TW201416777A - Liquid crystal alignment agent and liquid crystal alignment film for PSA-mode liquid crystal display device, liquid crystal display device and method for manufacturing the same - Google Patents

Abstract

A liquid crystal alignment agent and a liquid crystal alignment film for a PSA-mode liquid crystal display device, a liquid crystal display device and a method for manufacturing the same are provided. A PSA-mode liquid crystal display device is provided, which shows a high voltage holding ratio even after the liquid crystal unit is irradiated with light, and the device does not tend to produce residual image. A polymer having a polymeric unsaturated bond (A1) is contained in a liquid crystal alignment agent for a PSA-mode liquid crystal display device. A group including the polymeric unsaturated bond contained in the polymer (A1) is preferably at least one selected from a group consisting of a group represented by the following formula (f1), a group represented by the following formula (f2) and a group represented by the following formula (f3).

Description

Liquid crystal alignment agent and liquid crystal alignment for liquid crystal display elements in PSA mode Film, liquid crystal display element and method of manufacturing same

The present invention relates to a liquid crystal alignment agent for a polymer suspension alignment (PSA) mode liquid crystal display device, a liquid crystal alignment film, and a PSA mode liquid crystal display device, and a method for fabricating the same, and in particular, the present invention relates to a A technique for improving the voltage holding characteristics of a PSA mode liquid crystal display element.

Conventionally, regarding the liquid crystal display element, various driving methods have been developed in which the electrode structure or the physical properties of the liquid crystal molecules to be used are different. For example, a twisted nematic (TN) type or a super twisted nematic (Super Twisted Nematic) is known. Various liquid crystal display elements such as STN), Vertical Alignment (VA) type, and In-Plane Switching (IPS) type. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As the material of the liquid crystal alignment film, for example, polylysine or polyphthalate, polyimide, polyester, polyorganosiloxane or the like is known.

Further, in recent years, regarding a liquid crystal display element, a Polymer Sustained Alignment (PSA) mode has been proposed as a new driving mode for controlling the alignment of liquid crystal molecules. The PSA mode is a technique in which a photopolymerizable compound is mixed in a liquid crystal material, and after a liquid crystal cell is assembled, a liquid crystal cell is irradiated with light in a state in which a voltage is applied between a pair of electrodes sandwiching the liquid crystal layer. The photopolymerizable compound is polymerized to control the molecular alignment of the liquid crystal molecules. According to this technique, there is an advantage that an expansion of the viewing angle or a high-speed response can be achieved.

However, in the case of the PSA mode, if the amount of light irradiation is insufficient, the unreacted photopolymerizable compound remains in the liquid crystal layer, and image retention (after-image) is likely to occur due to the unreacted product. In addition, when the amount of light irradiation is increased in order to completely react the photopolymerizable compound, the quality of the liquid crystal molecules or the liquid crystal alignment film may be lowered, and the display quality of the panel may be lowered. In order to eliminate such a problem, various techniques for reducing the amount of the photopolymerizable compound remaining in the liquid crystal layer without increasing the amount of light irradiation have been proposed (for example, see Patent Document 1). In the liquid crystal layer, a liquid crystal compound having a terphenyl ring structure (hereinafter also referred to as "triphenyl liquid crystal") is disclosed in Patent Document 1.

Further, in recent years, a further high-speed response of a PSA type liquid crystal panel has been studied. As a technique of this technique, a monofunctional liquid crystal compound having an alkenyl group and a fluoroalkenyl group (hereinafter also referred to as "ene" has been tried. The base liquid crystal ") is introduced into the liquid crystal layer (see, for example, Patent Document 2 to Patent Document 4).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2009/050869

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-285499

[Patent Document 3] Japanese Patent Laid-Open No. Hei 9-104644

[Patent Document 4] Japanese Patent Laid-Open No. Hei 6-108053

However, even when a terphenyl liquid crystal is introduced into the liquid crystal layer, there are many unreacted photopolymerizable compounds remaining after light irradiation, and there is room for further improvement in afterimage characteristics. Further, in the case of a liquid crystal display device using an alkenyl liquid crystal, although the response speed can be increased, it is understood that the light retention rate is lowered and the liquid crystal layer does not contain an enerene due to light irradiation on the liquid crystal cell. The liquid crystal cell of the base liquid crystal becomes larger in comparison. From the viewpoint of further improving the display quality of the liquid crystal display element, it is required to suppress a decrease in the voltage holding ratio caused by light irradiation as much as possible.

The present invention has been made in view of the above problems, and a main object thereof is to provide a liquid crystal alignment agent which can exhibit a high voltage holding ratio even after light irradiation of a liquid crystal cell, and which is less likely to cause afterimages. PSA mode liquid crystal display element.

The inventors of the present invention have diligently studied in order to achieve the problems of the prior art as described above, and as a result, have found that liquid crystal alignment agents containing a specific polymer are used to form liquid crystals in the process of manufacturing a PSA mode liquid crystal display device. Orientation The film can solve the above problems, and the present invention has been completed. Specifically, the liquid crystal alignment agent for a PSA mode liquid crystal display element, a liquid crystal alignment film, a liquid crystal display element, and a method for producing the same are provided by the present invention.

The present invention provides, in one aspect, a liquid crystal alignment agent for a PSA mode liquid crystal display element comprising a polymer (A1) having a polymerizable unsaturated bond.

The liquid crystal alignment 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 by using such a liquid crystal alignment agent, it is possible to obtain a high voltage holding ratio even after light irradiation of the liquid crystal cell in the manufacturing process of the PSA mode liquid crystal display element, Further, a liquid crystal display element in which an afterimage is less likely to occur. In particular, by using the liquid crystal alignment agent of the present invention for producing a liquid crystal display element containing a monofunctional liquid crystal compound having any one of an alkenyl group and a fluoroalkenyl group in the liquid crystal layer, it is possible to more suitably obtain light even in light. It also exhibits an effect of high voltage holding ratio or an effect of not easily generating afterimages after irradiation.

According to another aspect of the present invention, a method of manufacturing a liquid crystal display element, comprising: a first step of separately applying the liquid crystal alignment agent of the present invention to the conductive layer of a pair of substrates having a conductive film a film is then heated to form a coating film, and in the second step, the pair of substrates on which the coating film is formed are disposed to face each other with the coating film facing each other via a liquid crystal layer containing a liquid crystal compound. In the third step, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.

The present invention provides, in another aspect, a liquid crystal alignment agent using the present invention. A liquid crystal alignment film for a PSA mode liquid crystal display device to be formed, and a PSA mode liquid crystal display element including the liquid crystal alignment film.

1‧‧‧ITO electrode

2‧‧‧ Department

3‧‧‧Shade film

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

2 is a view showing electrode patterns of transparent electrode films used in Examples and Comparative Examples.

3 is a view showing electrode patterns of transparent electrode films used in Examples and Comparative Examples.

Hereinafter, each component contained in the liquid crystal alignment agent for a PSA mode liquid crystal display device of the present invention, and other components arbitrarily formulated as needed will be described.

<Polymer (A1)>

The liquid crystal alignment 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, and preferred examples thereof include a group represented by the following formula (f1), a group represented by the following formula (f2), and the following A group represented by the formula (f3) or the like.

[Chemical 1]

(In the formula (f1), R ¹ , R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms. In the formula (f2), R ² is hydrogen. An 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. In the formula (f1) to (f3), * represents a bonding bond)

Examples of the alkyl group having 1 to 5 carbon atoms of 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. These groups may be The linear shape can also be branched. In addition, the substituted alkyl group having 1 to 5 carbon atoms may be a group in which at least one hydrogen atom of the above-exemplified alkyl group is substituted with, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like). Mission and so on. R ¹ , R ⁴ and R ^{6 are} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms or a substituted alkyl group, more preferably a hydrogen atom or a methyl group.

The monovalent hydrocarbon group having 1 to 20 carbon atoms of R ² in the formula (f2) may, for example, be a monovalent chain hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, decyl group, dodecyl group, tridecyl group, and tenth. Tetraalkyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, phenyl, tolyl, xylyl, benzyl, Biphenylyl, 4,4'-dicyclohexyl, 4-cyclohexylphenyl, ethylphenyl, propylphenyl, pentylphenyl, and the like.

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

The main skeleton of the polymer (A1) is exemplified by polyglycine, polyimine, polyphthalate, polyester, polyamine, polyorganosiloxane, cellulose derivative, polycondensation. A skeleton formed of an aldehyde derivative, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate derivative, or the like. Regarding which of these skeletons is applied, it is only necessary to appropriately select according to the use of the liquid crystal display element, etc., wherein the polymer (A1) is particularly preferably selected from the group consisting of polylysine, polyphthalate, and polyphthalamide. At least one selected from the group consisting of amines and polyorganosiloxanes is more preferably at least one selected from the group consisting of polyglycolic acid, polyimine, and polyorganosiloxane. Hereinafter, polyphthalic acid, polyphthalate, polyimine, and polyorganosiloxane which are the polymer (A1) of the present invention will be described in detail.

[polyaminic acid (A1)]

In the present invention, the polylysine as the polymer (A1) has a polymerizable unsaturated bond, and it is preferred to have the polymerizable unsaturated bond in the side chain. Such a polyamic acid having a polymerizable unsaturated bond (hereinafter also referred to as "polyproline (A1)") can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine having a polymerizable unsaturated bond. .

[tetracarboxylic dianhydride]

Examples of the tetracarboxylic dianhydride used for the synthesis of the polyamic acid (A1) of the present invention include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride, for example, 1,2,3,4-butanetetracarboxylic dianhydride, and the like; for example, an alicyclic tetracarboxylic dianhydride can be mentioned. Out: 1,2,3,4-cyclobutane tetracarboxylic 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, 1,3,3a,4,5,9b-six Hydrogen-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo [3.2.1] Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6- Anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ] Monoalkane-3,5,8,10-tetraketone, cyclohexanetetracarboxylic dianhydride, etc., and aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, etc., other than this, Japan can be used. A tetracarboxylic dianhydride or the like disclosed in Japanese Laid-Open Patent Publication No. 2010-97188. Further, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

The tetracarboxylic dianhydride for synthesizing polyamic acid preferably comprises an alicyclic tetracarboxylic dianhydride, more preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2 At least one of 3,4-cyclobutanetetracarboxylic dianhydride. The content of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 1,2,3,4-cyclobutane tetracarboxylic dianhydride relative to the total amount of tetracarboxylic dianhydride used in the synthesis ( The total amount is preferably 60 mol% or more, more preferably 80 mol% or more.

[diamine]

The diamine for synthesizing the poly-proline of the present invention preferably contains a diamine having a polymerizable unsaturated bond (hereinafter also referred to as "specific diamine"). The specific structure of the specific diamine is not particularly limited as long as it has a polymerizable unsaturated bond and two primary amino groups. For example, the following compounds are exemplified as preferred examples: the diamine having the group represented by the formula (f1) may be a compound represented by the following formula (E1-1) to formula (E1-3). The diamine having a group represented by the formula (f2) may, for example, be a compound represented by the following formula (E1-5); and the diamine having the group represented by the formula (f3) may be used. A compound represented by the following formula (E1-4) and the like are given.

