KR20190102074A - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal element, and polyorganosiloxane - Google Patents

Abstract

The silicon-containing compound which has a cyclic ether group and the functional group (B) which reacts with a cyclic ether group is contained in a liquid crystal aligning agent. An example of the functional group (B) which a silicon-containing compound has is a functional group which reacts with a cyclic ether group by heat. One example of a silicon-containing compound is polymer [P] having a siloxane skeleton.

Description

Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal element, and polyorganosiloxane

(Cross-reference of related application)

This application is based on the JP Patent application 2017-43288 of an application on March 7, 2017, and uses the content of the description here.

The present disclosure relates to a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal element, and a polyorganosiloxane.

As the liquid crystal element, a liquid crystal element using a nematic liquid crystal having positive dielectric anisotropy, represented by a twisted nematic (TN) type, a super twisted nematic (STN) type, or the like, or a vertical using a nematic liquid crystal having negative dielectric anisotropy A homogeneous oriented liquid crystal represented by a VA (Vertical Alignment) type liquid crystal device, an In-Plane Switching (IPS) type, a FFS (Fringe Field Switching) type, and the like in a meotropic alignment mode is provided in parallel with the substrate. Various liquid crystal elements, such as a transverse electric field type liquid crystal element for switching, are known.

These liquid crystal elements are provided with the liquid crystal aligning film which has a function which orientates liquid crystal molecules in a fixed direction. As a material used for preparation of this liquid crystal aligning film, polyamic acid, polyimide, polyamide, polyester, polyorganosiloxane, etc. are known, In particular, polyamic acid and polyimide have heat resistance, mechanical strength, and affinity with liquid crystal molecules. It is used preferably from a long time in view of this outstanding point etc. (for example, refer patent documents 1-3). At the time of manufacture of a liquid crystal element, a liquid crystal aligning film is formed using the liquid crystal aligning agent in which these polymer components are melt | dissolved in the organic solvent.

In addition, Patent Document 4 discloses a liquid crystal aligning agent containing a polyorganosiloxane obtained by reacting a mixture of a trifunctional and tetrafunctional hydrolyzable silane compound in the presence of oxalic acid and an alcohol. In patent document 4, it is demonstrated that the liquid crystal aligning film formed from such a liquid crystal aligning agent is excellent in a perpendicular alignment property and heat resistance.

In the past, televisions, mobile tablets, and the like have been major markets for liquid crystal devices, but in recent years, the field of activity as display devices has been expanded. Liquid crystal devices have been found in a wide variety of new applications such as in-vehicle devices, digital signage, and industrial applications, and have been used in various cases.

Japanese Patent Application Laid-open No. Hei 4-153622 Japanese Laid-Open Patent Publication No. 56-91277 Japanese Patent Application Laid-Open No. 11-258605 Japanese Patent Laid-Open No. 9-281502

The new market of liquid crystal elements may require durability in an excessive use environment, and high reliability is required in the prior art. For example, in the case of high temperature in summer and use in a tropical region, long-term heat resistance (thermal reliability) is required. On the other hand, the display quality of a liquid crystal display panel has the large contribution rate of the liquid crystal aligning film which is in direct contact with a liquid crystal layer. Therefore, as a liquid crystal aligning film, even when a liquid crystal display panel is exposed to high temperature conditions, it is hard to change a voltage holding ratio and a drive characteristic, and it is necessary that it is hard to produce the fall of display quality.

The present disclosure has been made in view of the above circumstances, and one object thereof is to provide a liquid crystal device having excellent heat reliability.

According to the present disclosure, the following means are provided.

Liquid crystal aligning agent containing the silicon-containing compound which has a functional group (B) which reacts with a <1> cyclic ring ether group and a cyclic ether group.

<2> The liquid crystal aligning film formed using the liquid crystal aligning agent of said <1>.

<3> The liquid crystal element provided with the liquid crystal aligning film of said <2>.

Polyorganosiloxane which has a functional group (B) which reacts with a <4> 'cyclic ether group and a cyclic ether group.

According to the liquid crystal aligning agent of this indication, the liquid crystal element excellent in the heat | fever reliability can be obtained.

(Form to carry out invention)

≪Liquid crystal aligning agent≫

The liquid crystal aligning agent of this indication contains the silicon-containing compound (henceforth "a silicon-containing compound [A]") which has a cyclic ether group and the functional group which reacts with a cyclic ether group. Silicon-containing compound [A] has a high thermal stability silicon containing structure and self-crosslinkable group. Below, each component contained in the liquid crystal aligning agent of this indication, and the other component arbitrarily mix | blended as needed are demonstrated.

<Silicon-containing compound [A]>

Since the cyclic ether group which silicon-containing compound [A] has is high in heat reactivity, it is preferable that it is an oxetanyl group or an oxiranyl group, and it is more preferable that it is an oxiranyl group. Since the functional group (henceforth "functional group (B)") which reacts with a cyclic ether group can self-crosslink using heating at the time of postbaking, it can make storage stability of a liquid crystal aligning agent more favorable, It is preferable that it is a functional group which reacts with a cyclic ether group by heat. Specific examples of the functional group (B) include a carboxyl group, an isocyanate group, a hydroxyl group, an amino group, an alkoxymethyl group, and a group in which a carboxyl group, an isocyanate group, a hydroxyl group, or an amino group is protected with a protecting group. The functional group (B) is better in storage stability and higher in reactivity with a cyclic ether group by heating, and among them, the carboxyl group or the protected carboxyl group (hereinafter also referred to as "protective carboxyl group"). It is preferable.

It is preferable that a protective carboxyl group detach | desorbs by heat and produces | generates a carboxyl group. As a specific example of a protective carboxyl group, the structure represented by following formula (1), the acetal ester structure of carboxylic acid, the ketal ester structure of carboxylic acid, etc. are mentioned.

(In formula (1), R <^11> , R <^12> and R <^13> is respectively independently a C1-C10 alkyl group or a C3-C20 monovalent alicyclic hydrocarbon group, or R <^11> and R <^12> mutually couple | bonds each other. and R ¹¹ and R ¹² are together with the carbon atom to form a divalent alicyclic hydrocarbon group or a cyclic ether of 4 to 20 carbon atoms, which, coupled also R ¹³ is an alkyl group of 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms Or an aryl group having 6 to 20 carbon atoms, where "*" represents a bond.)

As a silicon-containing compound [A], a low molecular silane compound, a polyorganosiloxane, etc. are mentioned. When silicon-containing compound [A] is a low molecular silane compound, the alkoxysilane compound etc. which have a cyclic ether group and a functional group (B) are mentioned, for example. The silicon-containing compound [A] has a siloxane skeleton especially in the point that the liquid crystal element with a more improved effect of the reliability about heat, the solvent resistance of the liquid crystal aligning film obtained is high, and a liquid crystal alignability and a voltage holding ratio more favorable are obtained. It is preferable that it is a polymer, ie, polyorganosiloxane (henceforth "polymer [P]") which has a cyclic ether group and a functional group (B).

<Polymer [P]>

Although the synthesis | combining method of polymer [P] is not specifically limited, The following methods 1-method 3 are mentioned as a preferable synthesis method.

Method 1; The polyorganosiloxane which has a cyclic ether group in a side chain by hydrolytically condensing a hydrolyzable silane compound (S1) which has a cyclic ether group, or a mixture of a silane compound (S1) and another hydrolyzable silane compound (following) , Also referred to as "polyorganosiloxane (E)", followed by reacting the polyorganosiloxane (E) with a carbonic acid having an amino group (hereinafter also referred to as "amino group-containing carbonic acid"). The method which obtains the polyorganosiloxane which has in a side chain, and makes the obtained amino group containing polyorganosiloxane and carbonic anhydride react.

Method 2; The amino group and A method of synthesizing a polyorganosiloxane (hereinafter also referred to as "polyorganosiloxane (M)") having a cyclic ether group in a side chain, and then reacting the obtained polyorganosiloxane (M) with a carboxylic anhydride.

Method 3; Polyorganosiloxane (E) is synthesize | combined by hydrolyzing and condensing a silane compound (S1) alone or the mixture of a silane compound (S1) and another hydrolysable silane compound, and then a polyorganosiloxane (E) And a method for reacting the amino group-containing carboxylic acid.

Among these, it is preferable to use the method 1 from the point which the polymer which is simple and has high solubility with respect to a solvent, and high heat resistance is obtained.

As the silane compound (S1), a hydrolyzable silane compound having an oxetanyl group or an oxiranyl group can be preferably used. As specific examples thereof, for example, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (meth (Acrylic acid) (3-ethyloxetan-3-yl) methyl, (meth) acrylic acid (3-methyloxetan-3-yl) methyl, etc. are mentioned. In addition, a silane compound (S1) may be used individually by 1 type, and may be used in combination of 2 or more type.

As the silane compound (S2), a hydrolyzable silane compound having a primary amino group or a secondary amino group can be preferably used. As specific examples thereof, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like. In addition, a silane compound (S2) may be used individually by 1 type, and may be used in combination of 2 or more type.

Other silane compounds are silane compounds other than the silane compound (S1) and the silane compound (S2), and are not particularly limited. Examples thereof include tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane;

Alkyl group or aryl group containing alkoxysilane compounds, such as methyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, and dimethyl diethoxysilane;

Sulfur-containing alkoxysilane compounds such as 3-mercaptopropyltriethoxysilane and mercaptomethyltriethoxysilane;

Unsaturated bond-containing alkoxy such as 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane Silane compounds;

Acid anhydride group-containing alkoxysilane compounds such as trimethoxysilylpropylsuccinic anhydride;

N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Nitrogen containing alkoxysilane compounds, such as dimethyl- butylidene) propylamine, etc. are mentioned. As other silane compounds, these 1 type may be used independently and may be used in combination of 2 or more type.

