated bond. The method according to claim 1,
Wherein the liquid crystal layer contains a monofunctional liquid crystal compound having one of an alkenyl group and a fluoroalkenyl group in the liquid crystal layer. The method according to claim 1,
The polymer (A1) is a group containing a polymerizable unsaturated bond and is a polymerizable unsaturated bond and contains at least a group selected from the group consisting of a group represented by the following formula (f1), a group represented by the following formula (f2) A liquid crystal aligning agent for a PSA mode liquid crystal display element,

(Formula (f1) of, R ^1, R ⁴ and R ⁶ are, each independently, a hydrogen atom, an alkyl group or substituted alkyl group having 1 to 5 carbon atoms of 1 to 5 carbon atoms; formula (f2) of, R ² is, A hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent group having -O- between at least one carbon-carbon bond of the hydrocarbon group, and * in the formulas (f1) to (f3) Indicating a combined hand). The method according to claim 1,
Wherein the polymer (A1) is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane. A method for manufacturing a liquid crystal display device, comprising the steps of: applying the liquid crystal aligning agent according to any one of claims 1 to 4 on a conductive film of a pair of substrates each having a conductive film;
A second step of constructing a liquid crystal cell by arranging a pair of substrates on which the coating film is formed, with the liquid crystal layer containing a liquid crystal compound interposed therebetween so as to face the coating film,
A third step of irradiating the liquid crystal cell with light while a voltage is applied between the conductive films of the pair of substrates
Wherein the liquid crystal display element is a liquid crystal display element. 6. The method of claim 5,
Wherein the liquid crystal layer contains a monofunctional liquid crystal compound having any one of an alkenyl group and a fluoroalkenyl group. A liquid crystal alignment film for a PSA mode liquid crystal display element formed using the liquid crystal aligning agent according to any one of claims 1 to 4. A PSA mode liquid crystal display element comprising the liquid crystal alignment film according to claim 7.

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