(In the formula (E1-1), R ¹ , R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms. X ¹ , Y ¹ and Z ¹ Each of them is independently a phenylene group, a cyclohexylene group or an oxygen atom. 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 , h ¹ , k ¹ and l ^{1 is} independently 0 or 1. Among them, a ¹ ~ l ¹ does not become a combination of oxygen atoms adjacent to each other, a combination of "-CO-O-" and a carbonyl group, and "-CO-O-" and an oxygen atom. Adjacent combination)

[Chemical 3]

(In the formula (E1-2), two R ¹ , R ⁴ and R ⁶ each independently represent 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 respectively Independently phenyl or exocyclohexyl. a ²¹ , a ²² and f ³ are each independently an integer from 0 to 12, b ²¹ , b ²² , c ² , d ² , e ² , g ² , h ² , k ²¹ And k ²² are each independently 0 or 1. Among them, 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 do not become oxygen. a combination of atoms adjacent to each other, a combination of "-CO-O-" adjacent to a carbonyl group, and a combination of "-CO-O-" adjacent to an oxygen atom)

(In the formula (E1-3), R ¹ , R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms; and R ³ is a hydrogen atom or a carbon number; An alkyl group of 1 to 12 or "-(CH ₂ ) n-OH" (where n is an integer of 1 to 4). a ³ and c ³ are each independently an integer of 1 to 12, and b ³ is 2 or 3. d ³ is an integer of 0 to 12, and e ³ , f ³ and k ³ are each independently 0 or 1. Among them, 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)

(In the formula (E1-4), 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 are each independently an integer of 0 to 12, and b ⁴ and c ⁴ are each independently. , d ⁴ , e ⁴ , f ⁴ , h ⁴ and i ⁴ are each independently 0 or 1. Among them, a ⁴ to i ⁴ do not become a combination of oxygen atoms adjacent to each other, and "-CO-O-" is adjacent to the carbonyl group. Combination, and the combination of "-CO-O-" and the oxygen atom)

(In the formula (E1-5), R ⁵ is a hydrogen atom or a methyl group, and W ⁵ , X ⁵ , Y ⁵ and Z ⁵ are each independently a phenyl group, a cyclohexylene group, an oxygen atom or an alkane having 1 to 12 carbon atoms. The dibasic group f ⁵ is an integer of 0 to 12, and a ⁵ , b ⁵ , c ⁵ , d ⁵ , e ⁵ , g ⁵ and h ⁵ are each independently 0 or 1. Among them, a ⁵ to h ⁵ do not become oxygen atoms. a combination adjacent to each other, a combination of "-CO-O-" adjacent to a carbonyl group, and a combination of "-CO-O-" adjacent to an oxygen atom)

In the formula (E1-1), from the viewpoint of improving the afterimage characteristics, it is preferred that k ¹ =1, and R ⁴ and R ⁶ are hydrogen atoms. Further, from the viewpoint of improving the high-speed response of the liquid crystal display element, k ¹ =0 is preferable.

a ¹ to l ¹ in the formula (E1-1) does not become a combination of oxygen atoms adjacent to each other, a combination of "-CO-O-" adjacent to a carbonyl group, and "-CO-O-" and an oxygen atom. Adjacent combination. Specifically, when a ¹ =0, at least one of b ¹ and k ¹ is 0. 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 do not form a combination of oxygen atoms adjacent to each other or a combination of an oxygen atom and a carbonyl group. When a ¹ ~ g ^{1 are} all 0, at least 2 of h ¹ , k ¹ and l ¹ are 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 do not become oxygen atoms with each other. Adjacent combinations, a combination of "-CO-O-" adjacent to a carbonyl group, and a combination of "-CO-O-" adjacent to an oxygen atom. 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 0. When f ² =0, at least two of e ² , g ² and h ² are 0, or e ² =0 and g ² = h ² =1.

Examples of the alkyl group having 1 to 12 carbon atoms of R ³ in the formula (E1-3) 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 and a decyl group. , mercapto, dodecyl and the like. Further, these groups may be linear or branched.

In the formula (E1-4), a ⁴ to i ^{4 are} not a combination of oxygen atoms adjacent to each other, a combination of "-CO-O-" adjacent to a carbonyl group, and "-CO-O-" and an oxygen atom. Adjacent combination. 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 do not form a combination of oxygen atoms adjacent to each other or a combination of an oxygen atom and a carbonyl group. When c ⁴ ~ g ^{4 are} all 0, at least 2 of b ⁴ , h ⁴ and i ⁴ are 0, or b ⁴ =0 and h ⁴ = i ⁴ =1.

Further, examples of the alkanediyl group having 1 to 12 carbon atoms of W ⁵ , X ⁵ , Y ⁵ and Z ⁵ in the formula (E1-5) include a methylene group, an ethylidene group and a propane-1. 3-diyl, propane-1,2-diyl, butane-1,4-diyl, butane-1,3-diyl, pentane-1,5-diyl, heptane-1,7 - Diyl, octane-1,8-diyl, decane-1,10-diyl, dodecane-1,12-diyl and the like.

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

Specific examples of the compound represented by the formula (E1-1) to the formula (E1-5), the compound represented by the formula (E1-1), for example, the following formula (E1-1-1) And a compound represented by the formula (E1-1-9), and the compound represented by the formula (E1-2) is, for example, the following formula (E1-2-1) to (E1-2-). 5) The compound represented by the formula (E1-3), and the compound represented by the formula (E1-3-1) to the formula (E1-3-5), etc. The compound represented by the formula (E1-4) is, for example, a compound represented by the following formula (E1-4-1) to (E1-4-6); The compound represented by the following formula (E1-5-1) to the formula (E1-5-5), and the like are exemplified.

[Chemistry 7]

[Chemistry 9]

In the compound, the specific diamine is preferably a group having a group represented by the formula (f1) or the formula (f2) as a group containing a polymerizable unsaturated bond. Among the compounds represented by the formula (E1-1) to the formula (E1-5), more preferably, it is selected from the compound represented by the formula (E1-1) and the formula (E1- 4) At least one of the group consisting of the compounds represented. Further, in the case of having the group represented by the formula (f1), the group is preferably a part of an acryloyl group or a methacrylic group from the viewpoint of improving afterimage characteristics. The inclusion is preferably an alkenyl group from the viewpoint of improving high-speed responsiveness.

The diamine used for the synthesis of the poly-proline (A1) of the present invention may be used singly as the specific diamine, but the specific diamine may also be used together with a diamine other than the specific diamine (hereinafter also referred to as For "other diamines").

Here, examples of the other diamine include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamine organic decane, and the like. Specific examples of the other diamines include aliphatic methylene diamine, 1,3-propane diamine, tetramethylene diamine, pentamethylene diamine, and hexamethylene group. Diamines and the like; examples of the alicyclic diamines include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and 1,3-bis(aminomethyl) Cyclohexane or the like; examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5 -diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-Diaminoguanidine, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis ( 4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-bis(4-aminophenoxyl) Benzo, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3 ,6-diaminoacridine, 3,6-diamine Ketrazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N , N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-( 4-aminophenyl)-pyridazine, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene , pentadecyloxy-2,4-diaminobenzene, cetyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy Base-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2,5 -diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestaneyl-3,5-diaminobenzene, cholesteneoxy -3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3 , cholesteryl 5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoic acid, 3,6-bis ( 4-aminobenzimidyloxy)cholestane, 3,6-bis(4-aminobenzene Cholesterol, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzoate醯oxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1 ,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl) -4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 1-(4) -aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indol-5-amine, 3-(3,5-diaminobenzylideneoxy)cholesterol An alkane, a compound represented by the following formula (D-1), and the like,

(In the formula (D-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, and R ^I is an alkanediyl group having 1 to 3 carbon atoms, and 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. wherein a and b are not 0) at the same time; and the diamine-based organodecane may, for example, be 1,3-double (3-Aminopropyl)-tetramethyldioxane or the like; in addition to the above, a diamine disclosed in Japanese Laid-Open Patent Publication No. 2010-97188 can be used.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the formula (D-1) is preferably an alkanediyl group having a carbon number of 1 to 3, *-O-, * -COO- or *-OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group).

Specific examples of the group "-C _c H _2c+1 " include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and the like. N-decyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, N-nonadecyl, n-icosyl and the like. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative 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).

[Chemistry 13]

Further, the other diamine may be used alone or in combination of two or more kinds of these compounds.

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

[Molecular weight regulator]

In the case of synthesizing polyamic acid, a terminal-modified polymer may be synthesized by using an appropriate molecular weight modifier together with the tetracarboxylic dianhydride and the diamine as described above. By the polymer which is set to the terminal modification type, the coating property (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

Examples of the molecular weight modifier include an acid monoanhydride, a monoamine compound, and a monoisocyanate compound. Specific examples of the molecular weight modifier include, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, and n-decyl succinic anhydride; and examples of the monoamine compound include aniline and cyclohexane. An amine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc., and a monoisocyanate compound, for example, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned.

100 weights relative to the total amount of tetracarboxylic dianhydride and diamine used The proportion of the molecular weight modifier to be used is preferably 20 parts by weight or less, more preferably 10 parts by weight or less.

<Synthesis of polylysine>

With respect to the use ratio of the tetracarboxylic dianhydride and the diamine in the synthesis reaction of the polyaminic acid to be used in the present invention, it is preferred that the acid anhydride group of the tetracarboxylic dianhydride becomes 1 equivalent to the amine group of the diamine. More preferably, the ratio of the acid anhydride group of the tetracarboxylic dianhydride is from 0.3 equivalents to 1.2 equivalents. Further, the synthesis reaction of polyproline is preferably carried out in an organic solvent. The reaction temperature at this time is preferably from -20 ° C to 150 ° C, more preferably from 0 to 100 ° C. Further, the reaction time is preferably from 0.5 to 24 hours, more preferably from 2 hours to 10 hours.

Here, the organic solvent used in the reaction may be one which dissolves the synthesized polyamic acid (A1), and specific examples thereof include N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone. , N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, 1,3-dimethyl-2-imidazolidinone (1,3-dimethyl-2) -imidazolidinone), aprotic polar solvents such as γ-butyrolactone, tetramethylurea, hexamethyl phosphortriamide; m-cresol, xylenol, phenol, halogenated phenol, etc. A solvent or the like. Further, these organic solvents may be used alone or in combination of two or more.

Further, as the organic solvent used in the reaction, a poor solvent of polyglycine (A1) may be used in a range in which the polyamic acid (A1) does not precipitate. Examples of such a poor solvent include alcohols such as methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl ether; and acetone. ,methyl Ketones such as ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxypropionic acid Ethyl ester, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate, etc.; diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, diisoamyl ether and other ethers; dichloromethane, 1,2-dichloroethane a halogenated hydrocarbon such as 1,4-dichlorobutane, trichloroethane, chlorobenzene or o-dichlorobenzene; a hydrocarbon such as hexane, heptane, octane, benzene, toluene or xylene. Further, these poor solvents may be used alone or in combination of two or more.

Using a poor solvent of the polyamic acid (A1) as a reaction In the case of the organic solvent, the use ratio of the poor solvent is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30% by weight or less based on the total amount of the organic solvent used for the synthesis. .