Examples of the amino group-containing carbonic acid include 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, 6-amino-2-naphthoic acid, β-alanine, and glycine. And 3-aminocyclopentanecarboxylic acid, 5-aminopentanoic acid, 4-aminohydrocinnamic acid, 4-aminophenylacetic acid, 4- (aminomethyl) benzoic acid, and the like. An amino group containing carboxylic acid may be used individually by 1 type, and may be used in combination of 2 or more type.

Carbonic anhydride should just have one acid anhydride group, and the remainder of structure is not specifically limited. Examples of the carbonic anhydride include trimellitic anhydride, 4-nitrophthalic anhydride, 3-nitrophthalic anhydride, 4-ethynylphthalic anhydride, 4- (1-propynyl) phthalic anhydride, and 4-phenylethynylphthalic acid. Anhydride, 4-methylphthalic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, allyl succinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic acid anhydride, cis- 4-cyclohexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, homophthalic anhydride, glutaric anhydride, 3-trimethoxysilylpropyl succinic anhydride, cyclohexane-1 And 2,4-tricarboxylic acid-1,2-anhydride. Carbonic anhydride may be used individually by these 1 type, and may be used in combination of 2 or more type.

(Hydrolysis condensation reaction)

In the method 1 to method 3, the hydrolytic condensation reaction using the hydrolyzable silane compound comprises one or two or more kinds of the hydrolyzable silane compound as described above and water, preferably in the presence of a suitable catalyst and an organic solvent. The reaction is carried out. In the method 1 and the method 3, it is preferable that it is 5 mol% or more with respect to the total amount of the monomer used for the synthesis | combination of a polyorganosiloxane, and, as for the usage ratio of a silane compound (S1), it is more preferable that it is 10 mol% or more.

In addition, in the method 2, it is preferable to set it as 5-99 mol% with respect to the use amount of a silane compound (S1) with respect to the total amount of the monomer used for the synthesis of polyorganosiloxane, and to set it as 10-95 mol%. It is more preferable. It is preferable to set it as 0.5-50 mol% with respect to the total amount of the monomer used for the synthesis | combination of polyorganosiloxane, and, as for the usage ratio of a silane compound (S2), it is more preferable to set it as 1-40 mol%.

At the time of a hydrolysis condensation reaction, the use ratio of water is 1-30 mol with respect to 1 mol of the silane compound (total amount) used for reaction. As a catalyst to be used, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, etc. are mentioned, for example. Especially, tertiary organic amine or quaternary organic amine is preferable, For example, tertiary, such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine Organic amines of the present invention include quaternary organic amines such as tetramethylammonium hydroxide. Although the usage-amount of a catalyst changes with reaction conditions, such as a kind of catalyst, temperature, etc., and should be set suitably, For example, it is 0.01-3 times mole with respect to the total amount of a silane compound.

As an organic solvent used at the time of a hydrolysis condensation reaction, a hydrocarbon, a ketone, ester, an ether, alcohol, etc. are mentioned, for example. As these specific examples, As a hydrocarbon, For example, toluene, xylene, etc .;

As a ketone, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone etc .;

As ester, For example, ethyl acetate, butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .;

As the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran and the like;

Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like;

Each can be mentioned. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent becomes like this. Preferably it is 10-10,000 mass parts with respect to 100 mass parts in total of the silane compound used for reaction.

It is preferable to perform said hydrolysis condensation reaction by heating by an oil bath etc., for example. In that case, it is preferable to make heating temperature into 130 degrees C or less, and it is preferable to make heating time into 0.5 to 12 hours. After completion | finish of reaction, after drying the organic solvent layer fractionated from the reaction liquid with a drying agent as needed, the target polyorganosiloxane is obtained by removing a solvent. In addition, the synthesis | combination method of polyorganosiloxane is not limited to said hydrolysis condensation reaction, For example, you may carry out by the method of making a hydrolyzable silane compound react in presence of oxalic acid and alcohol.

(Reaction (1) of polyorganosiloxane (E) and amino group containing carboxylic acid)

In the method 1, the cyclic ether group which polyorganosiloxane (E) has has made, and the carboxyl group of amino group containing carbonic acid is made to react, and the polyorganosiloxane which has an amino group in a side chain is obtained. This reaction is preferably performed in the presence of a suitable catalyst and an organic solvent.

As a catalyst used in reaction, an organic base can be used suitably, for example, and a hardening accelerator can be used. As these specific examples, As an organic base, For example, primary or secondary organic amine, tertiary organic amine, quaternary organic amine salt, etc .;

As the curing accelerator, for example, tertiary amines, imidazole derivatives, organophosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, quaternary ammonium halides, metal halide compounds, latent curing accelerators, and the like, Each can be mentioned. As a latent hardening accelerator, a high melting | dispersion type latent hardening accelerator (for example, an amine addition type accelerator, etc.), a microcapsule type latent hardening accelerator, an amine salt type latent hardening accelerator, a high temperature dissociation type thermal cationic polymerization type Latent curing accelerators, etc. are mentioned. As a catalyst, it is preferable to use quaternary organic amine salt or the quaternary ammonium halide among these.

As a specific example of such a catalyst, As a quaternary organic amine salt, For example, tetramethylammonium hydroxide etc .;

As quaternary ammonium halide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, etc .;

Each can be mentioned. As the catalyst, one or more selected from these can be used. The use ratio of a catalyst becomes like this. Preferably it is 0.01-100 mass parts with respect to 100 mass parts of polyorganosiloxane (E), More preferably, it is 0.1-20 mass parts.

As an organic solvent used in reaction of a polyorganosiloxane (E) and a carbonic acid, a ketone, an ether, ester, an amide, alcohol, etc. are mentioned, for example. As a specific example of such an organic solvent, For example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone etc .;

As said ether, For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc .;

As said ester, For example, ethyl acetate, n-butyl acetate, iso-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc .;

As the amide, for example, formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N- Formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like;

As the alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, and the like can be mentioned, respectively, and one or more selected from these can be used.

The use ratio of an organic solvent is a ratio which the total mass of components other than the organic solvent in a reaction solution occupies for the total amount of reaction solution, It is preferable to set it as the ratio which becomes 0.1-50 mass%, and becomes 5-50 mass% It is more preferable to set it as a ratio.

Although the use ratio of amino group containing carbonic acid is suitably set according to the number of functional groups (B) introduce | transduced into the side chain of polyorganosiloxane (E), the thermal reliability of a liquid crystal element by introduction of a functional group (B), and of a liquid crystal aligning film From a viewpoint of fully obtaining the improvement effect of solvent resistance, it is preferable to set it as 0.005-0.5 mol with respect to 1 mol of silane compounds (total amount) used for the synthesis | combination of polyorganosiloxane. With respect to the lower limit of the said use ratio, More preferably, it is 0.01 mol or more, More preferably, it is 0.05 mol or more. The upper limit is more preferably 0.4 mol or less, and still more preferably 0.3 mol or less.

In the method 1, in the reaction of a polyorganosiloxane (E) and an amino-group containing carboxylic acid, the functional group (henceforth a "functional group") which gives a polymer a desired function is called polyorganosiloxane (E). You may use together the carbonic acid (henceforth a "functional group containing carbonic acid") which has a functional group for the purpose of introduce | transducing into. When using a functional group containing carboxylic acid with an amino group containing carboxylic acid, in order to enable introduction | transduction of a sufficient amount of functional group, and to prevent introduction of an amino group, the use ratio of the sum total of functional group containing carboxylic acid is poly It is preferable to set it as 0.05-0.8 mol with respect to 1 mol of silane compounds (total amount) used for the synthesis | combination of organosiloxane, and it is more preferable to set it as 0.1-0.7 mol.

The reaction of the polyorganosiloxane (E) and the amino group-containing carbonic acid is preferably 0 to 200 ° C, more preferably 50 to 150 ° C, preferably 0.1 to 50 hours, more preferably 0.5 It is performed for 20 hours. After completion | finish of reaction, after drying the organic solvent layer fractionated from the reaction liquid with a desiccant as needed, an amino group containing polyorganosiloxane can be obtained by removing a solvent.

(Reaction of polyorganosiloxane and amino acid anhydride having an amino group)

In the method 1 and the method, the amino group which polyorganosiloxane has, and the acid anhydride group which carbonic anhydride has are made to react. Thereby, the polyorganosiloxane which has an epoxy group and a carboxyl group in a side chain as a polymer [P] can be obtained.

The use ratio of carbonic anhydride is poly from the viewpoint of fully obtaining the thermal reliability of the liquid crystal element by the introduction of the functional group (B) (here carboxyl group) into the polyorganosiloxane side chain, and the effect of improving the solvent resistance of the liquid crystal aligning film. It is preferable to set it as 0.1-2.0 mol with respect to 1 mol of amino groups (total amount) which organosiloxane has. With respect to the lower limit of the said use ratio, More preferably, it is 0.2 mol or more, More preferably, it is 0.3 mol or more. Moreover, an upper limit becomes like this. More preferably, it is 1.5 mol or less, More preferably, it is 1.2 mol or less.

The reaction is preferably performed in a suitable organic solvent. As an organic solvent used, an aprotic polar solvent, a phenolic solvent, alcohol, a ketone, ester, an ether, a halogenated hydrocarbon, a hydrocarbon, etc. are mentioned, for example. Preferred organic solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, and hexamethylphosphortria. 1 or more types chosen from the group which consists of a mead, m-cresol, a xylenol, and a halogenated phenol.

