TWI572676B - Silicon liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display components - Google Patents

Description

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

The present invention relates to a liquid crystal alignment agent comprising a polyoxyalkylene obtained by polycondensing an alkoxysilane; a liquid crystal alignment film obtained by the liquid crystal alignment agent; and a liquid crystal display element having the liquid crystal display element Liquid crystal alignment film.

In recent years, among display modes of liquid crystal display elements, vertical (VA) type liquid crystal display elements have been widely used in large-screen liquid crystal televisions or high-definition mobile phone applications (display positions of digital cameras or mobile phones).

Regarding the VA type, there is known a MVA type (Multi Vertical Alignment) which forms a protrusion for controlling the direction in which the liquid crystal falls down in the TFT panel or the color filter substrate; or a PVA (Patterned Vertioal Alignment) type, which is attached to The ITO electrode of the substrate forms a slit, and the direction in which the liquid crystal falls down is controlled by an electric field.

Other alignment methods include the PSA (Polymer sustained Alignment) type. Among the VA types, the PSA type is a technology that has attracted attention in recent years. In this manner, after a liquid crystal panel is added to a liquid crystal to produce a liquid crystal panel, an electric field is applied to cause the liquid crystal to fall, and in this state, the liquid crystal panel is irradiated with UV. As a result, photopolymerization of the polymerizable compound causes the alignment direction of the liquid crystal to be fixed, and pre-tilt occurs, and the reaction rate is improved. A slit is formed in the one-side electrode constituting the liquid crystal panel, and is characterized in that even the opposite electrode pattern is not provided with a protrusion like MVA or a PVA. The construction of the slit can also be operated, the manufacturing process is simplified or excellent panel transmittance can be obtained. (Refer to Patent Document 1)

A known liquid crystal alignment film material includes an inorganic liquid crystal alignment film material such as polyimine which is conventionally used, and an inorganic liquid crystal alignment film material. For example, there has been proposed a composition of an alignment agent containing a reaction product of a tetraalkanooxane, a trialkoxide, an alcohol, and an oxalic acid as a material of a coating type inorganic alignment film, and a liquid crystal alignment film is reported. It is excellent in vertical alignment, heat resistance, and uniformity on the electrode substrate of the liquid crystal display element. (Refer to Patent Document 2)

In addition, there is also a liquid crystal alignment agent composition which contains a reaction product with a tetraalkoxysilane, a specific trialkoxysilane and water and a specific glycol ether solvent, and reports the formation of a liquid crystal alignment film. In order to prevent display failure, the afterimage characteristics are also good after a long period of driving, the ability to align the liquid crystal is not lowered, and the reduction in the voltage holding ratio of light and heat is small. (Refer to Patent Document 3)

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-302061

Patent Document 2: Japanese Laid-Open Patent Publication No. 09-281502

Patent Document 3: Japanese Laid-Open Patent Publication No. 2005-250244

Among the PSA type liquid crystal display elements, polymerization added to the liquid crystal The solubility of the compound is low, and if the amount of addition is increased, there is a problem that it precipitates at a low temperature. On the other hand, when the addition amount of a polymeric compound is reduced, a favorable alignment state cannot be obtained. Further, since the unreacted polymerizable compound remaining in the liquid crystal becomes an impurity (contaminant) in the liquid crystal, there is a problem that the reliability of the liquid crystal display element is lowered. In this case, by introducing a side chain capable of undergoing a polymerization reaction into the alignment film, even when a liquid crystal to which a polymerizable compound is not added is used, characteristics equivalent to those of the PSA type can be obtained.

In the vertically aligned VA type, a strong vertical alignment force is required in order to generate a vertical alignment. However, this method does not use a polymerizable compound. If the vertical alignment force is increased, the reaction speed after UV irradiation becomes slower. The reaction speed after UV irradiation reduces the vertical alignment force. The vertical alignment force and the increase in the reaction speed after UV irradiation are mutually trade-off.

An object of the present invention is to provide a liquid crystal alignment agent which can be used in the same manner as the PSA type by using a liquid crystal which does not contain a polymerizable compound, and can form a liquid crystal alignment film, even in a liquid crystal display which improves the reaction speed after UV irradiation. Among the elements, the vertical alignment force is not lowered, and the reaction speed after UV irradiation can be improved; and a liquid crystal display element having a liquid crystal alignment film obtained by the liquid crystal alignment agent.

The gist of the present invention is as follows.

[1] A liquid crystal alignment agent comprising the following polyoxyalkylene (A) and Polyoxane (B):

Polyoxane (A): a polyoxyalkylene obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (1) and an alkoxydecane represented by the formula (2): R ¹ Si (OR) _{^{2) 3 (1) (R}} 1 to be substituted with a fluorine atom and a hydrocarbon group having a carbon number of 8 to 30, R ² represents an alkyl group having 1 to 5 carbon atoms of)

R ³ Si(OR ⁴ ) ₃ (2) (R ³ is an alkyl group having 1 to 30 carbon atoms substituted by an acryl fluorenyl group, a methacryl fluorenyl group or an aryl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms )

Poly Silicon siloxane (B): containing the formula (3) represented by the alkoxy silane-70% to 100% of the alkoxy silane-polycondensation of the resulting poly silicon _{^{siloxane: Si (OR 5) 4 (}} 3) (R ⁵ represents an alkyl group having 1 to 5 carbon atoms).

[2] The liquid crystal alignment agent according to the above [1], wherein the polyoxyalkylene (B) is a polyoxoxane obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (2). .