The amount of the organic solvent used (a) is preferably set to tetracarboxylic dianhydride and two The total amount of the amines (b) is an amount of 0.1% by weight to 50% by weight based on the total amount (a+b) of the reaction solution.

As described above, it is possible to dissolve poly-proline (A1) Reaction solution. The reaction solution may be directly supplied to prepare a liquid crystal alignment agent, or may be separated from the poly-proline (A1) contained in the reaction solution to prepare a liquid crystal alignment agent, or the separated polyamic acid (A1) may be used. After purification, it is used to prepare a liquid crystal alignment agent. Further, in the case where polylysine (A1) is dehydrated and closed to form a polyimine, the reaction solution may be directly supplied to a dehydration ring-closure reaction, or a polylysine contained in the reaction solution may be used. (A1) After separation, it is supplied to a dehydration ring closure reaction, or the isolated polyamic acid (A1) may be purified and then subjected to a dehydration ring closure reaction. The separation and purification of polyamic acid (A1) can be carried out in accordance with a well-known method.

<Polyurethane (A1)>

The polyphthalamide which is the polymer (A1) of the present invention has a polymerizable unsaturated bond. Such a polyglycolate having a polymerizable unsaturated bond (hereinafter also referred to as "polyphthalate (A1)") can be obtained, for example, by the following method: [I] a polymerization obtained by permeating the synthesis reaction a method for synthesizing a polyphthalate by reacting a proline (A1) with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like; [II] reacting a tetracarboxylic acid diester with a diamine Method; [III] A method of reacting a tetracarboxylic acid diester dihalide with a diamine.

Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol, and propanol; and phenols such as phenol and cresol. Further, examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearin chloride, 1,1,1-trifluoro-2-iodoethane, and the like. Examples of the compound of the group include propylene oxide and the like. The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by subjecting the tetracarboxylic dianhydride exemplified in the synthesis of the polyproline to ring opening using the alcohol. Further, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting a tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as sulfinium chloride. The diamine used in the method [II] and the method [III] may be The diamine or the like exemplified in the synthesis of the polyamic acid (A1) is used. Further, the polyphthalate (A1) may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist.

<Polyimine (A1)>

In the present invention, the polyimine as the polymer (A1) has a polymerizable unsaturated bond. Such a polyiminoimine having a polymerizable unsaturated bond (hereinafter also referred to as "polyimine (A1)") can be obtained, for example, by a polylysine synthesized as described above (A1) The dehydration ring is closed and the oxime is imidized.

The polyimine (A1) may be a fully ruthenium imide formed by dehydration ring closure of all of the proline structures of the polyamic acid (A1) as its precursor, or may be only a part of The proline structure is dehydrated and closed, and the guanidinoic acid structure and the quinone imine ring structure coexist. The polyamidimide (A1) of the present invention preferably has a ruthenium iodide ratio of 40% or more, more preferably 50% to 99%. The ruthenium imidization ratio is a percentage of the number of quinone ring structures in the total amount of the guanidine structure of the polyimine and the total number of quinone ring structures. Further, a part of the quinone ring may also be an isoindole ring.

The dehydration ring closure of polylysine (A1) is carried out by heating a polyaminic acid (A1) or by dissolving polyglycine (A1) in an organic solvent and adding it to the solution. Dehydrating agent and dehydration ring-closing catalyst, if necessary, heating. Among them, it is preferable to use the latter method.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the solution of the polyamic acid, for example, acetic anhydride, propionic anhydride, trifluoroacetic anhydride, or the like can be used as the dehydrating agent. Anhydride. The amount of the dehydrating agent to be used is preferably set to 0.01 mol to 20 mol, relative to the proline structure of poly-proline. As the dehydration ring-closing catalyst, for example, a tertiary amine such as N-methyl acridine, pyridine, collidine, lutidine or triethylamine can be used. The amount of the dehydration ring-closure catalyst to be used is preferably set to 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent to be used. The organic solvent to be used in the dehydration ring-closure reaction is exemplified as the organic solvent used for the synthesis of the polyamic acid (A1). The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 0.5 to 20 hours, more preferably from 1.0 to 8 hours.

Thus, a reaction solution containing polyimine (A1) can be obtained. The reaction solution may be directly used for preparing a liquid crystal alignment agent, or may be used for preparing a liquid crystal alignment agent after removing a dehydrating agent and a dehydration ring-closing catalyst from the reaction solution, or may be used for preparing a liquid crystal alignment after separating the polyimine (A1). Alternatively, the isolated polyimine (A1) may be purified and then used to prepare a liquid crystal alignment agent. These purification operations can be carried out in accordance with well-known methods.

The polyaminic acid (A1), the polyphthalate (A1) and the polyimine (A1) obtained as described above preferably have a concentration of 10 m% when formed into a solution having a concentration of 10% by weight. s~800mPa. The solution viscosity of s, more preferably 15mPa. s~500mPa. s solution viscosity. Further, the solution viscosity (mPa.s) of the polymer is prepared by using an E-type rotational viscometer for a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using these polymers. The concentration of the 10% by weight polymer solution was measured at 25 ° C.

The polystyrene-reduced weight average of the polyperuric acid (A1), the polyamidomate (A1), and the polyimine (A1) as measured by Gel Permeation Chromatography (GPC) The molecular weight is preferably from 500 to 300,000, more preferably from 1,000 to 200,000.

[polyorganooxane (A1)]

In the present invention, the polyorganosiloxane having the polymer (A1) has a polymerizable unsaturated bond. Such a polyorganosiloxane having a polymerizable unsaturated bond (hereinafter also referred to as "polyorganosiloxane (A1)") can be synthesized by appropriately combining a common method of organic chemistry. Examples thereof include (I) a method of hydrolyzing and condensing a hydrolyzable decane compound (s1) having a polymerizable unsaturated bond, or a mixture of the decane compound (s1) and another decane compound; The hydrolyzable decane compound (s2) of the epoxy group or the mixture of the decane compound (s2) and another decane compound is subjected to hydrolysis condensation to obtain the obtained polymer (hereinafter also referred to as "epoxy group-containing polyorganosiloxane" a method of reacting an alkane ") with a carboxylic acid (c1) having a polymerizable unsaturated bond; (III) a mixture of the decane compound (s1) or the decane compound (s1) with another decane compound in an alcohol solvent, A method of heating in the presence of an oxalic acid catalyst.

[decane compound (s1)]

The decane compound (s1) is a hydrolyzable decane compound having a polymerizable unsaturated bond, and specific examples thereof include 3-(meth) propylene methoxy propylene. Trichlorodecane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 2-(methyl)propenyloxy Ethyltrichloromethane, 2-(methyl)propenyloxyethyltrimethoxydecane, 2-(methyl)propenyloxyethyltriethoxydecane, 4-(methyl)propeneoxime Butyl trichlorodecane, 4-(methyl)propenyloxybutyltrimethoxydecane, 4-(methyl)propenyloxybutyltriethoxydecane, vinyltrichlorodecane, vinyl Trimethoxy decane, vinyl triethoxy decane, allyl trichloro decane, allyl trimethoxy decane, allyl triethoxy decane, and the like. The decane compound (s1) may be used alone or in combination of two or more. Further, in the present specification, "(meth)acryloxy" is a meaning including an acryloxy group and a methacryloxy group.

[decane compound (s2)]

The decane compound (s2) is a hydrolyzable decane compound having an epoxy group, and specific examples thereof include 3-glycidoxypropyltrimethoxydecane and 3-glycidoxypropyltriethyl. Oxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxy Decane, 3-glycidoxypropyl dimethyl ethoxy decane, 2-glycidoxyethyl trimethoxy decane, 2-glycidoxyethyl triethoxy decane, 2-glycidyl oxygen Ethylethyldimethoxydecane, 2-glycidoxyethylmethyldiethoxydecane, 2-glycidoxyethyldimethylmethoxydecane, 2-glycidoxy B Dimethyl ethoxy decane, 4-glycidoxy butyl trimethoxy decane, 4-glycidoxy butyl triethoxy decane, 4-glycidoxy butyl dimethyl dimethoxy decane, 4-glycidoxybutylmethyldiethoxylate Baseline, 4-glycidoxybutyl dimethyl methoxy decane, 4-glycidoxy butyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4- Epoxycyclohexyl)propyltriethoxydecane, and the like. The decane compound (s2) may be used alone or in combination of two or more.

In each of the methods (I) to (III), it can be used as needed Other decane compounds (hereinafter also referred to as decane compounds (s3)) include, for example, methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, phenyltrichlorodecane, and phenyltrimethyl. Oxydecane, phenyltriethoxydecane, methyldichlorodecane, methyldimethoxydecane, methyldiethoxydecane, dimethyldichlorodecane, dimethyldimethoxydecane, Dimethyldiethoxydecane, diphenyldichlorodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, chlorodimethylsilane, methoxydimethylsilane, ethoxy Dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, methoxy trimethyl decane, ethoxy trimethyl decane, tetramethoxy decane, tetraethoxy Decane, octadecyltrichlorodecane, octadecyltrimethoxydecane, octadecyltriethoxydecane, and the like. The other decane compound (s3) may be used alone or in combination of two or more.

When the polyorganosiloxane (A1) is synthesized by the method (I), The decane compound to be used preferably contains 1 mol% to 80 mol% of the decane compound (s1), more preferably 5 mol% to 50 mol% of the decane compound (s1), based on the total amount of the decane compound. Further, in order to easily introduce a structure such as a vertical alignment group described later into a side chain of the polymer, the decane used in the synthesis is used. The compound preferably contains a decane compound (s2). The use ratio of the decane compound (s2) is preferably from 20 mol% to 90 mol%, more preferably from 50 mol% to 80 mol%, based on the total amount of the decane compound used for the synthesis. The content ratio of the other decane compound (s3) is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total amount of the decane compound used for the synthesis.

In the synthesis of the polyorganosiloxane (A1) by the method (II), the decane compound to be used preferably contains 10 mol% to 100 mol% of the decane compound (s2) based on the total amount of the decane compound. More preferably, it contains 20 mol% to 100 mol% of the decane compound (s2). Further, the content ratio of the other decane compound (s3) is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total amount of the decane compound used for the synthesis.

In the synthesis of the polyorganosiloxane (A1) by the method (III), the decane compound to be used preferably contains 1 mol% to 80 mol% of the decane compound (s1) with respect to the total amount of the decane compound. More preferably, it contains 5 mol% - 50 mol% of said decane compound (s1). Further, the use ratio of the decane compound (s2) is preferably 20 mol% or less, more preferably 10 mol% or less, based on the total amount of the decane compound used for the synthesis. The content ratio of the other decane compound (s3) is preferably 99 mol% or less, more preferably 95 mol% or less, based on the total amount of the decane compound used for the synthesis.

The hydrolysis and condensation reaction of the decane compound of the method (I) and the method (II) can be carried out by reacting one or two or more kinds of decane compounds as described above with water, preferably Is in the proper catalyst and there is The reaction with water is carried out in the presence of an organic solvent. In the hydrolysis and condensation reaction, the use ratio of water is preferably from 0.5 mol to 100 mol, more preferably from 1 mol to 30 mol, based on 1 mol of the decane compound (total amount).