In the said reaction, -20 degreeC-100 degreeC is preferable, and, as for reaction temperature, 0 degreeC-80 degreeC is more preferable. 1 hour-48 hours are preferable and, as for reaction time, 2 hours-12 hours are more preferable. The obtained reaction solution may be provided as it is to preparation of a liquid crystal aligning agent, or may be used for preparation of a liquid crystal aligning agent after isolating the polymer [P] contained in a reaction solution using a well-known isolation method.

(Reaction (2) of polyorganosiloxane (E) and amino group-containing carboxylic acid)

In the method 3, the cyclic ether group which polyorganosiloxane (E) has, and the amino group which amino group containing carboxylic acid has are made to react. Thereby, the polyorganosiloxane which has an epoxy group and a carboxyl group in a side chain as a polymer [P] can be obtained.

The use ratio of the amino group-containing carboxylic acid is used for the synthesis of the polyorganosiloxane from the viewpoint of sufficiently obtaining the effect of improving the thermal reliability of the liquid crystal device and the solvent resistance of the liquid crystal alignment film by introducing a carboxyl group into the side chain of the polyorganosiloxane. It is preferable to set it as 0.005-0.5 mol with respect to 1 mol of silane compounds (total amount) to be used. About the lower limit of the said use ratio, More preferably, it is 0.01 mol or more, More preferably, it is 0.05 mol or more. Moreover, about an upper limit, More preferably, it is 0.4 mol or less, More preferably, it is 0.3 mol or less.

The said reaction is performed in a suitable solvent in presence of a suitable catalyst as needed. As a catalyst, magnesium oxide, calcium oxide, potassium carbonate, etc. are mentioned, for example. As a solvent, it is preferable that amino group containing polyorganosiloxane and carbonic anhydride can be melt | dissolved or disintegrated uniformly, For example, N-methyl- 2-pyrrolidone, tetrahydrofuran, etc. are mentioned. In the said reaction, -20 degreeC-180 degreeC is preferable, and, as for reaction temperature, 10 degreeC-120 degreeC is more preferable. 1 hour-72 hours are preferable, and, as for reaction time, 2 hours-48 hours are more preferable. What is necessary is just to isolate the polymer [P] contained in a reaction solution, and to provide the preparation of a liquid crystal aligning agent, using the well-known isolation method.

In the method 2 and the method 3, when obtaining the polyorganosiloxane which has a functional group as a polymer [P], about the method 2, about the method 3, before making the polyorganosiloxane which has an amino group, and carbonic anhydride react, What is necessary is just to react the polyorganosiloxane which has a cyclic ether group, and a functional group containing carbonic acid before making polyorganosiloxane and amino group containing carbonic acid react. The description of Method 1 applies to the reaction conditions of the polyorganosiloxane having a cyclic ether group and the functional group-containing carbon acid.

Examples of the methods 1 to 3 are shown in the following schemes A1, A2, B and C. In the method 1, when an epoxy-group containing silane compound is used as a silane compound (S1), 3-aminobenzoic acid is used as an amino-group containing carbonic acid, and trimellitic anhydride is used as a carbonic anhydride, following Reaction Formula A1 ( The polymer [P] can be obtained by β cleavage of an epoxy group and Scheme A2 (α cleavage of an epoxy group).

(L <^1> is bivalent coupling group and R <^1> is a hydrogen atom in reaction formula A1 and A2.)

In the method 2, when an epoxy-group containing silane compound is used as a silane compound (S1), and trimellitic anhydride is used as a carboxylic anhydride, a polymer [P] can be obtained by the following Reaction Scheme B.

(L <^1> and L <^2> are bivalent coupling groups each independently in reaction formula B.)

In the method 3, when an epoxy group containing silane compound is used as a silane compound (S1), and 4-aminobenzoic acid is used as an amino group containing carboxylic acid, a polymer [P] can be obtained by the following Reaction Scheme C.

(In Scheme C, L ¹ is a divalent linking group, and R ³ is a hydrogen atom.)

According to the above Reaction Schemes A1, A2 and B, as the polymer [P], a polyorganosiloxane having a cyclic ether group (here an oxiranyl group) and a carboxyl group and a polyorganosiloxane having a cyclic ether group and an amino group can be obtained. have. In addition, according to the reaction scheme C, a polyorganosiloxane having a cyclic ether group and a carboxyl group can be obtained as the polymer [P].

(Functional group)

It is preferable that polymer [P] has a functional group in a side chain according to the drive mode of the liquid crystal element to apply. For example, when using a liquid crystal aligning agent for manufacture of the liquid crystal element of a vertical alignment type or a horizontal alignment type, it is preferable that polymer [P] has the orientation expression site | part which orientates liquid crystal molecules as a functional group. Moreover, when providing liquid crystal aligning ability with respect to the polymer thin film formed with the liquid crystal aligning agent by the photo-alignment method, it is preferable that polymer [P] has a photo-alignment group as a functional group. Moreover, when heightening the orientation control force of liquid crystal molecule by irradiating light from the outer side of a liquid crystal cell after construction of a liquid crystal cell, it is preferable that polymer [P] has a group containing a carbon-carbon unsaturated bond as a functional group.

[Oriental Expression Site]

An orientation expression site | part is group which can control the orientation direction of the liquid crystal molecule in a liquid crystal layer with respect to the polymer thin film formed using the liquid crystal aligning agent. In addition, the orientation expression site | part can control the orientation of a liquid crystal molecule, without irradiating light. As a specific example of an orientation expression site | part, the group etc. which are represented by following formula (3) are mentioned, for example.

(In Formula (3), R ^I is a monovalent group, a cyano group, in which at least one hydrogen atom of an alkyl group of 1 to 40 carbon atoms, a fluoroalkyl group of 1 to 40 carbon atoms, or an alkyl group of 1 to 40 carbon atoms is substituted with a cyano group. Nitro group, or a fluorine atom, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton, Z ^I represents a single bond, ^* -O-, ^* -COO- or ^* -OCO- (wherein "*" the coupling is attached hand cheukim R ^I). R ^ⅱ is a cyclohexylene group or a phenylene group, and represents a hydrogen atom a cyano group, a nitro group, a fluorine atom, trifluoromethyl group or 1 to 3 carbon atoms bonded to the ring And n1 is 1 or 2, and when n1 is 2, two R ^IIs may be the same as or different from each other, n2 is 0 or 1. Z ^II is a single bond, ^* -O-, ^* -COO- or ^* -OCO- (single, combined hand R ^ⅱ cheukim tagged "*") is. n3 is an integer from 0 to 2, and n4 is 0 or 1. However, n2 = 0 again For n4 = 0, R ^I is not less than 4 carbon atoms.)

As a bivalent group represented by "-( ^RII ) _n1- " in the said Formula (3), it is a 1, 4- phenylene group, a 1, 4- cyclohexylene group, a 4,4'-biphenylene group, for example. , 4,4'-bicyclohexylene group, the following formula

(In the formula, the bonding hand with "*" is bonded to Z ^I. )

The group etc. which are represented by each of these are mentioned as a preferable thing.

[Optical alignment group]

A photoalignable group is a functional group which provides anisotropy to a film | membrane by the photoisomerization reaction by light irradiation, a photodimerization reaction, a photolysis reaction, and a photo fleece potential reaction. As a specific example of a photo-orientation group, the cinnamic-acid structure containing group containing azobenzene or its derivative (s) as a base skeleton, cinnamic acid, or its derivatives (cinnamic acid structure) as a base skeleton, a chalcon, or derivatives thereof, for example Includes a chalcone-containing group, a benzophenone-containing group containing benzophenone or a derivative thereof as a basic skeleton, a coumarin-containing group comprising a coumarin or a derivative thereof as a basic skeleton, a cyclobutane or a derivative thereof, as a basic skeleton Cyclobutane containing structure etc. are mentioned. It is preferable to have a cinnamic-acid structure containing group represented by following formula (5) among the points which are high in sensitivity to light, and the point which is easy to introduce | transduce into a polymer side chain. A polymer [P] is preferable at the point which can improve the high speed response of the liquid crystal element obtained by having a pretilt angle expression site | part with the structure represented by following formula (5).

(In formula (5), R is a fluorine atom or a cyano group. A 'is an integer of 0 to 4. When a' is 2 or more, some R may be same or different. "*" Represents a bond. Indicates.)

[Groups containing carbon-carbon unsaturated bonds]

As group containing a carbon-carbon unsaturated bond, the group etc. which are represented by following formula (4) are mentioned, for example.

(In formula (4), R is a hydrogen atom or a methyl group, X <^I> and X <^II> are a 1, 4- phenylene group and a C1-C8 alkanediyl group, respectively, Z is an oxygen atom, -COO - ^* Or -OCO- ^* (wherein the bond to which "*" is attached is bonded to X ^II ), and a, b, c and d are each 0 or 1, provided that c is 0 and d is When 1, X ^II is a 1,4-phenylene group and when b is 0, c is 0.)

As a specific example of group represented by said Formula (4), a vinyl group, an allyl group, p-vinylphenyl group, (meth) acryloxyalkyl group, 4-((meth) acryloxy) alkyl) phenyl group, ((meth) Acryloxy) phenyl) alkyl group, 4-((meth) acryloxyalkoxy) phenyl group, (meth) acryloxyalkoxyalkyl group, 6-{[6- (acryloyloxy) hexanoyl] oxy} hexyl group, etc. are mentioned. have.