Examples of the catalyst which can be used in the hydrolysis and condensation reaction include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Specific examples of the catalyst include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and phosphoric acid; and examples of the alkali metal compound include sodium hydroxide. Potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, etc.; the organic base is, for example, ethylamine, diethylamine, oxazine, acridine, pyrrolidine, pyrrole Primary to secondary organic amines; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene; A quaternary organic amine such as tetramethylammonium.

Among these compounds, the catalyst is preferably an alkali metal compound or an organic base from the viewpoint of suppressing side reactions such as ring opening of an epoxy group, or improving the rate of hydrolysis condensation, and excellent storage stability. , especially good for organic bases. Further, the organic base is preferably a tertiary organic amine or a tertiary organic amine.

The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions, and the like, and is appropriately set. For example, it is preferably 0.01 to 3 moles, more preferably 0.05 moles, per mole of the decane compound. ~1 times Moule.

Examples of the organic solvent which can be used in the hydrolysis and condensation reaction include a hydrocarbon, a ketone, an ester, an ether, and an alcohol. Specific examples of these organic solvents, hydrocarbons such as Examples of the ketone include toluene, xylene, and the like; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone; : ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, acetic acid-3-methoxybutyl ester, ethyl lactate, etc.; ether, for example, ethylene glycol Ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and B. Glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among these solvents, a water-insoluble organic solvent is preferably used. Further, these organic solvents may be used alone or in combination of two or more.

The proportion of the organic solvent used in the hydrolysis condensation reaction is preferably from 10 parts by weight to 10,000 parts by weight, more preferably from 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of all the decane compounds used in the reaction.

The hydrolysis and condensation reaction is preferably carried out by dissolving a decane compound as described above in an organic solvent, mixing the solution with an organic base and water, and heating by, for example, an oil bath. In the case of hydrolysis or condensation reaction, it is preferred to set the heating temperature to 130 ° C or lower, and more preferably to 40 ° C to 100 ° C. The heating time is preferably set to 0.5 hours to 12 hours, and more preferably set to 1 hour to 8 hours. The mixture may be stirred during heating or placed under reflux. Further, after the completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid by water. In the cleaning, it is preferred to use a water containing a small amount of salt (for example, an aqueous solution of ammonium nitrate of about 0.2% by weight or the like) for cleaning from the viewpoint of easy cleaning. Cleaning is performed until the water layer after cleaning becomes neutral, Thereafter, the organic solvent layer is dried by using a desiccant such as anhydrous calcium sulfate or molecular sieve, and the solvent is removed, whereby the target polyorganosiloxane can be obtained, that is, in the case of the method (I) A polyorganosiloxane having a polymerizable unsaturated bond is obtained, and in the case of the method (II), a polyorganosiloxane having an epoxy group (hereinafter also referred to as "epoxy-containing polyorganosiloxane" can be obtained. alkyl").

In the method (II), the epoxy group-containing polyorganosiloxane obtained by the hydrolysis and condensation reaction is then reacted with a carboxylic acid (c1) having a polymerizable unsaturated bond. Thus, a polyorganosiloxane (A1) having a polymerizable unsaturated bond can be obtained. The carboxylic acid used in the reaction may be a carboxylic acid (c1) alone or a group having a vertical alignment property with respect to the coating film (hereinafter also referred to as "liquid crystal alignment group") together with the carboxylic acid (c1). Carboxylic acid (c2), other carboxylic acid (c3).

Further, in the method (I), when the polyorganosiloxane having a permeation reaction of the decane compound has an epoxy group, the epoxy group having the polyorganosiloxane has a liquid crystal and has a liquid crystal. The carboxylic acid (c2) reaction of the alignment group imparts liquid crystal alignment to the polyorganosiloxane. Further, in the method (I), when a polyorganosiloxane having an epoxy group and a polymerizable unsaturated bond is reacted with a carboxylic acid, it may be used together with the carboxylic acid (c2) to be selected from a carboxylic acid (c1). And at least one of the group consisting of carboxylic acids (c3).

[carboxylic acid (c1)]

The carboxylic acid (c1) is not particularly limited as long as it has a polymerizable unsaturated bond and a carboxyl group. Specifically, for example, the carboxylic acid having the group represented by the formula (f1) may be represented by the following formula (C1-1) to formula (C1-3). A carboxylic acid having a group represented by the formula (f2): a compound represented by the following formula (C1-5); and a carboxylic acid having a group represented by the formula (f3) The compound represented by the following formula (E1-4) is mentioned.

(In the formula (C1-1), R ¹ , R ⁴ and R ⁶ each independently represent 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 Each of them is independently a phenylene group, a cyclohexylene group or an oxygen atom. a ⁶ and g ⁶ are each independently an integer of 0 to 12, and b ⁶ , c ⁶ , d ⁶ , e ⁶ , f ⁶ and k ⁶ are each independently 0 or 1. Among them, a ⁶ ~ g ⁶ and k ⁶ do not become a combination of oxygen atoms adjacent to each other, a combination of "-CO-O-" adjacent to a carbonyl group, and "-CO-O-" adjacent to an oxygen atom. combination)

(In the formula (C1-2), a plurality of R ¹ , R ⁴ and R ⁶ each independently represent 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 ⁷ and Y ⁷ respectively Independently, it is a phenyl or a cyclohexyl group. a ⁷¹ , a ⁷² and f ⁷ are each independently an integer of 0 to 12, and b ⁷¹ , b ⁷² , c ⁷ , d ⁷ , e ⁷ , k ⁷¹ and k ⁷² are each independently 0 or 1. Among them, a ⁷¹ , a ⁷² , b ⁷¹ , b ⁷² , c ⁷ , d ⁷ , e ⁷ , f ⁷ , k ⁷¹ and k ⁷² do not become a combination of oxygen atoms adjacent to each other, "-CO-O -" a combination adjacent to a carbonyl group, and a combination of "-CO-O-" adjacent to an oxygen atom)

(In the formula (C1-3), R ¹ , R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms; and R ⁸ is a hydrogen atom or a carbon number; An alkyl group of 1 to 12 or "-(CH ₂ ) n-OH" (where n is an integer of 1 to 4). a ⁸ , c ⁸ and d ⁸ are each independently an integer of 1 to 12, and b ⁸ is 2 Or 3, k ⁸ is 0 or 1. wherein, a plurality of R ¹ , R ⁴ , R ⁶ , a ⁸ and k ⁸ each independently have the definition)

(In the formula (C1-4), X ⁹ , Y ⁹ and Z ⁹ are each independently a phenyl group, a cyclohexylene group or an oxygen atom. A ⁹ and g ⁹ are each independently an integer of 0 to 10, and b ⁹ , c ⁹ , d ⁹ , e ⁹ and f ⁹ are each independently 0 or 1. Among them, a ⁹ to g ⁹ do not become a combination of oxygen atoms adjacent to each other, a combination of "-CO-O-" adjacent to a carbonyl group, and "- CO-O-" combination adjacent to an oxygen atom)

(In the formula (C1-5), R ¹⁰ is a hydrogen atom or a methyl group, and W ¹⁰ , X ¹⁰ , Y ¹⁰ and Z ¹⁰ are each independently a phenyl group, a cyclohexylene group, an oxygen atom or an alkane having 1 to 12 carbon atoms. Two bases, f ¹⁰ is an integer of 0 to 12, and a ¹⁰ , b ¹⁰ , c ¹⁰ , d ¹⁰ and e ¹⁰ are each independently 0 or 1. Wherein, when e ¹⁰ is 1, f ¹⁰ is an integer of 1 or more)

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

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

a ⁶ to g ⁶ and k ⁶ in the formula (C1-1) do not become a combination of oxygen atoms adjacent to each other, a combination of "-CO-O-" adjacent to a carbonyl group, and "-CO-O-" A combination adjacent to an oxygen atom. Specifically, when a ⁶ =0, at least one of b ⁶ and k ⁶ is zero. When g ⁶ =0, f ⁶ =0. When c ⁶ =d ⁶ =e ⁶ =0, at least one of b ⁶ and f ⁶ is zero. X ⁶ , Y ⁶ and Z ⁶ do not form a combination of oxygen atoms adjacent to each other or a combination of an oxygen atom and a carbonyl group. When all of a ⁶ to g ⁶ are 0, g 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 do not become a combination of oxygen atoms adjacent to each other, a combination of -CO-O-" adjacent to a carbonyl group, and a combination of "-CO-O-" adjacent to an oxygen atom. Specifically, 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 0. When f ⁷ =0, e ⁷ =0.

In the formula (C1-4), a ⁹ to g ⁹ do not become a combination of oxygen atoms adjacent to each other, a combination of "-CO-O-" adjacent to a carbonyl group, and "-CO-O-" and an oxygen atom. Adjacent combination. 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 to a phenylene group, a cyclohexylene group or an alkanediyl group. When c ⁹ =d ⁹ =e ⁹ =0, at least one of b ⁹ and f ⁹ is zero. X ⁹ , Y ⁹ and Z ⁹ do not form a combination of oxygen atoms adjacent to each other or a combination of an oxygen atom and a carbonyl group. When c ⁹ ~g ^{9 are} all 0, b ⁹ =0.

Specific examples of the compound represented by the formula (C1-1) to the formula (C1-5), the compound represented by the formula (C1-1), for example, the following formula (C1-1-1) The compound represented by the formula (C1-1-10), etc., and the compound represented by the formula (C1-2), for example, the following formula (C1-2-1) to the formula (C1-2-) 5) The compound represented by the formula (C1-3), and the compound represented by the formula (C1-3-1) to the formula (C1-3-5), etc. The compound represented by the formula (C1-4), for example, a compound represented by the following formula (C1-4-1) to the formula (C1-4-5); and the formula (C1-5) The compound represented by the formula (C1-5-1) to the formula (C1-5-5), for example, may be mentioned.

In the compound, the carboxylic acid (c1) preferably has a group represented by the formula (f1) or a group represented by the formula (f2) as a polymerizable unsaturated group. The compound of the group of the bond is more preferably a compound having the group represented by the formula (f1). Further, in the case of having the group represented by the formula (f1), the group is preferably a part of an acryloyl group or a methacrylic group from the viewpoint of improving afterimage characteristics. The inclusion is preferably an alkenyl group from the viewpoint of improving high-speed responsiveness. Further, the carboxylic acid (c1) may be used alone or in combination of two or more.

[carboxylic acid (c2)]

The carboxylic acid (c2) is not particularly limited as long as it has a liquid crystal alignment group and a carboxyl group. Examples of the liquid crystal alignment 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, and a group having a steroid skeleton having 17 to 51 carbon atoms. a group having a polycyclic structure or the like.