When polymer [P] is a polymer which has a functional group in a side chain, the said polymer is synthesize | combined by superposition | polymerization using the monomer which has (I) functional group, (II) cyclic ether group which polymer [P] or its precursor has The method introduce | transduced into a side chain using this etc. are mentioned. Among these, (II) is preferable at the point which is simple and it is easy to adjust the introduction ratio of a functional group. Among them, a polyorganosiloxane having a cyclic ether group (polyorganosiloxane (E) in Method 1 and Method 3, polyorganosiloxane (M) in Method 2), a compound having a functional group (B) and a functional group (hereinafter , Also referred to as "side chain precursor [C]").

In addition, polymer [P] may have only 1 type of groups containing an orientation expression site | part, a photoalignable group, and a carbon-carbon unsaturated bond as a functional group, and may have multiple types. When polymer [P] has two or more types of the said functional groups, one functional group and another functional group may exist in the same side chain, and may exist in separate side chains. Moreover, the whole of each functional group may be contained in the polymer of a single type, and may be used as a mixture of the polymer which has a part of desired functional group, and the polymer which has a remainder of functional groups. Of course, three or more types of polymers may be mixed and used as a polymer [P], and two or more types of polymers which have the same functional group may be mixed and used. Since any embodiment may be sufficient, polymer [P] should just have each functional group as a whole or a mixture.

The weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC) of polymer [P] becomes like this. Preferably it is 1,000-300,000, More preferably, it is 2,000-100,000. However, when polymer [P] is a modified polymer modified | denatured using the compound which has a functional group, it is preferable that the weight average molecular weight of the polymer before the modification is the said range. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw and the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 5 or less, and more preferably 4 or less. In addition, 1 type of polymers [P] used for preparation of a liquid crystal aligning agent may be good, and may combine 2 or more types.

Since the content rate of the polymer [P] in a liquid crystal aligning agent can fully acquire the improvement effect of the thermal reliability of the liquid crystal element obtained, it is 0.1 mass part or more with respect to 100 mass parts of all the polymers contained in a liquid crystal aligning agent. It is preferable, it is more preferable that it is 0.5 mass part or more, and it is still more preferable that it is 1 mass part or more. Moreover, when mix | blending another polymer, it is preferable that it is 50 mass parts or less with respect to 100 mass parts of other polymers contained in a liquid crystal aligning agent, and, as for the content rate of polymer [P], it is more preferable that it is 25 mass parts or less, It is more preferable that it is 20 mass parts or less.

<Other components>

Although the liquid crystal aligning agent of this indication contains the above polymer [P], you may contain the other components shown below as needed.

(Other polymers)

The liquid crystal aligning agent of this indication is a polymer different from polymer [P] for the purpose of obtaining the improvement effect of various performances, such as an electrical characteristic, liquid crystal alignability, and reliability, and aiming at cost reduction, etc. Other polymer ”). The main skeleton of the other polymer is not particularly limited. As other polymers, for example, polyamic acid, polyimide, polyamic acid ester, polyamide, polyorganosiloxanes other than polymer [P], polyester, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmalee) Mid) derivative, a poly (meth) acrylate, etc. can mention the polymer which has a main skeleton. In addition, in this specification, "(meth) acrylate" is the meaning containing an acrylate and a methacrylate.

The other polymer has a polyamic acid, a polyamic acid ester, a polyimide, and a polymerizable unsaturated bond among the above from a viewpoint of electrical property, affinity with a liquid crystal, mechanical strength, affinity with a polymer [P], etc. It is preferable to use at least 1 sort (s) of polymer (henceforth "polymer [Q]") chosen from the group which consists of a polymer of a monomer.

It is preferable to set it as 100 mass parts or more with respect to 100 mass parts of polymers [P] used for preparation of a liquid crystal aligning agent, and, as for the mixture ratio of polymer [Q], it is more preferable to set it as 100-2000 mass parts, and 200- It is more preferable to set it as 1500 mass parts.

(Polyamic acid, polyamic acid ester and polyimide)

The polyamic acid, polyamic acid ester, and polyimide contained in a liquid crystal aligning agent can be synthesize | combined according to a conventionally well-known method. For example, polyamic acid can be obtained by making tetracarboxylic dianhydride and diamine react. The polyamic acid ester can be obtained by, for example, reacting the polyamic acid with an esterifying agent (for example, methanol, ethanol, N, N-dimethylformamide diethyl acetal, or the like). Polyimide can be obtained, for example, by dehydrating and ring-closing polyamic acid and imidizing it. Moreover, it is preferable that the imidation ratio is 20 to 95%, and, as for a polyimide, it is more preferable that it is 30 to 90%. This imidation ratio shows the ratio which the number of the number of the imide ring structures to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage.

As tetracarboxylic acid used for superposition | polymerization, For example, Aliphatic tetracarboxylic dianhydride, such as butane tetracarboxylic dianhydride and ethylenediamine tetraacetic acid dianhydride;

1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid 2 Anhydride, 5- (2,5-dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 5- ( 2,5-dioxotetrahydrofuran-3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphtho [1,2-c] furan-1,3-dione, 2,4, Alicyclic tetracarboxylic acid dianhydrides, such as 6,8-tetracarboxy bicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, cyclopentane tetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride. ;

Pyromellitic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylenebis (trimelitic acid monoester anhydride), ethylene glycol bis (anhydrotrimellitate), 1, Aromatic tetracarboxylic dianhydride, such as 3-propylene glycol bis (anhydro trimellitate), etc. are mentioned, The tetracarboxylic dianhydride of Unexamined-Japanese-Patent No. 2010-97188 can be used. In addition, tetracarboxylic dianhydride may be used individually by 1 type, and may be used in combination of 2 or more type.

Moreover, as a diamine used for the said superposition | polymerization, For example, Aliphatic diamines, such as ethylenediamine and tetramethylenediamine;

alicyclic diamines such as p-cyclohexanediamine and 4,4'-methylenebis (cyclohexylamine);

Hexadecaneoxydiaminobenzene, cholestanyloxydiaminobenzene, diaminobenzoic acid cholestanyl, diaminobenzoic acid cholesteryl, diaminobenzoic acid ranostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 2,5-diamino-N, N- Diallyl aniline, formulas (8-1) to (8-3)

Branched aromatic diamines such as compounds represented by each of;

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 3 , 5-diaminobenzoic acid, 1,5-bis (4-aminophenoxy) pentane, bis [2- (4-aminophenyl) ethyl] hexane diacid, bis (4-aminophenyl) amine, N, N- Bis (4-aminophenyl) methylamine, N, N'-bis (4-aminophenyl) -benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (tri Fluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'- (Phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4- (4-aminophenoxycarbonyl) -1- (4-aminophenyl) piperidine, 4, Non-branched aromatic diamines such as 4 '-[4,4'-propane-1,3-diylbis (piperidine-1,4-diyl)] dianiline;

Diamino organosiloxane, such as 1, 3-bis (3-aminopropyl)-tetramethyl disiloxane, etc. are mentioned, The diamine of Unexamined-Japanese-Patent No. 2010-97188 can be used. In addition, diamine may be used individually by 1 type, and may be used in combination of 2 or more type.

About the polyamic acid, polyamic acid ester, and polyimide contained in a liquid crystal aligning agent, the weight average molecular weight (Mw) of polystyrene conversion measured by GPC becomes like this. Preferably it is 1,000-500,000, More preferably, it is 2,000-300,000. . The molecular weight distribution (Mw / Mn) is preferably 7 or less, and more preferably 5 or less. In addition, only 1 type may be sufficient as the polyamic acid, polyamic acid ester, and polyimide to be contained in a liquid crystal aligning agent, or may combine 2 or more types.

(Polymer of Monomer Having Polymeric Unsaturated Bond)

As a polymerizable unsaturated bond which the monomer which comprises a polymer (PAc) has with respect to the polymer of the monomer which has a polymerizable unsaturated bond (henceforth "polymer (PAc)"), for example, a (meth) acryloyl group, Vinyl group, styryl group, maleimide group, etc. are mentioned. As a specific example of the monomer which has these polymerizable unsaturated bonds, For example, (meth) acrylic-type compounds, such as unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated polyhydric carboxylic acid anhydride;

Aromatic vinyl compounds such as styrene, methyl styrene and divinylbenzene;

Conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene;

Maleimide compounds, such as N-methyl maleimide, N-cyclohexyl maleimide, and N-phenyl maleimide, etc. are mentioned. In addition, the monomer which has a polymerizable unsaturated bond can be used individually by 1 type or in combination of 2 or more types.

It is preferable that a polymer (PAc) is poly (meth) acrylate. The poly (meth) acrylate may be a polymer composed of only a (meth) acrylic compound or a polymer composed of a monomer different from the (meth) acrylic compound. As said other monomer, a conjugated diene compound, an aromatic vinyl compound, a maleimide compound, etc. are mentioned. The poly (meth) acrylate preferably has 30% by mass or more of the structural unit derived from the (meth) acrylic compound, more preferably 40% by mass or more, still more preferably 50% by mass or more, 70 It is especially preferable to have mass% or more.

Although the (meth) acrylic compound used at the time of superposition | polymerization is not specifically limited, As an example of the unsaturated carbonic acid, (meth) acrylic acid, (alpha)-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, vinyl benzoic acid etc. are mentioned, for example. ;

As unsaturated carboxylic acid ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid Tricyclo [5.2.1.0 ^2,6 ] deca-8-yl, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) Trimethoxysilylpropyl acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, methoxyethyl (meth) acrylate, ( Meta) acrylic acid-N, N-dimethylaminoethyl, (meth) acrylic acid methoxypolyethylene glycol, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid glycidyl, (meth) ) Acrylic acid 3,4-epoxycyclohexylmethyl, (meth) acrylic acid 3,4-epoxy part Methyl, 4-hydroxybutyl glycidyl ether, and the like;

As unsaturated polyhydric carboxylic anhydride, maleic anhydride, itaconic anhydride, a cis-1,2,3,4- tetrahydrophthalic anhydride etc. are mentioned, for example. In addition, these (meth) acrylic compounds can be used individually by 1 type or in combination of 2 or more types.