Specific examples of the carboxylic acid (c2) having a liquid crystal alignment group include, for example, hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, stearic acid, and the like. Chain fatty acid; 4-n-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid, 4-stearyl Benzoic acid having a long-chain alkyl group such as benzoic acid; 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-dodecyloxybenzoic acid, 4 a benzoic acid having a long-chain alkoxy group such as n-hexadecyloxybenzoic acid or 4-stearyloxybenzoic acid; cholestyloxybenzoic acid, cholestyloxybenzoic acid, lanostatinoxy Benzoic acid, cholestyloxycarbonylbenzoic acid, cholestyloxycarbonylbenzoic acid, lanostatinoxycarbonylbenzoic acid, succinic acid-5 ξ-cholest-3-yl ester, succinic acid-5 ξ a steroid skeleton such as cholesten-3-yl ester or succinic acid-5 fluorene-lanostan-3-yl ester Acid; 4-(4-pentyl-cyclohexyl)benzoic acid, 4-(4-hexyl-cyclohexyl)benzoic acid, 4-(4-heptyl-cyclohexyl)benzoic acid, 4'-pentyl-bicyclic Hexyl-4-carboxylic acid, 4'-hexyl-dicyclohexyl-4-carboxylic acid, 4'-heptyl-dicyclohexyl-4-carboxylic acid, 4'-pentyl-biphenyl-4-carboxylic acid, 4' -hexyl-biphenyl-4-carboxylic acid, 4'-heptyl-biphenyl-4-carboxylic acid, 4-(4-pentyl-dicyclohexyl-4-yl)benzoic acid, 4-(4-hexyl- Dicyclohexyl-4-yl)benzoic acid, 4-(4-heptyl-dicyclohexyl-4-yl)benzoic acid, 6-(4'-cyanobiphenyl-4-yloxy)hexanoic acid, 11- a benzoic acid having a polycyclic structure such as (4-cyclohexylphenoxy)undecanoic acid; 6,6,6-trifluorohexanoic acid, 4-(4,4,4-trifluorobutyl)benzoic acid, etc. A fluoroalkyl group-containing carboxylic acid or the like. Further, the carboxylic acid (c2) may be used alone or in combination of two or more.

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

In the method (I), the carboxylic acid which is reacted with the polyorganosiloxane having a polymerizable unsaturated bond and an epoxy group is preferably an epoxy group which is different from the polyorganosiloxane. The carboxylic acid (c2) is set to be 0.7 mol or less, and more preferably set to 0.1 mol to 0.6 mol. Further, as for the ratio of use of the carboxylic acid (c1), it is preferred to set the carboxylic acid (c1) to 0.5 mol or less with respect to 1 mol of the epoxy group of the polyorganosiloxane, and more preferably Set to 0.3 m or less. With respect to the use ratio of the carboxylic acid (c3), it is preferred to set the carboxylic acid (c3) to 0.3 mol or less with respect to 1 mol of the epoxy group of the polyorganosiloxane, and it is more preferable to set it to 0.2 moles below.

Further, in the method (II), regarding the polyorganosiloxane containing an epoxy group The alkane-reacted carboxylic acid preferably has the carboxylic acid (c1) set to 0.02 mol to 0.7 mol with respect to the epoxy group having 1 mole of the polyorganooxane. More preferably, it is set. It is 0.1 mole to 0.5 mole. Further, as for the ratio of use of the carboxylic acid (c2), it is preferred to set the carboxylic acid (c2) to 0.6 mol or less with respect to 1 mol of the epoxy group of the polyorganosiloxane, and more preferably Set to 0.2 m to 0.6 m. With respect to the use ratio of the carboxylic acid (c3), it is preferred to set the carboxylic acid (c3) to 0.3 mol or less with respect to 1 mol of the epoxy group of the polyorganosiloxane, and it is more preferable to set it to 0.2 moles below.

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

The reaction of the epoxy group of the polyorganosiloxane with the carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. Here, as the catalyst to be used in the reaction, for example, a compound known as a so-called curing accelerator which promotes the reaction of an organic base or an epoxy compound can be used.

The organic base may, for example, be a primary to secondary organic amine such as ethylamine, diethylamine, pyridazine, acridine, pyrrolidine or pyrrole; such as triethylamine, tri-n-propylamine or tri-n-butylamine. a tertiary organic amine such as pyridine, 4-dimethylaminopyridine or diazabicycloundecene; a quaternary organic amine such as tetramethylammonium hydroxide. Among these compounds, the organic base is preferably a tertiary organic amine or a tertiary organic amine.

Further, examples of the curing accelerator include a tertiary amine such as benzyldimethylamine; an imidazole compound such as 2-methylimidazole; an organic phosphorus compound such as diphenylphosphine; and benzyltriphenylphosphonium chloride. Tertiary cerium salt; 1,8-diazabicyclo[5.4.0]undecene-7 and other diazabicycloalkenes; organotin compounds such as zinc octoate and tin octylate; tetrabasic ammonium such as tetraethylammonium bromide A salt; a boron compound such as boron trifluoride; a metal halogen compound such as zinc chloride or tin chloride; and a compound known as a latent curing accelerator.

The catalyst can be preferably 100 parts by weight or less, more preferably 0.01 parts by weight to 100 parts by weight, still more preferably 0.1 parts by weight to 20 parts by weight, based on 100 parts by weight of the polyorganosiloxane. Use in proportions.

Examples of the organic solvent which can be used in the reaction of the polyorganosiloxane and the carboxylic acid include a hydrocarbon compound, an ether, an ester, a ketone, a decylamine, an alcohol, and the like. Among these organic solvents, from the viewpoints of solubility of the raw materials and products and ease of purification of the product, ethers, esters, and ketones are preferred, and specific examples of the particularly preferable solvent include 2-butanone and 2- Hexanone, methyl isobutyl ketone and butyl acetate. The organic solvent is preferably used in a ratio of a solid content concentration (a ratio of a total weight of components other than the solvent in the reaction solution to the total weight of the solution) of 0.1% by weight or more, more preferably a solid. The component concentration is used in a ratio of 5 wt% to 50 wt%.

The reaction temperature is preferably from 0 ° C to 200 ° C, more preferably from 50 ° C to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours. Further, after completion of the reaction, it is preferred to wash the organic solvent layer taken out from the reaction liquid with water. After washing, use an appropriate desiccant to remove the organic solvent layer as needed. After drying, the solvent is removed, whereby the desired polyorganosiloxane can be obtained.

On the other hand, in the case of the method (III), an oxalic acid alcohol solution may be prepared by previously adding oxalic acid to an alcohol, and the solution is combined with a decane compound (the decane compound (s1), an optional decane compound (s2) And other decane compound (s3)) are mixed and heated, thereby obtaining a solution containing the target polyorganosiloxane.

Here, 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, and diethylene glycol monoethyl ether. Wait.

The proportion of the alcohol used in the reaction is preferably from 10 parts by weight to 10,000 parts by weight, more preferably from 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of all the decane compounds used in the reaction. The amount of oxalic acid used in the reaction is preferably set to 0.2 mol to 2 mol with respect to 1 mol of all alkoxy groups possessed by the decane compound. Further, the heating temperature is preferably from 50 ° C to 180 ° C, and the heating time can be set, for example, from several tens of minutes to ten hours.

Thus, by the method (III), a reaction solution containing a polyorganosiloxane (A1) having a polymerizable unsaturated bond can be obtained. The reaction solution may be directly supplied to prepare a liquid crystal alignment agent, and if necessary, the reaction solution may be concentrated or diluted to prepare a liquid crystal alignment agent. Further, in the case where the polyorganosiloxane (A1) obtained by the reaction has an epoxy group, the carboxylic acid (c2) having a liquid crystal alignment group may be further reacted with the polyorganosiloxane. . Through the reaction, a polyorganosiloxane can be further introduced into a liquid crystal alignment group.

The specific polyorganosiloxane contained in the liquid crystal alignment agent of the present invention is preferably The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is 500 to 100,000, more preferably 1,000 to 30,000.

From the viewpoint of appropriately obtaining the effects of the present invention, the content of the polymer (A1) in the total amount of the polymer contained in the liquid crystal alignment agent is preferably 1% by weight or more, more preferably 3 The weight% or more is more preferably 5% by weight or more. Further, the content ratio of the polymerizable unsaturated bond to the total amount of the polymer component in the liquid crystal alignment agent is preferably set to be a polymerization property of 0 mmol/g to 15 mmol/g in total. The saturated bond is more preferably set to contain a polymerizable unsaturated bond of from 0.5 millimoles/g to 10 millimoles/g.

<Other ingredients>

The liquid crystal alignment agent of the present invention may contain other components as needed. Examples of the other component include a polymer other than the polymer (A1), a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), a functional decane compound, and the like.

[Other polymers]

The other polymers can be used to improve solution properties or electrical properties. The other polymer is a polymer having no polymerizable unsaturated bond, and specifically, for example, it may include a polyglycolic acid, a polyimine, a polyphthalate, a polyester, a polyamide, or the like. Polyorganosiloxane, cellulose derivative, polyacetal derivative, polystyrene derivative, poly(styrene-phenylmaleimide) derivative, poly(meth)acrylate derivative, etc. A main skeleton and a polymer having no polymerizable unsaturated bond in its side chain. Among these polymers, other polymers are preferably selected from the group consisting of polylysine, polyphthalate, At least one selected from the group consisting of polyimine and polyorganooxane, more preferably at least one selected from the group consisting of polylysine, polyimine, and polyorganosiloxane. .

Further, polyamic acid having no polymerizable unsaturated bond can be synthesized, for example, by reacting the tetracarboxylic dianhydride with the other diamine. A polyglycolate having no polymerizable unsaturated bond can be synthesized, for example, by a method of esterifying a polyamic acid having no polymerizable unsaturated bond; and a tetracarboxylic acid diester dichloride A method of reacting other diamines; a method of reacting a tetracarboxylic acid diester with the other diamine. Further, the polyimine which does not have a 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 can be synthesized, for example, by hydrolyzing at least one monomer selected from the group consisting of the decane compound (s2) and the decane compound (s3). The condensation is carried out, if necessary, with at least one selected from the group consisting of carboxylic acid (c2) and carboxylic acid (c3).

In the case where the other polymer is added to the liquid crystal alignment agent, the other polymer in the total amount of the polymer contained in the liquid crystal alignment agent from the viewpoint of not impairing the effects of the present invention The blending ratio is preferably 99% by weight or less, more preferably 96% by weight or less, still more preferably 0.1% by weight to 90% by weight.

The liquid crystal alignment agent of the present invention contains the polymer (A1) as an essential component, and preferred embodiments thereof include (I) an embodiment comprising only a polyorganosiloxane (A1) as a polymer component; (II) Carrying out only at least one selected from the group consisting of polyproline (A1) and polyimine (A1) as a polymer component And (III) an embodiment comprising a polyorganosiloxane (A1) and at least one selected from the group consisting of polyamic acid (A1) and polyimine (A1) as a polymer component; (IV) comprising a polyorganosiloxane (A1) and another polymer as a polymer component, and the other polymer is selected from the group consisting of polylysine and polyimine without a polymerizable unsaturated bond. An embodiment of at least one of the following; (V) comprising at least one selected from the group consisting of poly-proline (A1) and polyimine (A1), and other polymers as polymer components, and others The polymer is an embodiment selected from at least one selected from the group consisting of polyorganosiloxanes having no polymerizable unsaturated bonds, poly-proline and polyimine. Further, the blending ratio of the polyorganosiloxane, the polyamic acid, and the polyimine in each embodiment can be arbitrarily set depending on the use of the liquid crystal display element to be applied or the like.

In these embodiments, from the viewpoint of making the afterimage characteristics of the liquid crystal display element (especially, the characteristic of the afterimage which is less likely to be generated by the application of the AC voltage, hereinafter also referred to as "AC afterimage characteristic") is good, Preferably, the embodiments of (III) and (IV) are described. Further, the ratio of use of the polyorganooxane (A1) to the polyamic acid and the polyamidene (total) in the embodiments (III) and (IV) is preferably relative to the polyfluorene. 100 parts by weight of the total amount of the amine acid and the polyimine, and 1 part by weight to 50 parts by weight of the polyorganosiloxane (A1), more preferably 2 parts by weight to 35 parts by weight of the polyorganooxane (A1), further preferably, it contains 3 parts by weight to 25 parts by weight of the polyorganosiloxane (A1).

Further, in the present invention, it is presumed that a liquid crystal alignment film of a PSA mode liquid crystal display element can be formed by using a liquid crystal alignment agent containing a polymer (A1). When the liquid crystal cell is irradiated with light, the reaction of the photopolymerizable compound contained in the liquid crystal layer is also promoted from the liquid crystal alignment film side, and as a result, the effects of the present invention can be obtained.

[epoxy compound]

The epoxy compound can be used to improve the adhesion or electrical properties of the liquid crystal alignment film to the surface of the substrate. Here, examples of the epoxy compound include the following compounds: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol dihydrate. Glycerol ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol Diglycidyl ether, N,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-diglycidyl-amine Methylcyclohexane, N,N-diglycidyl-cyclohexylamine, and the like. In the case where the epoxy compound is added to the liquid crystal alignment agent, the compounding ratio of the epoxy compound is preferably 40 parts by weight or less based on 100 parts by weight of the total amount of the polymer contained in the liquid crystal alignment agent. More preferably, it is 0.1 weight part - 30 weight part.

[functional decane compound]

A functional decane compound can be used in order to improve the printability of the liquid crystal alignment agent. Examples of such a functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropylpropane. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxyfluorene Alkane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-triethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7-triaza Decane, 9-trimethoxydecyl-3,6-diazadecyl acetate, methyl 9-trimethoxydecyl-3,6-diazadecanoate, N-benzyl-3 -Aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, glycidoxymethyltrimethoxydecane, 2-glycidoxyethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, and the like.

In the case where these functional decane compounds are added to the liquid crystal alignment agent, the compounding ratio of the functional decane compound is preferably 2 parts by weight or less, more preferably 0.02% by weight based on 100 parts by weight of the total amount of the polymer. Parts ~ 0.2 parts by weight.

Further, in addition to the above-exemplified compounds, the other components may be a compound having at least one oxetanyl group in the molecule, an antioxidant, or the like.

<solvent>

The liquid crystal alignment agent of the present invention is preferably one which is obtained by dissolving a polymer component or other components arbitrarily formulated as needed in an organic solvent.

Here, examples of the solvent for preparing the liquid crystal alignment agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, and N,N-dimethylformamide. , N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, B Ethyl oxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, B Glycol ether acetate, two 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, Dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, propyl carbonate, and the like. These solvents may be used alone or in combination of two or more.

The solid content concentration of the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably selected. A range of 1% by weight to 10% by weight. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described below, and is preferably a coating film which is formed as a liquid crystal alignment film by heating or a coating film which becomes a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small, and it is difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large, and it is difficult to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases, and the coating property deteriorates.

The range of the particularly preferable solid content concentration differs depending on the method used when the liquid crystal alignment agent is coated on the substrate. For example, in the case of using the rotator method, it is particularly preferable to set the solid content concentration to a range of 1.5% by weight to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% by weight to 9% by weight, thereby setting the solution viscosity to 12 mPa. s~50mPa. The scope of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% by weight to 5% by weight, thereby setting the solution viscosity to 3 mPa. s~15mPa. s range. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C, more preferably from 20 ° C to 30 ° C.

<Liquid alignment film and liquid crystal display element>

The liquid crystal alignment film of the present invention is formed using a liquid crystal alignment agent prepared as described above, and is used as a liquid crystal alignment film of a PSA mode liquid crystal display element. Further, the PSA mode liquid crystal display device of the present invention includes the liquid crystal alignment film. The manufacturing method of the liquid crystal display element includes the following (i) to (iii); (i) the first step of applying the liquid crystal alignment agent of the present invention to the conductive film of a pair of substrates having a conductive film, and then (ii) in the second step, the liquid crystal cell is formed by arranging the pair of substrates on which the coating film is formed so as to face each other with the liquid crystal layer interposed therebetween through the liquid crystal layer containing the liquid crystal compound; (iii) In the third step, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates. Hereinafter, each of these steps will be described in detail.

[Step 1: Formation of coating film]

For the substrate, for example, glass such as float glass or soda glass may be used; and polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate may be used. A transparent substrate of plastic such as poly(alicyclic olefin). The conductive film preferably uses a transparent conductive film. For example, a Nesser (NESA) film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA) may be used, and indium oxide-tin oxide (In ₂ O ₃ - may be used). An Indium Tin Oxide (ITO) film of SnO ₂ ). The conductive film is preferably a patterned conductive film that is divided into a plurality of regions. When such a conductive film is provided, when a voltage is applied between the conductive films, the direction of the pretilt angle of the liquid crystal molecules can be changed in each region by applying a different voltage to each region, whereby the viewing angle characteristics can be further expanded.

The method of applying the liquid crystal alignment agent of the present invention on the formation surface of the transparent conductive film in a pair of substrates is preferably carried out by a plate printing method, a spin coating method, a roll coater method or an inkjet printing method. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, it is also possible to apply a functional decane compound or a functional titanium to the surface on the surface of the substrate where the coating film is to be formed. Pretreatment of compounds and the like.

After the liquid crystal alignment agent is applied onto the substrate, preheating (prebaking) is preferably performed in order to prevent dripping of the liquid crystal alignment agent to be applied. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, and particularly preferably from 40 ° C to 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Thereafter, a calcination (post-baking) step is carried out in order to completely remove the solvent and, if necessary, to thermally imidize the proline structure present in the polymer. The post-baking temperature is preferably from 80 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. Thus, the film thickness of the formed film is preferably 0.001 μm to 1 μm, more preferably 0.005 μm to 0.5 μm.

The organic solvent is removed by heating after coating the liquid crystal alignment agent to form a coating film (the coating film serves as an alignment film). At this time, the polymer contained in the liquid crystal alignment agent of the present invention is a polyamic acid, or a polyphthalate, or has a quinone imine. In the case of a quinone imidized polymer having a ring structure and a proline structure, a dehydration ring-closure reaction may be carried out by further heating after the formation of the coating film to form a coating film which is further imidized.

The coating film thus formed may be directly supplied to the second step described below, or may be subjected to a rubbing treatment on the surface of the coating film as needed, and then supplied to the second step. This rubbing treatment can be carried out by rubbing the surface of the coating film in a direction with a roll on which a cloth containing fibers such as nylon, rayon, cotton or the like is wound.

[Step 2: Construction of liquid crystal cell]

Two liquid crystal cells containing a liquid crystal compound and a photopolymerizable compound were placed between two substrates arranged in the opposite direction, and a liquid crystal cell was produced by preparing a liquid crystal cell containing a liquid crystal compound and a photopolymerizable compound. When manufacturing a liquid crystal cell, the following two methods are mentioned, for example. The first method is a method that has been known for a long time (vacuum injection method). First, the gaps (cell gaps) are left in the liquid crystal alignment film, and the two substrates are arranged to face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the cell gap is defined by the surface of the substrate and the sealant. After filling the liquid crystal compound and the photopolymerizable compound into the inside, the injection hole is sealed to produce a liquid crystal cell. The second method is a method called a One Drop Fill (ODF) method. Applying, for example, an ultraviolet curable sealing material to a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, and further instilling a liquid crystal compound and light on a predetermined portion of the liquid crystal alignment film surface After the mixture of the polymerizable compounds, the other substrate is bonded in such a manner that the liquid crystal alignment film faces each other, and the liquid crystal compound is pushed over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant. Thereby, a liquid crystal cell is manufactured.

In the case of using any of the methods, the liquid crystal cell produced as described above can be further heated until the liquid crystal compound used has a temperature in the in-phase direction, and then gradually cooled to room temperature. The flow alignment at the time of liquid crystal filling is removed.

As the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used.

As the liquid crystal compound, a nematic liquid crystal having a negative dielectric anisotropy can be preferably used. For example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, or an oxygen couple can be used. A nitrogen-based liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, a terphenyl liquid crystal, or the like. In addition, from the viewpoint of further increasing the response speed of the PSA mode liquid crystal display device, the liquid crystal compound preferably uses an alkenyl liquid crystal in combination, and the alkenyl liquid crystal is a single one having an alkenyl group and a fluoroalkenyl group. A functional liquid crystalline compound. As the above-mentioned alkenyl-based liquid crystal, a compound which is conventionally known can be used, and examples thereof include a compound represented by the following formula (L1-1) to formula (L1-9).

[Chem. 24]

The photopolymerizable compound can be used with an acrylonitrile group or a methacrylium group. A compound capable of undergoing radical polymerization of a functional group such as a group or a vinyl group. From the viewpoint of reactivity, it is preferred to use a polyfunctional compound having an acryloyl group or a methacryl group. In addition, from the viewpoint of stably maintaining the alignment property of the liquid crystal molecules, the photopolymerizable compound is preferably a compound having a total of two or more cyclohexane rings and a benzene ring as a liquid crystal skeleton. Further, as the photopolymerizable compound, a compound which is conventionally known can be used. The compounding ratio of the photopolymerizable compound is preferably set to 0.1% by weight to 0.5% by weight based on the total amount of the liquid crystalline compound to be used. Further, the thickness of the liquid crystal layer is preferably set to 1 μm to 5 μm.

[Step 3: Light irradiation step]

After the liquid crystal cell is constructed, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be set, for example, to a direct current or an alternating current of 5V to 50V. Further, as the light to be irradiated, for example, ultraviolet light and visible light including light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet light containing light having a wavelength of 300 nm to 400 nm is preferable. As the light source for illuminating light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. Further, the ultraviolet light preferably in the wavelength region can be obtained by a method of using a light source in combination with, for example, a filter, a diffraction grating, or the like. The irradiation amount of light is preferably 1,000 J/m ² or more and less than 200,000 J/m ² , more preferably 1,000 J/m to 100,000 J/m ² .

Then, a polarizing plate is attached to the outer surface of the liquid crystal cell after light irradiation, whereby a PSA mode liquid crystal display element can be obtained. The polarizing plate used herein may be a polarizing plate called a "H film" obtained by stretching a polyvinyl alcohol while absorbing iodine on one side of a polyvinyl acetate protective film, or may contain only H. The polarizing plate of the film itself.

The PSA mode liquid crystal display element of the present invention can be effectively applied to various devices, for example, can be used for a clock, a handheld game machine, a word processor, a notebook computer, a car navigation system, a video camera ( Various display devices such as camcorder), personal digital assistant (PDA), digital camera, mobile phone, smart phone, various monitors, LCD TVs, information displays, and the like.