It is preferable to perform the polymerization reaction using a (meth) acrylic compound by radical polymerization. As a polymerization initiator used at the time of the said polymerization reaction, 2,2'- azobis (isobutyronitrile), 2,2'- azobis (2, 4- dimethylvaleronitrile), 2,2, for example Azo compounds, such as' -azobis (4-methoxy-2,4-dimethylvaleronitrile), are used preferably. The use ratio of a polymerization initiator becomes like this. Preferably it is 0.01-40 mass parts with respect to a total of 100 mass parts of monomers used for reaction.

The polymerization reaction of the (meth) acrylic compound is preferably performed in an organic solvent. As an organic solvent used for the said reaction, an alcohol, an ether, a ketone, an amide, ester, a hydrocarbon compound etc. are mentioned, for example. Among these, it is preferable to use at least 1 sort (s) chosen from the group which consists of alcohol and ether, and it is more preferable to use the partial ether of polyhydric alcohol. As the preferable specific example, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, etc. are mentioned, for example. Moreover, as an organic solvent, these can be used individually by 1 type or in combination of 2 or more types.

In the case of the polymerization reaction of a (meth) acrylic-type compound, it is preferable to make reaction temperature into 30-120 degreeC, and it is preferable to make reaction time into 1 to 36 hours. In addition, it is preferable that the usage-amount (a) of the organic solvent shall be an amount which will be 0.1-50 mass% with respect to the total amount (a + b) of the reaction solution of the total amount (b) of the monomer used for reaction.

It is preferable that it is 250-500,000, as for the number average molecular weight (Mn) of polystyrene conversion measured by GPC with respect to poly (meth) acrylate, it is more preferable that it is 500-100,000, and it is still more preferable that it is 1,000-50,000.

As other components, the above-mentioned, for example, the compound which has at least 1 epoxy group in a molecule (except the compound corresponding to silicon-containing compound [A]), and a functional silane compound (however, a silicon-containing compound [A ], Antioxidants, metal chelate compounds, curing accelerators, crosslinking agents, surfactants, fillers, dispersants, photosensitizers and the like. The compounding ratio of another component can be suitably selected according to each compound in the range which does not impair the effect of this indication.

(solvent)

The liquid crystal aligning agent of this indication is preferably prepared as a solution composition in which the polymer component and the component mix | blended arbitrarily as needed are melt | dissolved or dispersed in the organic solvent preferably. As an organic solvent to be used, an aprotic polar solvent, a phenol type solvent, alcohol, a ketone, ester, an ether, a halogenated hydrocarbon, a hydrocarbon, etc. are mentioned, for example. One type of these solvent components may be sufficient, and 2 or more types of mixed solvents may be sufficient as them.

As a specific example of the organic solvent to be used, For example, N-methyl- 2-pyrrolidone, N-ethyl- 2-pyrrolidone, 1,2-dimethyl- 2-imidazolidinone, (gamma) -butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl me Oxypropionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve ), 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, diisobutyl ketone, isoamyl propionate, isoamyl isobutylate, diisopentyl ether, ethylene carbonate, propylene carbonate, cyclohexane, octanol, tetrahydrofuran and the like. In addition, the hydrocarbon solvent which does not contain the said amide structure can be used for the purpose of enabling application to a plastic base material and low temperature baking.

As a solvent component, it is at least 1 sort (s) chosen from the group which consists of a compound represented by each of following formula (E-1)-a formula (E-5), and also the solvent whose boiling point in 1 atmosphere is 180 degrees C or less (hereinafter, "specifically Solvent "). While these specific solvents can improve the coating property (printability) of a liquid crystal aligning agent, even when the heating at the time of film formation is performed at low temperature (for example, 200 degrees C or less), they are excellent in liquid crystal orientation and electrical property. It is preferable at the point which can obtain a liquid crystal element.

(In formula (E-1), R ⁴¹ is a C1-C4 alkyl group or CH ₃ CO-, and R ⁴² is a C1-C4 alkanediyl group or-(R ⁴⁷ -O) rR ^48- ( However, R ⁴⁷ and R ⁴⁸ are each independently a C 2 or 3 alkanediyl group, r is an integer of 1 to 4), and R ⁴³ is a hydrogen atom or an alkyl group of 1 to 4 carbon atoms.)

(In formula (E-2), R ⁴⁴ is a C1-C4 alkanediyl group.)

(In formula (E-3), R <^45> and R <^46> are respectively independently C1-C8 alkyl groups.)

(In formula (E-4), R <^49> is a hydrogen atom or a hydroxyl group. R <^50> is a C1-C9 hydrocarbon group when R <^49> is a hydrogen atom, and when R <^49> is a hydroxyl group, C1-C is A divalent hydrocarbon group of 9 or a divalent group having an oxygen atom between the carbon-carbon bonds.)

(In formula (E-5), R ⁵¹ and R ⁵² are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent group having an oxygen atom between the carbon-carbon bonds.)

As a specific example of a specific solvent, As a compound represented by said Formula (E-1), For example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxy-1- butanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, and the like. ;

As a compound represented by said Formula (E-2), For example, cyclobutanone, cyclopentanone, cyclohexanone;

As a compound represented by said Formula (E-3), for example, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n- Pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2 , 4-pentanedione, acetonyl acetone, diisobutyl ketone and the like;

As the compound represented by the formula (E-4), for example, methanol, ethanol, propanol, butanol, pentanol, 3-methoxybutanol, hexanol, heptanol, octanol, furfuryl alcohol, phenol, cyclohexanol , Monocyclo alcohols such as methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4 Polyhydric alcohols such as pentanediol;

As a compound represented by said Formula (E-5), For example, partial ester of polyhydric alcohol (for example, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethyl Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene Partial esters of polyhydric alcohols such as glycol monopropyl ether), methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, i-butyl acetate, t-butyl acetate, 3-methoxybutyl acetate, 2-ethylhexyl acetate, Acetoacetic acid methyl, acetoacetic acid ethyl, ethylene glycol monometh Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetate propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetic acid glycol Methoxytriglycol acetate, ethyl propionate, n-butyl propionate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and the like, respectively. Can be. In addition, as a specific solvent, you may use individually by 1 type, and may use in combination of 2 or more type.

It is preferable to use 10 mass% or more with respect to the total amount of the solvent used for preparation of a liquid crystal aligning agent, as for the usage ratio of a specific solvent, it is more preferable to set it as 20 mass% or more, and it is further made into 50 mass% or more. desirable. Moreover, it is preferable to set it as 95 mass% or less with respect to the total amount of the solvent used for preparation of a liquid crystal aligning agent, and, as for the upper limit of the use ratio of a specific solvent, it is more preferable to set it as 90 mass% or less, 80 mass% or less It is more preferable to set it as.

Solid content concentration (the ratio which the total mass of components other than the solvent of a liquid crystal aligning agent occupies for the total mass of a liquid crystal aligning agent) in a liquid crystal aligning agent is selected suitably in consideration of viscosity, volatility, etc., Preferably it is 1- It is the range of 10 mass%. When solid content concentration is less than 1 mass%, the film thickness of a coating film will become small and it will become difficult to obtain a favorable liquid crystal aligning film. On the other hand, when solid content concentration exceeds 10 mass%, the film thickness of a coating film becomes excess and it is difficult to obtain a favorable liquid crystal aligning film, and also there exists a tendency for the viscosity of a liquid crystal aligning agent to increase, and applicability | paintability falls.

`` Liquid crystal aligning film and liquid crystal element ''

The liquid crystal aligning film of this indication is formed of the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal element of this indication is equipped with the liquid crystal aligning film formed using the liquid crystal aligning agent demonstrated above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, and for example, TN type, STN type, VA type (including VA-MVA type, VA-PVA type, etc.), IPS (In-Plane Switching) type It can be applied to various modes such as FFS (Fringe Field Switching), OCB (Optically Compensated Bend), PSA (Polymer Sustained® Alignment). A liquid crystal element can be manufactured by the method containing the following process 1-process 3, for example. The process board | substrate differs in process 1 according to a desired operation mode. Process 2 and process 3 are common to each operation mode.

<Step 1: Formation of Coating Film>

First, a liquid crystal aligning agent is apply | coated on a board | substrate, Preferably a coating film is formed on a board | substrate by heating a coating surface. As a board | substrate, For example, glass, such as float glass and a soda glass;

A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG Co., Ltd.) made of tin oxide (SnO ₂ ), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used. Can be. When manufacturing a TN type, STN type, or VA type liquid crystal element, two board | substrates with which the patterned transparent conductive film is provided are used. On the other hand, when manufacturing the IPS type or FFS type liquid crystal element, the board | substrate with which the electrode patterned by the comb-tooth type is formed, and the opposing board | substrate with which the electrode is not formed are used. Application | coating of the liquid crystal aligning agent to a board | substrate is preferably performed by the offset printing method, the flexographic printing method, the spin coating method, the roll coater method, or the inkjet method on an electrode formation surface.

After apply | coating a liquid crystal aligning agent, preheating (prebaking) is preferably performed for the purpose of liquid flow prevention of the apply | coated liquid crystal aligning agent. The prebaking temperature is preferably 30 to 200 ° C, and the prebaking time is preferably 0.25 to 10 minutes. Thereafter, the solvent is completely removed, and if necessary, a firing (postbaking) step is performed for the purpose of thermally imidizing the dark acid structure present in the polymer. The baking temperature (post-baking temperature) at this time becomes like this. Preferably it is 80-300 degreeC, and the post-baking time becomes like this. Preferably it is 5-200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 m.