[Examples]

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

The weight average molecular weight, the epoxy equivalent of each polymer in each synthesis example, the solution viscosity of each polymer solution, and the oxime imidization ratio of a poly Method to determine.

[weight average molecular weight of polymer]

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

Pipe column: manufactured by Tosoh (stock), TSK gel GRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf/cm ²

[epoxy equivalent]

The epoxy equivalent is a value measured by the "hydrochloric acid-methyl ethyl ketone method" according to Japanese Industrial Standards (JIS) C2105.

[Solid viscosity of polymer solution]

Solution viscosity of polymer solution [mPa. s] was prepared by using a predetermined solvent to prepare a polymer concentration of 10% by weight, and the obtained solution was measured at 25 ° C using an E-type rotational viscometer.

[醯Iminization rate of polyimine]

The solution of polyimine is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, and tetramethyl decane is used as a standard substance at room temperature. ¹ H-NMR (Nuclear Magnetic Resonance, NMR) was measured. From the obtained ¹ H-NMR spectrum, the oxime imidization ratio [%] was determined from the formula represented by the following formula (x).

醯imination rate [%]=(1-A ¹ /A ² ×α)×100...(x)

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

<Synthesis of Polymer>

[Synthesis Example P1: Polyimine synthesis of polymer (A1)]

220 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 3-(2,4-diaminophenoxy)cholesterium as diamine 150 g (0.3 mol), 2-(2,4-diaminophenoxy)ethyl methacrylate (the compound represented by the formula (E1-1-6)) 47 g (0.2 mol), And 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine 133 g (0.5 mol) dissolved in N-methyl-2 In 2,200 g of pyrrolidone (NMP), the reaction was carried out at 60 ° C for 6 hours to obtain a solution containing poly-proline. The obtained polyamic acid solution is divided into small amounts and the measured solution viscosity is about 1,400 mPa. s.

Then, 2,800 g of NMP was added to the obtained polyamic acid solution, and 79 g of pyridine and 100 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system is subjected to solvent replacement using a new NMP (by this operation, pyridine and acetic anhydride used in the dehydration ring-closure reaction are removed to the outside of the system), thereby obtaining about 15% by weight of the polymer as a polymer. (A1) a solution of polyimine (P-1). The obtained ruthenium imine (P-1) had a ruthenium iodide ratio of about 51%.

[Synthesis Example P2: Polylysine Synthesis of Polymer (A1)]

200 g (1.0 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, and 3-(3,5-diaminobenzyl hydrazine as diamine Cetyl 52g (0.1 mol), 4-(2-propynyloxy)benzene-1,3-diamine (the compound represented by the formula (E1-5-1)) 26 g (0.2 mol) And 2,2'-dimethyl-4,4'-diaminobiphenyl 150g (0.7 mole) dissolved in a mixed solvent containing NMP 3,100g and γ-butyrolactone 760g at 40 ° C The reaction was carried out for 3 hours, whereby a solution containing 10% by weight of poly-proline (P-2) as the polymer (A1) was obtained. The solution viscosity of the polyaminic acid solution is 170 m Pa. s.

[Synthesis Example P3: Polyimine synthesis of other polymers]

220 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 3-(2,4-diaminophenoxy)cholestane as diamine 74 g (0.15 mol), 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine 40 g (0.15 mol), and 110 g (0.7 mol) of 3,5-diaminobenzoic acid was dissolved in 1,800 g of NMP, and reacted at 60 ° C for 6 hours to obtain a solution containing polyglycine. The obtained polyglycine solution was fractionated to determine a solution viscosity of about 1,300 mPa. s.

Then, 2,200 g of NMP was added to the obtained polyamic acid solution, and 120 g of pyridine and 150 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was subjected to solvent replacement using a new NMP, thereby obtaining a solution containing about 15% by weight of polyimine (P-3) as another polymer. The obtained ruthenium imine (P-3) had a ruthenium amination ratio of about 67%.

[Synthesis Example P4: Polylysine Synthesis of Other Polymers]

220 g (1.0 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 4-(2-(4-pentylcyclohexyl) as diamine Phenoxy)ethoxy)benzene-1,3-diamine 79g (0.2 mol), 4,4'-diaminodiphenylmethane 40 g (0.2 mol), and 2,5-diamino group 91 g (0.6 mol) of benzoic acid was dissolved in a mixed solvent containing 2,700 g of NMP and 1,200 g of γ-butyrolactone, and reacted at 40 ° C for 3 hours, thereby obtaining a polymer containing 10% by weight as another polymer. A solution of proline (P-4). The solution viscosity of the polyaminic acid solution is 160 mPa. s.

[Synthesis Example S1: Synthesis of Polyorganosiloxane of Polymer (A1)]

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECETS) 197 g and 3- as a hydrolyzable decane compound were added to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. Methyl propylene methoxy propyl trimethoxy decane (GMPTS) 50 g (ECETS: GMPTS = 80:20 (mole ratio)), methyl isobutyl ketone 500 g as a solvent, and triethylamine 10.0 g as a catalyst , mix at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was stirred under reflux for 6 hours at 80 ° C while stirring. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the water after washing became neutral, and the solvent and water were distilled off under reduced pressure to obtain a viscous transparent liquid. A hydrolysis condensate of an epoxy group.

When ¹ H-NMR analysis of the hydrolysis-condensation product was carried out, a peak attributed to the theoretical strength to the epoxy group was obtained in the vicinity of the chemical shift (δ) = 3.2 ppm, and it was confirmed that the side reaction of the epoxy group was not caused in the reaction.

Then, the obtained hydrolysis condensate is reacted with a carboxylic acid. First, at 200mL In the three-necked flask, the obtained hydrolysis-condensation product having an epoxy group was added, and 30.0 g of methyl isobutyl ketone as a solvent and 75.1 g of 4-octyloxybenzoic acid (OCTBA) as a carboxylic acid were added ( 30 mol% of the total amount of the hydrolyzable decane compound used as a raw material, 38 mol%) and 11-(4-cyclohexylphenoxy) with respect to the epoxy group which the said hydrolyzed condensate has. 36.1 g of undecanoic acid (corresponding to 10 mol% based on the total amount of the hydrolyzable decane compound used as a raw material), UCAT 18X (trade name, San-Apro), epoxy as a catalyst 0.10 g of a hardening accelerator of the compound was stirred at 100 ° C for 48 hours to carry out a reaction. After the completion of the reaction, ethyl acetate was added to the reaction mixture, and the obtained organic layer was washed with water three times, dried over magnesium sulfate, and then the solvent was distilled away to obtain a polyorganooxane as a polymer (A1). S-1) 287.2 g. The polystyrene-equivalent weight average molecular weight Mw obtained by measuring the polyorganosiloxane (S-1) by gel permeation chromatography (GPC) was 7,300.

[Synthesis Example S2 - Synthesis Example S4, Synthesis Example S6: Synthesis of Polyorganosiloxane)

In the same manner as in Synthesis Example S1, except that the type and amount of the hydrolyzable decane compound and the carboxylic acid were set as described in the following Table 1, the polyorganosiloxane was obtained as the polymer (A1). S-2)~ polyorganosiloxane (S-3), polyorganosiloxane (S-6), and polyorganosiloxane (S-4) as another polymer. The yield and Mw of these polyorganosiloxanes are shown in Table 1 below.

The abbreviations of the respective compounds in Table 1 are respectively the following meanings.

(hydrolyzable decane compound)

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

GMPTS: 3-methacryloxypropyltrimethoxydecane

TEOS: tetraethoxy decane

ODES: octadecyltriethoxydecane

VTES: vinyl triethoxy decane

(carboxylic acid)

OCTBA: 4-octyloxybenzoic acid

CPUA: 11-(4-cyclohexylphenoxy)undecanoic acid

PCHBA: 4-(4-pentylcyclohexyl)benzoic acid

ABAMPO: 4-(3-(propylene decyloxy)-2,2-bis((acryloxy)methyl)propoxy)-4-oxobutanoic acid (the formula ( Compound represented by C1-3-1)

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

SACY: succinic acid = 5 ξ-cholest-3-yl ester

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

VCHCHUA: 11-((4'-vinyl-[1,1'-bis(cyclohexane))-4-yl)oxy)undecanoic acid (expressed by the formula (C1-1-10)) compound of)

[化25]

Further, the "mol ratio" of the hydrolyzable decane compound in Table 1 indicates the ratio of use of each decane compound to the total amount of the hydrolyzable decane compound to be used. Further, the "mol ratio" of the carboxylic acid means the ratio of use of each carboxylic acid to the total amount of the hydrolyzable decane compound to be used. In Synthesis Example S1 to Synthesis Example S4 and Synthesis Example S6, two kinds of carboxylic acids were used for each synthesis example.

[Synthesis Example S5: Synthesis of Polyorganosiloxane of Polymer (A1)]

52.8 g of ethanol was placed in a four-neck reaction flask equipped with a reflux tube, and 20.0 g of oxalic acid was added little by little to the ethanol under stirring to prepare an ethanol solution of oxalic acid. Then, the solution was heated to its reflux temperature, and 20.8 g of tetraethoxysilane, 4.2 g of octadecyltriethoxydecane, and 1.9 g of vinyltriethoxydecane were added dropwise to the solution under reflux. mixture. After the completion of the dropwise addition, the mixture was further heated under reflux for 5 hours, and then cooled, and 75 g of butyl cellosolve was added to prepare a solution containing polyorganosiloxane (S-5), which was prepared. 5) SiO ₂ concentration of 4% by weight. The solution was analyzed by gas chromatography, and as a result, no alkoxydecane monomer was detected.

<Preparation of liquid crystal composition>

[Preparation of Liquid Crystal Composition LC1]

5% by weight of the liquid crystal compound represented by the above formula (L1-1) and 0.3% by weight of the following formula (L2-1) were added to 10 g of a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-6608). The photopolymerizable compound is mixed and mixed A liquid crystal composition LC1 was obtained.

[Preparation of Liquid Crystal Composition LC2]

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

<Example 1>

[Preparation of Liquid Crystal Aligning Agent]

The solution containing polyimine (P-1) and the solution containing poly-proline (P-2) are made into polyimine (P-1): poly-proline (P-) by weight of each solid component. 2) = 20:80, and NMP and butyl cellosolve (BC) as an organic solvent are added to the mixed solution to prepare a solvent composition of NMP: BC = 50:50 (weight ratio), and the solid content concentration is 6.0% by weight solution. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent.

[Manufacture of liquid crystal cell]

Using the prepared liquid crystal alignment agent, the presence or absence of the pattern of the transparent electrode and the amount of ultraviolet irradiation (2 levels) were changed to produce a total of four liquid crystal cells. In addition, various characteristics of these liquid crystal cells were evaluated.

[Manufacture of liquid crystal cell with transparent electrode without pattern]

The prepared liquid crystal alignment agent was applied on a transparent electrode surface of a glass substrate having a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Nippon Photographic Co., Ltd.), and a hot plate at 80 ° C was used. After heating (prebaking) for 1 minute to remove the solvent, it was heated (post-baked) on a hot plate at 150 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å.