<Step 2: Orientation Treatment>

When manufacturing the TN type, STN type, IPS type, or FFS type liquid crystal element, the process (alignment process) which gives a liquid-crystal orientation capability to the coating film formed in the said process 1 is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film. As the orientation treatment, a rubbing treatment for imparting liquid crystal alignment ability to the coating film by rubbing the coating film in a predetermined direction with a roll wound with a cloth made of fibers such as nylon, rayon or cotton, and irradiating the coating film formed on the substrate with light irradiation The photo-alignment process etc. which give a liquid-crystal orientation ability to this are mentioned. On the other hand, when manufacturing the liquid crystal element of a vertical alignment type, although the coating film formed at the said process 1 can be used as a liquid crystal aligning film as it is, you may perform an orientation process with respect to the said coating film.

The light irradiation for the light orientation is during the heating of the coating film in at least one of a method of irradiating the coating film after the postbaking step, a method of irradiating the coating film before the postbaking step as a prebaking step, a prebaking step and a postbaking step. It can carry out by the method of irradiating a coating film, etc. As radiation to irradiate a coating film, the ultraviolet-ray and visible ray which contain the light of a wavelength of 150-800 nm can be used, for example. Preferably, it is an ultraviolet-ray containing light of the wavelength of 200-400 nm. When radiation is polarized light, linearly polarized light or partial polarized light may be sufficient. When the radiation used is linearly polarized light or partial polarized light, irradiation may be performed from the direction perpendicular | vertical to a board | substrate surface, may be performed from a diagonal direction, or it may combine them. The irradiation direction in the case of non-polarized radiation is an inclined direction.

As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. are mentioned, for example. The radiation dose is preferably 400 to 50,000 J / m 2, more preferably 1,000 to 20,000 J / m 2. After light irradiation for providing orientation, the surface of the substrate is, for example, water or an organic solvent (for example, methanol, isopropyl alcohol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.). Or you may perform the process which wash | cleans using these mixtures, and the process which heats a board | substrate.

<Step 3: Construction of Liquid Crystal Cell>

The liquid crystal cell is manufactured by preparing two board | substrates with a liquid crystal aligning film as mentioned above, and arrange | positioning a liquid crystal between two board | substrates which oppose. In order to manufacture a liquid crystal cell, two board | substrates are opposingly arranged through a clearance gap so that a liquid crystal aligning film may oppose, for example, the peripheral part of two board | substrates is joined using a sealing agent, and the board | substrate surface and the sealing agent are enclosed. The method of sealing an injection hole by injecting and filling a liquid crystal in a cell gap, the method by ODF system, etc. are mentioned. As the sealing agent, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals, and among them, nematic liquid crystals are preferable. In the PSA mode (including the case where a compound having a polymerizable group (low molecular weight or polymer) is contained in the liquid crystal alignment film), after construction of the liquid crystal cell, the liquid crystal cell is applied in a state where a voltage is applied between the conductive films of the pair of substrates. The light irradiation process is performed.

Subsequently, a polarizing plate is bonded to the outer surface of a liquid crystal cell as needed, and it is set as a liquid crystal element. As a polarizing plate, the polarizing plate which interposed the polarizing film called "H film | membrane" which absorbed iodine while extending | stretching polyvinyl alcohol in the cellulose acetate protective film, or the polarizing plate which consists of H film itself is mentioned.

The liquid crystal element of the present disclosure can be effectively applied to various uses, and includes, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smart phone, Various display apparatuses, such as various monitors, a liquid crystal television, and an information display, a light control film, etc. can be used. In addition, the liquid crystal element formed using the liquid crystal aligning agent of this indication can also be applied to retardation film.

Example

Hereinafter, although an Example demonstrates concretely, this invention is not limited to these Examples.

In this Example, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer were measured by the following method.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)>

By gel permeation chromatography (GPC), Mw and Mn were measured on condition of the following. In addition, molecular weight distribution (Mw / Mn) was computed from obtained Mw and Mn.

Device: Showa Denko Co., Ltd.``GPC-101 ''

GPC column: Combines "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-804" manufactured by Shimadzu Corporation

Mobile phase: tetrahydrofuran (THF)

Column temperature: 40 ℃

Flow rate: 1.0mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 μL

Detector: parallax refractometer

Standard material: monodisperse polystyrene

<Synthesis of Polymer>

Example 1A

Polymer (P-1) was synthesized according to Scheme 1 below.

Into a 1000 ml three-necked flask, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were added and mixed at room temperature. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, mixing under reflux. After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure. Methyl isobutyl ketone was added suitably and the 50 mass% solution of the polyorganosiloxane (E-1) which has an epoxy group was obtained.

500 ml three-necked flask containing 26.69 g (0.3 mol equivalent) of side chain precursor (ca-1), 3.09 g (0.1 mol equivalent) of m-aminobenzoic acid, 2.00 g of tetrabutylammonium bromide, polyorganosiloxane (E-1) 80g of solutions and 239g of methyl isobutyl ketones were added, and it stirred at 110 degreeC for 4 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. Thereafter, the organic layer was recovered, concentrated twice with NMP dilution with a rotary evaporator, and a 15% by mass NMP solution of the polymer (P-1) intermediate was obtained. After adding 0.44 g (0.1 mol equivalent) of trimellitic anhydride to 50 g of this intermediate solutions, it prepared by using NMP so that solid content concentration might be 10 mass%, and it stirred at room temperature for 4 hours, and the polymer (P-1) of An NMP solution was obtained.

[Examples 2A to 12A and Comparative Synthesis Examples 1 to 4]

Polymerization was carried out in the same manner as in Example 1A, except that the kind and amount of the compound used in the synthesis were set as the kind and amount shown in Table 1 below, and the polymers (P-2) to (P-12) and (R-1). Each polymer of)-(R-4) was obtained.

The numerical value of Table 1 shows the usage ratio (mol%) of a carbonic acid and a carbonic anhydride with respect to the number of the epoxy groups which an epoxy-group containing polyorganosiloxane has. The abbreviation of the compound of Table 1 is as follows.

(Side chain precursor [C])

ca-1 to ca-5: a compound represented by each of the following formulas (ca-1) to (ca-5)

(Amino group-containing carboxylic acid)

cb-1: 3-aminobenzoic acid

cb-2: 4-aminobenzoic acid

(Carboxylic anhydride)

an-1: trimellitic anhydride

an-2: 4-nitrophthalic anhydride

an-3: 4-ethynylphthalic anhydride

an-4: maleic anhydride

an-5: cyclohexane-1,2,4-tricarboxylic acid-1,2- anhydride

Example 13A

A polymer (P-13) was synthesized according to Scheme 2 below.

Into a 1000 ml three-necked flask, 90.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 7.3 g of 3-aminopropyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were added thereto. Mixed in. Subsequently, 100 g of deionized water was dripped over 30 minutes from the dropping funnel, and reaction was performed at 80 degreeC for 6 hours, mixing under reflux. After completion | finish of reaction, the organic layer was taken out and this was wash | cleaned by 0.2 mass% ammonium nitrate aqueous solution until the water after washing became neutral, and the solvent and water were distilled off under reduced pressure. A suitable amount of methyl isobutyl ketone was added to obtain a 50 mass% solution of polyorganosiloxane (E-2) having an epoxy group and an amino group.

To a 500 ml three-necked flask, 26.69 g (0.3 mol equivalent) of side chain precursor (ca-1), 2.00 g of tetrabutylammonium bromide, 80 g of a solution containing polyorganosiloxane (E-2), and 239 g of methyl isobutyl ketone were added. It stirred at 110 degreeC for 4 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. Thereafter, the organic layer was recovered, concentrated twice with NMP dilution with a rotary evaporator to obtain a 15 mass% NMP solution of the polymer (P-13) intermediate. After adding 0.45 g (0.1 mol equivalent) of trimellitic anhydride to 50 g of this intermediate solutions, it prepared so that solid content concentration might be 10 mass% using NMP, and it stirred at room temperature for 4 hours, and a polymer (P-13) of An NMP solution was obtained.

Example 14A

Polymer (P-14) was synthesized according to Scheme 3 below.

500 ml three-necked flask containing 26.69 g (0.3 mol equivalent) of side chain precursor (ca-1), 3.09 g (0.1 mol equivalent) of m-aminobenzoic acid, 2.00 g of tetrabutylammonium bromide, polyorganosiloxane (E-1) 80g of solutions and 239g of methyl isobutyl ketones were added, and it stirred at 110 degreeC for 4 hours. After cooling to room temperature, the liquid separation washing operation was repeated 10 times with distilled water. Then, an organic layer was collect | recovered, 15 mass% of polyorganosiloxane (it calls this "polymer (R-1)") which has an epoxy group and a functional group by repeating concentration and NMP dilution twice with a rotary evaporator. An NMP solution was obtained.

Subsequently, 0.13 g (0.1 mol equivalent) of magnesium oxide and 0.44 g (0.1 mol equivalent) of m-aminobenzoic acid were added to 50 g of the polymer (R-1) containing solution, and it stirred at 80 degreeC for 24 hours. After cooling to room temperature, it was poured into water to dissolve magnesium oxide. Next, the mixture was extracted using a mixed solution of diethylene glycol diethyl ether and cyclohexane, and the liquid separation washing operation was repeated 10 times with distilled water. Then, the organic layer was collect | recovered and the 10 mass% NMP solution of the polymer (P-14) was obtained by repeating concentration and NMP dilution twice with a rotary evaporator.

Synthesis Example 1

13.8 g (70.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, 16.3 g (76.9) of 2,2'-dimethyl-4,4'-diaminobiphenyl as diamine mmol) was dissolved in 170 g of NMP, and reacted at 25 ° C for 3 hours to obtain a solution containing 10% by mass of polyamic acid. This polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. Methanol wash | cleaned this deposit, and it dried under reduced pressure at 40 degreeC for 15 hours, and polyamic acid (PAA-1) was obtained.

Synthesis Example 2

In a 200 mL two-neck flask under nitrogen, 16.0 g (113 mmol) of methacrylic acid glycidyl and 4.0 g (46.5 mmol) of methacrylic acid as a polymerization monomer and 2,2'-azobis (2,4- as a radical polymerization initiator) Dimethylvaleronitrile) 0.6 g (2.4 mmol), 1.0 g (4.2 mmol) of 2,4-diphenyl-4-methyl-1-pentene as a chain transfer agent, and 86.4 g of NMP as a solvent were added, and it was 5 hours at 70 degreeC. By polymerizing, the target polymer (this was referred to as "polymer (PM-1)") was obtained. About the obtained polymer (PM-1), the weight average molecular weight (Mw) measured by polystyrene conversion by GPC was 20000, and molecular weight distribution (Mw / Mn) was 2.1.

Comparative Synthesis Example 5A

A polymer (PM-2) was synthesized according to Scheme 4 below.

In a 1000 mL eggplant flask containing a stirrer, 10.0 g of 3,4-epoxycyclohexylmethyl methacrylate, 20.1 g (1 mol equivalent) of the side chain precursor (ca-1), 500 g of cyclopentanone, and tetrabutylammonium bromide 1.64 g (0.1 mol equivalent) was added and it stirred at 110 degreeC for 4 hours. Thereafter, 300 g of cyclohexane and 400 g of cyclopentanone were added to the reaction solution, and the liquid was washed five times with 400 g of distilled water. Thereafter, the organic layer was slowly concentrated by a rotary evaporator until the amount thereof became 50 g, and the white solid precipitated on the way was recovered by filtration. 23.0g of compounds (MI-6) were obtained by vacuum-drying this white solid.

Subsequently, in a 200 mL two-necked flask under nitrogen, 10.0 g (16.9 mmol) of compound (MI-6), 6.0 g (30.5 mmol) of 3,4-epoxycyclohexylmethyl methacrylate as a polymerization monomer, and meta 4.0 g (46.5 mmol) of krylic acid, 0.6 g (2.4 mmol) of 2,2'-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator, 2,4-diphenyl-4-methyl as a chain transfer agent 1.0 g (4.2 mmol) of 1-pentene and 86.4 g of NMP were added as a solvent, and it polymerized at 70 degreeC for 5 hours, and obtained the target polymer (this is called "polymer (PM-2)"). About the obtained polymer (PM-2), the weight average molecular weight (Mw) measured by polystyrene conversion by GPC was 20000, and molecular weight distribution (Mw / Mn) was 2.0.

<Production and Evaluation of Liquid Crystal Display Element (1)>

Example 1B

1. Preparation of liquid crystal aligning agent (AL-1)

NMP and butyl cellosolve (BC) were added as a solvent to 100 mass parts of polymers (P-1) obtained by the said Example 1A as a polymer [P], and a solvent composition is NMP / BC = 50/50 (mass ratio), Solid content concentration was made into the solution of 4.0 mass%. The liquid crystal aligning agent (AL-1) was prepared by filtering this solution with the filter of 1 micrometer of pore diameters.

2. Fabrication of Optical Vertical Liquid Crystal Display Device

The liquid crystal aligning agent (AL-1) prepared above was apply | coated using the spinner on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, and prebaking was performed for 1 minute on 80 degreeC hotplate. Then, it heated at 230 degreeC for 1 hour in the oven which carried out the nitrogen substitution of the inside of the oven, and formed the coating film of 0.1 micrometer in film thickness. Subsequently, 1,000 J / m <2> of polarized ultraviolet-ray containing 313 nm bright line was irradiated to this coating film surface from the direction which inclined 40 degrees from the board | substrate normal line using a Hg-Xe lamp and a glan tailor prism, and it was set as the liquid crystal aligning film. The same operation was repeated and a pair (two pieces) of board | substrates which have a liquid crystal aligning film were created.

After screen-printing the epoxy resin adhesive which contained the aluminum oxide sphere of 3.5 micrometers in diameter to the outer periphery of the surface which has one liquid crystal aligning film in the said board | substrate, the liquid crystal aligning film surface of a pair of board | substrates is made to oppose, It crimp | bonded so that the projection direction of the optical axis of an ultraviolet-ray to the board | substrate surface might become antiparallel, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) in the clearance gap between board | substrates in a liquid crystal injection hole, the liquid crystal injection hole was sealed with the epoxy adhesive. Furthermore, in order to remove the flow orientation at the time of liquid crystal injection, it heated to 130 degreeC, and then cooled slowly to room temperature. Next, the liquid crystal display element was manufactured by bonding the polarizing plate to the outer both surfaces of a board | substrate so that the polarization direction may mutually orthogonally cross, and also make the angle of 45 degrees with the projection direction to the substrate surface of the optical axis of the ultraviolet-ray of a liquid crystal aligning film. .

3. Evaluation of liquid crystal alignment

About the liquid crystal display element manufactured above, the presence or absence of the abnormal domain in the change of contrast when the voltage of 5V is ON / OFF (applied and released) is observed by an optical microscope, and the case where there is no abnormal domain is " A "and the case where there exist an abnormal domain in a part were" B "and the case where there was an abnormal domain as a whole was evaluated as" C ", and liquid-crystal orientation was evaluated. As a result, in this Example, the liquid crystal alignment property was "A".

4. Solvent resistance evaluation of liquid crystal aligning film

After apply | coating a liquid crystal aligning agent (AL-1) on the silicon substrate using the spinner, it prebaked at 90 degreeC on the hotplate for 2 minutes, and formed the coating film of 1.0 micrometer in film thickness. The obtained coating film was heated on 230 degreeC for 30 minutes on the hotplate. The obtained film was immersed in NMP for 1 minute, and it dried at 100 degreeC for 5 minutes. The change rate (DELTA) Dnmp of the film thickness before and behind immersion was calculated | required by following formula (1), and solvent resistance was evaluated by the change rate (DELTA) Dnmp.

ΔDnmp = [((Film thickness before immersion)-(Film thickness after immersion)) / (Film thickness before immersion)] x 100 k... (One)

Evaluation was "A" when the change rate (DELTA) Dmmp was -2% or more and 2% or less, "B" when it was in the range of -5% or more and less than -2%, or was larger than 2% and 5% or less, When it was larger than 5% or smaller than -5%, it was set as "C". In this example, the solvent resistance "A" was evaluated.

5. Evaluation of Voltage Integrity (VHR)

About the liquid crystal display element manufactured above, after applying the voltage of 5V by 60 microseconds of application time and 167 milliseconds of span, the voltage retention rate after 167 milliseconds after application | release cancellation was measured. The measurement apparatus used VHR-1 by Toyo Techniker Co., Ltd. At this time, when the voltage retention was 90% or more, "A", when 80% or more and less than 90%, "B", when 50% or more and less than 80%, "C" was set to "D" when it was less than 50%. As a result, in this Example, the voltage holding ratio was evaluation of "B".

6. Evaluation of thermal reliability

About the liquid crystal display element manufactured above, it heated for 500 hours in the oven set to 110 degreeC. The voltage holding ratio before and after heating was measured by the said method, and the fall of the voltage holding ratio after heating was evaluated. At this time, when the fall of the voltage holding ratio was 20% or less, "A", when 20% or more and less than 40%, "B" was set to "C" when 40% or more. As a result, the thermal reliability was evaluation of "A" in this Example.

7. Evaluation of printability

The liquid crystal aligning agent (AL-1) prepared above was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane using the offset type liquid crystal aligning film printer (made by Nippon Shashin Insatsu Co., Ltd.). After heating for 1 minute on a 80 degreeC hotplate, removing a solvent, and heating for 10 minutes on a 200 degreeC hotplate, the average film thickness measured with the stylus type film thickness meter (KLA Tenco Co., Ltd. product) was 800 Pa. Phosphorus film was formed.

This coating film was observed with the optical microscope of 20x magnification, and the printing nonuniformity and the presence or absence of the pinhole were investigated. The evaluation is "A" when neither the printing nonuniformity nor the pinhole was observed, and the case where at least one of the printing nonuniformity and the pinhole was observed in part is "B" and the case where at least one of the printing nonuniformity and the pinhole was observed as a whole. Was made into "C". As a result, in this Example, printability was evaluation of "B".

[Examples 2B to 15B and Comparative Examples 1B to 4B and 7B]

Except having changed the compounding composition as shown in following Table 2, it prepared at the solid content concentration similar to Example 1B, and obtained the liquid crystal aligning agent, respectively. Moreover, using each liquid crystal aligning agent, it carried out similarly to Example 1B, manufactured the optical vertical type liquid crystal display element, and performed various evaluation using the obtained liquid crystal display element. The result was combined with Table 2 below. In addition, in Table 2, the numerical value of a compound [A], another polymer, and an additive is about 100 mass parts of total polymer components used for preparation of a liquid crystal aligning agent about Example 1B, 8B, and Comparative Examples 1B, 2B. The usage ratio [mass part] of each compound is shown, and about Examples 2B-7B, 9B, 10B, 12B-18B, and Comparative Examples 3B, 4B, and 7B, the polyamic acid (PAA-1) used for preparation of a liquid crystal aligning agent is shown. The use ratio [mass part] of each compound with respect to a total of 100 mass parts of is shown, and about Example 11B, the use ratio of each compound with respect to a total of 100 mass parts of the polymer (PM-1) used for preparation of a liquid crystal aligning agent is shown. A mass part is shown.