The coating film was subjected to rubbing treatment under the conditions of a roller rotation speed of 400 rpm, a table moving speed of 3 cm/s, and a hair pressing length of 0.1 mm by using a friction machine having a roller on which the rayon cloth was wound. . Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a clean oven at 100 ° C for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two sheets) substrates having a liquid crystal alignment film. Further, this rubbing treatment is a weak rubbing treatment for the purpose of controlling the tilting of the liquid crystal and the alignment by a simple method.

Then, for one of the pair of substrates, an epoxy resin adhesive to which an alumina ball having a diameter of 3.5 μm is applied is coated on the outer edge of the surface having the liquid crystal alignment film, and then a pair of substrates are The liquid crystal alignment film faces are overlapped and crimped to harden the adhesive. Next, the prepared liquid crystal composition LC1 was filled between a pair of substrates from a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell.

The above operation was repeated to fabricate two liquid crystal cells having a transparent electrode without a pattern. One of them is directly supplied for the evaluation of the voltage holding ratio. In the other liquid crystal cell, an alternating current of 10 volts was applied to the conductive film at a frequency of 60 Hz, and the ultraviolet ray irradiation device using a metal halide lamp as a light source was used to irradiate the ultraviolet ray at an irradiation dose of 100,000 J/m ² in a liquid crystal driving state. . Further, the irradiation amount is a value measured by using a light meter measured with a wavelength of 365 nm.

[Evaluation of voltage retention rate]

A voltage of 5 V was applied to each of the liquid crystal cells manufactured at 23 ° C under the conditions of an application time of 60 μsec and a span of 167 msec, and the voltage holding ratio after 167 msec from the release of the application was measured. (VHR). The measurement results are shown in Table 2 below. Further, the measuring device was VHR-1 manufactured by Toyo Corporation (TOYO Corporation).

[Manufacture of liquid crystal cell having patterned transparent electrode]

The prepared liquid crystal alignment agent of Example 1 was coated with an ITO electrode (patterned as a strip as shown in FIG. 1) using a liquid crystal alignment film printer (manufactured by Nippon Photoprint Co., Ltd.). Each of the electrode faces of the two glass substrates divided into a plurality of regions was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated on a hot plate at 150 ° C for 10 minutes ( After baking, a coating film having an average film thickness of 600 Å was formed. The coating film was ultrasonically washed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of (two sheets) substrates having a liquid crystal alignment film. Further, the pattern of the electrodes used is the same pattern of the electrode patterns of the PSA mode.

Then, on the outer edges of the surfaces of the pair of substrates having the liquid crystal alignment film, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied, and the liquid crystal alignment film faces are opposed to each other. The method is overlapped and crimped to harden the adhesive. Then, the prepared liquid crystal composition LC1 was filled between a pair of substrates from a liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a liquid crystal cell.

The operation was repeated to fabricate a total of two liquid crystal cells having patterned transparent electrodes. One of them was directly supplied for evaluation of the characteristics of the AC afterimage described later. In the same manner as in the case of producing a liquid crystal display element having a transparent electrode having no pattern, the liquid crystal cell is irradiated with light at a dose of 100,000 J/m ² in a state where a voltage is applied between the conductive films. For evaluation of AC afterimage characteristics.

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

For the manufactured liquid crystal cell, according to "TJ Scheffer et. al., Applied Physics Journal (J. Appl. Phys.) vol 48, p1783 (1977)", and "F. Nakano et al. (F. Nakano, et. al.), Japanese Journal of Applied Physics (JPN. J. Appl. Phys.) vol. 19, p2013 (1980)", using a rotary crystallization method using a He-Ne laser The measurement was carried out. The measurement was performed on a pretilt angle (initial pretilt angle θ ini) before applying a voltage to the liquid crystal cell, and a pretilt angle (pretilt angle θ ac after driving) after driving for 13 hours at room temperature with an alternating current (AC) of 9 V. . Further, the pretilt angle change rate β [%] is calculated by the following formula (y). The case where the pretilt angle change rate β is less than 3% is evaluated as “good”, and the case where the pretilt angle change rate β is 3% or more and less than 5% is evaluated as “good”, and the pretilt angle change rate β is 5% or more. The situation was evaluated as "bad". The results are shown in Table 2 below.

Pretilt angle change rate β[%]=(θ ac-θ ini)/θ ini×100...(y)

Further, the "parts by weight" in the Table 2 indicates the blending amount of each component with respect to 100 parts by weight of the total amount of the liquid crystal alignment agent.

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

A liquid crystal alignment agent was prepared in the same manner as in Example 1 except that the kind and amount of the polymer used for preparing the liquid crystal alignment agent were changed as shown in Table 2. Further, polyorganosiloxane (S-1) to polyorganosiloxane (S-4) and polyorganosiloxane (S-6) are dissolved in NMP and then supplied to prepare a liquid crystal alignment agent. With regard to the polyorganosiloxane (S-5), the reaction solution is poured into a large excess of methanol to precipitate a reaction product, and the precipitate is washed with methanol, and then dried under reduced pressure at 40 ° C for 15 hours. The resulting powder was dissolved in NMP for preparation of a liquid crystal alignment agent. Further, using these liquid crystal alignment agents, liquid crystal cells were produced in the same manner as in Example 1, and evaluation of the liquid crystal cells produced was performed. Further, in Example 6, Example 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 of these are shown in Table 2.

[Evaluation of high speed responsiveness]

<Example 6A>

The liquid crystal cell having the transparent electrode having no pattern produced in Example 6 was used to evaluate the high-speed response of the liquid crystal molecules. The manufactured liquid crystal cell is sandwiched by two polarizing plates arranged in a state of orthogonal polarization, and then, the visible light lamp is first irradiated without applying a voltage, and the transmitted liquid crystal is measured by a photo multimeter. The brightness of the light of the unit, set its value to phase The transmittance is 0%. Then, an alternating current of 5 V was applied to the electrodes of the liquid crystal cell for 5 seconds, and the transmittance at this time was measured in the same manner as described above, and the value was set to 100% relative transmittance. When an alternating current of 5 V was applied to each liquid crystal cell, the time until the relative transmittance became 90% from 10% was measured, and this time was defined as the response speed. When the response speed was less than 5 msec, it was judged that the high-speed responsiveness was "good", and the case where the response speed was 5 msec or more was judged as high-speed responsiveness "good" and evaluated. As a result, the high-speed response of the liquid crystal cell of Example 6 was "good".

<Example 12A and Comparative Example 1A>

The response speed of the liquid crystal molecules was evaluated by the same operation as in the above-described Example 6A, except that the liquid crystal cells used were changed to the liquid crystal cells of Example 12 and Comparative Example 1. The results are shown in Table 3 below.

<Example 10>

[Preparation of Liquid Crystal Aligning Agent]

After dissolving the polyorganosiloxane (S-1) obtained in the synthesis example S1 in NMP, the solution containing the polyorganosiloxane and the other polymer obtained in the synthesis example P3 were used. The solution of the polyimine (P-3) was mixed so that the weight of the solid component became polyimine (P-3): polyorganosiloxane (S-1) = 90:5. Then, after adding NMP and BC, an equal amount (by weight) of N,N,N',N'-tetraglycidyl-4,4'-diamino group is added with polyorganosiloxane (S-1). Diphenylmethane was prepared as 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 size of 1 μm, thereby preparing a liquid crystal alignment agent. In addition, the liquid crystal cell was produced and evaluated in the same manner as in Example 1 except that the liquid crystal alignment agent used was changed. The evaluation results are shown together in Table 2.

In Comparative Example 1 and Comparative Example 2, the decrease in the voltage holding ratio caused by the ultraviolet irradiation and the decrease in the AC afterimage characteristics were remarkably exhibited. On the other hand, in Examples 1 to 12, even after the ultraviolet irradiation, the high voltage holding ratio was maintained, and the AC afterimage characteristics were also good. Among them, in Example 3, Example 6, Example 7, Example 9, Example 11, and Example 12, the AC afterimage characteristics were particularly good, and these examples were carried out using polyglycine and polyimine. At least any one of them is a liquid crystal alignment agent with a polyorganosiloxane (A1) as a polymer. According to these results, when an alkenyl-based liquid crystal is used in the PSA mode to achieve high-speed response of the liquid crystal panel, the liquid crystal alignment film can be formed by using a liquid crystal alignment agent containing the polymer (A1). The decrease in the voltage holding ratio caused by the ultraviolet irradiation is suppressed, and the AC afterimage characteristics can be made good. Further, from the results of Example 6A and Example 12A, it was found that a liquid crystal display element having high high-speed response can be obtained.

Further, the liquid crystal alignment of the first to twelfth embodiments was used except that the pattern of the ITO electrode on the glass substrate was changed to a fish bone-like electrode pattern as shown in FIGS. 2 and 3, respectively. A liquid crystal cell was produced and evaluated in the same manner as in Example 1. Also in this case, the same effects as those of the first to the twelfth embodiments are also exhibited.

1‧‧‧ITO electrode

2‧‧‧ Department

Claims (8)

A liquid crystal alignment agent for a PSA mode liquid crystal display device, which comprises a polymer (A1) having a polymerizable unsaturated bond. The liquid crystal alignment element for a PSA mode liquid crystal display device according to claim 1, wherein the liquid crystal display element is a liquid crystal display element containing a monofunctional liquid crystal compound in a liquid crystal layer, the monofunctional The liquid crystalline compound has either an alkenyl group or a fluoroalkenyl group. The liquid crystal alignment agent for a PSA mode liquid crystal display device according to the above aspect, wherein the polymer (A1) has a group selected from the group consisting of the following formula (f1), At least one of the group represented by the formula (f2) and the group represented by the following formula (f3) is a group containing a polymerizable unsaturated bond, In the formula (f1), R ¹ , R ⁴ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a substituted alkyl group having 1 to 5 carbon atoms; and in the formula (f2), 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; in the formulae (f1) to (f3), * represents a bonding bond. The liquid crystal alignment agent for a PSA mode liquid crystal display device according to claim 1 or 2, wherein the polymer (A1) is selected from the group consisting of polyproline, polyphthalate, and polyphthalamide. In the group consisting of amines and polyorganosiloxanes One less. A method of producing a liquid crystal display device, comprising the steps of: coating a liquid crystal alignment agent for a PSA mode liquid crystal display device according to any one of claims 1 to 4, respectively a conductive film formed on a pair of substrates having a conductive film, and then heated to form a coating film; and a second step of forming a pair of substrates on which the coating film is formed via a liquid crystal layer containing a liquid crystalline compound The liquid crystal cell is configured to face each other in such a manner that the coating film faces each other; and in the third step, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates. The method for producing a liquid crystal display device according to claim 5, wherein the liquid crystal layer contains a monofunctional liquid crystal compound having an alkenyl group and a fluoroalkenyl group. Any of them. A liquid crystal alignment film for a PSA mode liquid crystal display device, which is formed by using a liquid crystal alignment agent for a PSA mode liquid crystal display device according to any one of claims 1 to 4. A PSA mode liquid crystal display device comprising the liquid crystal alignment film for a PSA mode liquid crystal display device according to claim 7 of the invention.