<Production and Evaluation of Liquid Crystal Display Element (2)>

Example 16B

1. Preparation of liquid crystal aligning agent (AL-16)

100 parts by mass of the polyamic acid (PAA-1) obtained in Synthesis Example 1 as another polymer, 10 parts by mass of the polymer (P-8) obtained in Example 8A as the polymer [P], and 3-methoxy as a solvent. -1-Butanol (MB), NMP, and butyl cellosolve (BC) were added, and the solvent composition was made into the solution of MB / NMP / BC = 30/20/50 (mass ratio) and solid content concentration of 4.0 mass%. The liquid crystal aligning agent (AL-16) was prepared by filtering this solution with the filter of 1 micrometer of pore diameters.

2. Fabrication of Optical Horizontal Liquid Crystal Display Device

The liquid crystal aligning agent (AL-16) prepared above was apply | coated using the spinner on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, and prebaking was performed for 1 minute on 80 degreeC hotplate. Then, it heated at 230 degreeC for 1 hour in the oven which carried out the nitrogen substitution of the inside of the oven, and formed the coating film of 0.1 micrometer in film thickness. Subsequently, 1,000 J / m <2> of polarized ultraviolet-ray containing 313 nm bright line was irradiated to this coating film surface from the direction which inclined 90 degrees from the board | substrate normal line using a Hg-Xe lamp and a glan tailor prism, and it was set as the liquid crystal aligning film. The same operation was repeated and a pair (two pieces) of board | substrates which have a liquid crystal aligning film were created.

After screen-printing the epoxy resin adhesive which contained the aluminum oxide sphere of 3.5 micrometers in diameter to the outer periphery of the surface which has one liquid crystal aligning film in the said board | substrate, the liquid crystal aligning film surface of a pair of board | substrates is made to oppose, It crimp | bonded so that the projection direction of the optical axis of an ultraviolet-ray to the board | substrate surface might be horizontal, and the adhesive agent was thermosetted at 150 degreeC over 1 hour. Subsequently, after filling a positive liquid crystal (MLC-7028-100 by Merck Co., Ltd.) in the clearance gap between board | substrates in a liquid crystal injection hole, the liquid crystal injection hole was sealed with the epoxy adhesive. Furthermore, in order to remove the flow orientation at the time of liquid crystal injection, it heated to 130 degreeC, and then cooled slowly to room temperature. Next, the liquid crystal display element was manufactured by bonding the polarizing plate to the outer both surfaces of a board | substrate so that the polarization direction may mutually orthogonally cross, and also make the angle of 90 degrees with the projection direction to the board surface of the optical axis of the ultraviolet-ray of a liquid crystal aligning film. .

3. Evaluation

About the optical horizontal type liquid crystal display element manufactured above, it carried out similarly to Example 1B, and evaluated liquid crystal orientation, solvent resistance, voltage retention (VHR), thermal reliability, and printability. The results are shown in Table 2 below.

[Comparative Example 5B]

Except having changed the compounding composition as shown in following Table 2, it prepared at the solid content concentration similar to Example 16B, and obtained the liquid crystal aligning agent, respectively. Moreover, using the liquid crystal aligning agent, each optical liquid crystal display element was produced like Example 16B, and various evaluation was performed similarly to Example 1 B using the obtained liquid crystal display element. The results are shown in Table 2 below.

<Production and Evaluation of Liquid Crystal Display Element (3)>

Example 17B

1. Preparation of liquid crystal aligning agent (AL-17)

A liquid crystal aligning agent (AL-17) was prepared at the solid content concentration similar to the said Example 16B except having changed the compounding composition as shown in Table 2 below.

2. Fabrication of PSA type liquid crystal display device

The liquid crystal aligning agent (AL-17) prepared above was apply | coated using the spinner on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film, and prebaking was performed for 1 minute on 80 degreeC hotplate. Then, it heated in 230 degreeC for 1 hour in the oven which carried out the nitrogen substitution of the inside of the oven, and formed the coating film of 0.1 micrometer in film thickness. The same operation was repeated and a pair (two pieces) of board | substrates which have a liquid crystal aligning film were created.

After apply | coating by the screen printing the epoxy resin adhesive which put the aluminum oxide sphere of 3.5 micrometers in diameter on the outer periphery of the surface which has one liquid crystal aligning film among the said board | substrates, the liquid crystal aligning film surface of a pair of board | substrate is made to face at 150 degreeC. The adhesive was heat cured over 1 hour. Subsequently, after filling a negative liquid crystal (MLC-6608 by Merck Co., Ltd.) in the clearance gap between board | substrates in a liquid crystal injection hole, the liquid crystal injection hole was sealed with the epoxy adhesive. Furthermore, in order to remove the flow orientation at the time of liquid crystal injection, it heated to 130 degreeC, and then cooled slowly to room temperature.

Next, an alternating current of 10 Hz at a frequency of 60 Hz was applied between the pair of electrodes, and the ultraviolet light was irradiated at an irradiation amount of 100,000 J / m 2 using an ultraviolet irradiation device using a metal halide lamp to the light source while the liquid crystal was driven. . In addition, this irradiation amount is the value measured using the photometer measured with the wavelength 365nm reference. Then, the liquid crystal display element was manufactured by bonding the polarizing plate to the outer both surfaces of the board | substrate so that the polarization direction may mutually orthogonally cross, and also make the angle of 45 degrees with the projection direction to the substrate surface of the optical axis of the ultraviolet-ray of a liquid crystal aligning film. .

3. Evaluation

About the PSA type liquid crystal display element manufactured above, it carried out similarly to Example 1B, and evaluated liquid crystal orientation, solvent resistance, voltage retention (VHR), thermal reliability, and printability. The results are shown in Table 2 below.

Example 18B and Comparative Example 6B

Except having changed the compounding composition as shown in following Table 2, it prepared at the solid content concentration similar to Example 16B, and obtained the liquid crystal aligning agent, respectively. Moreover, using each liquid crystal aligning agent, it carried out similarly to Example 17B, and manufactured the liquid crystal display element, and performed various evaluations similarly to Example 1B using the obtained liquid crystal display element. The results are shown in Table 2 below.

In Table 2, the numerical value of a solvent shows the compounding ratio (mass part) of each solvent with respect to 100 mass parts of total amounts of the solvent used for preparation of a liquid crystal aligning agent. Abbreviated-name of a solvent is as follows.

NMB: N-methyl-2-pyrrolidone

BC: Butyl Cellosolve

MB: 3-methoxy-1-butanol

CPN: cyclopentanone

PGME: Propylene Glycol Monomethyl Ether

EDM: diethylene glycol methyl ethyl ether

PGMEA: propylene glycol monomethyl ether acetate

As can be seen from the results of the above examples, according to Examples 1B to 18B using the liquid crystal aligning agent containing the silicon-containing compound [A], a liquid crystal display device having excellent heat reliability was obtained. Moreover, the obtained liquid crystal display element was excellent also in liquid crystal alignability and a voltage holding ratio in addition to thermal reliability, and was also excellent in the solvent resistance and printability of a liquid crystal aligning film. On the other hand, Comparative Examples 1B-7B using the liquid crystal aligning agent which does not contain a silicon containing compound [A] were inferior to thermal reliability compared with the thing of an Example. Moreover, even if it considered not only thermal reliability but also solvent resistance, a voltage holding ratio, and printability collectively, the Example was improved in the balance.

Although the present disclosure has been described based on the embodiments, it is understood that the present disclosure is not limited to the above embodiments and structures. The present disclosure also includes various modifications and modifications within the equivalent range. In addition, various combinations and forms, and further, other combinations and forms including only one element, more, or less of them fall within the scope and spirit of the present disclosure.

Claims (12)

The liquid crystal aligning agent containing the cyclic ether group and the silicon containing compound which has a functional group (B) which reacts with a cyclic ether group. The method of claim 1,
The said functional group (B) is a liquid crystal aligning agent which is a functional group which reacts with a cyclic ether group by heat. The method according to claim 1 or 2,
The said silicon-containing compound is polymer [P] which has a siloxane skeleton, The liquid crystal aligning agent. The method of claim 3,
The said polymer [P] has a photoalignable group, The liquid crystal aligning agent. The method according to claim 3 or 4,
The said polymer [P] has a orientation expression site | part which orientates a liquid crystal molecule, The liquid crystal aligning agent. The method according to any one of claims 3 to 5,
The said polymer [P] has a group containing a carbon-carbon unsaturated bond, The liquid crystal aligning agent. The method according to any one of claims 3 to 6,
The liquid crystal aligning agent which further contains polymer [Q] different from the said polymer [P]. The method of claim 7, wherein
The said polymer [Q] is at least 1 sort (s) chosen from the group which consists of a polymer of a polyamic acid, a polyamic acid ester, a polyimide, and a monomer which has a polymerizable unsaturated bond. The method according to any one of claims 1 to 8,
The said functional group (B) is a carboxyl group or a protected carboxyl group, The liquid crystal aligning agent. The liquid crystal aligning film formed from the liquid crystal aligning agent in any one of Claims 1-9. The liquid crystal element provided with the liquid crystal aligning film of Claim 10. Polyorganosiloxane which has a cyclic ether group and the functional group (B) which reacts with a cyclic ether group.