[3] The liquid crystal alignment agent according to the above [1], wherein the polyoxyalkylene (B) is a polyoxane obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (4). : R ⁶ Si(OR ⁷ ) ₃ (4) (R ⁶ is an alkyl group having 1 to 5 carbon atoms, and R ⁷ represents an alkyl group having 1 to 5 carbon atoms).

[4] The liquid crystal alignment agent according to any one of the above [1], wherein at least one selected from the group consisting of polyoxyalkylene (A) and polyoxyalkylene (B) Further, the alkane further contains a polyoxyalkylene obtained by polycondensing an alkoxysilane having an alkoxysilane represented by the following formula (5).

(R ⁸ ) _n Si(OR ⁹ ) _4-n (5) (R ⁸ is a hydrogen atom or may be substituted with a hetero atom, a halogen atom, an amine group, a glycidyl ether group, a fluorenyl group, an isocyanate group or a urea group and carbon A hydrocarbon group of 1 to 12, R ⁹ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3).

[5] The liquid crystal alignment agent according to any one of the above [1], wherein the alkoxysilane used in the polyoxyalkylene (A) contains the above formula (1). The alkoxy oxane 1 mol% to 20 mol%, and the alkoxy decane represented by the above formula (2) contains 10 mol% of the alkoxy decane represented by the above formula (2). 80% by mole.

[6] A liquid crystal alignment film obtained by applying the liquid crystal alignment agent according to any one of the above [1] to [5], drying the film, and baking the liquid crystal alignment agent.

[7] A liquid crystal display element comprising the liquid crystal alignment film according to [6] above.

[8] A liquid crystal display device which is applied to a liquid crystal cell in which liquid crystal is sandwiched between two substrates which are fired by the liquid crystal alignment agent according to any one of the above [1] to [5]. It is obtained by irradiating UV under a voltage state.

[9] A method of producing a liquid crystal display device, wherein the liquid crystal alignment agent according to any one of the above [1] to [5] is applied, and the liquid crystal is sandwiched between two substrates, and is applied UV is irradiated under voltage conditions.

According to the present invention, by using a liquid crystal which does not contain a polymerizable compound and irradiating UV in the same manner as the PSA type, a liquid crystal alignment agent can be obtained which can be formed without lowering the vertical alignment force and improving the UV irradiation. A liquid crystal alignment film having a reaction rate; and a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment agent.

<polyoxane (A)>

The polyoxyalkylene (A) is a polyoxyalkylene obtained by polycondensing an alkoxysilane having an alkoxysilane represented by the formula (1) and an alkoxysilane represented by the formula (2).

In _{^{R 1 Si (OR 2) 3}} (1) of formula ^(1), R 1 to be substituted with a fluorine atom and a hydrocarbon group having a carbon number of 8 to 30, R ² represents an alkyl group having 1 to 5 carbon atoms of.

R ³ Si(OR ⁴ ) ₃ (2) In the formula (2), R ³ is an alkyl group substituted with an acryl fluorenyl group, a methacryl fluorenyl group or an aryl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms.

R ¹ (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by the formula (1) is a hydrocarbon group having a carbon number of 8 to 30 (preferably 8 to 22) which may be substituted by fluorine, as long as it has a liquid crystal vertical The substance of the effect of the alignment is not particularly limited.

Examples of the specific organic group include an alkyl group, a fluoroalkyl group, an alkenyl group, a phenethyl group, a styrylalkyl group, a naphthyl group, a fluorophenylalkyl group and the like. Among these, an alkoxydecane having R ¹ as an alkyl group or a fluoroalkyl group is easily obtained as a commercially available product having a relatively low price, and is therefore suitable. In the above fluoroalkyl group, the number of fluorine atoms is 1 or more, and all of the hydrogens may be substituted by a fluorine atom.

In particular, alkoxydecane wherein R ¹ is an alkyl group is preferred. The polyoxyalkylene (A) used in the present invention may also have a plurality of these specific organic groups.

R ² of the alkoxydecane represented by the formula (1) has 1 to 5 carbon atoms, preferably 1 to 3 alkyl groups. Preferably R ² is methyl or ethyl.

Specific examples of such alkoxydecane represented by the formula (1) are listed below, but are not limited thereto.

For example, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane, dodecyltrimethoxydecane, dodecyltriethoxy Decane, cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxydecane,octadecyltrimethoxydecane, ten Octaalkyltriethoxydecane, nonadecyltrimethoxynonane, nonadecyltriethoxydecane, undecyltriethoxydecane,undecyltrimethoxydecane,21-di Dodecenyltriethoxydecane, tridecafluorooctyltrimethoxydecane, tridecafluorooctyltriethoxydecane, heptadecafluorodecyltrimethoxydecane, heptadecafluorodecyltriethoxy Decane, isooctyltriethoxydecane, phenethyltriethoxydecane, pentafluorophenylpropyltrimethoxydecane, m-styrylethyltrimethoxydecane, p-styrylethyltrimethoxy Basear, (1-naphthyl)triethoxydecane, (1-naphthyl)trimethoxydecane, and the like. Among them, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, decyltriethoxydecane,dodecyltrimethoxydecane,dodecyltriethoxydecane , cetyltrimethoxydecane, cetyltriethoxydecane, heptadecyltrimethoxydecane, heptadecyltriethoxy Decane, octadecyltrimethoxydecane, octadecyltriethoxydecane, nonadecyltrimethoxydecane, pentadecyltriethoxydecane, undecyltriethoxydecane, Or undecyltrimethoxydecane is preferred.

In order to obtain good liquid crystal alignment, the alkoxysilane represented by the formula (1) having the above specific organic group accounts for 1 mole among all the alkoxysilanes used for obtaining the polyoxyalkylene (A). More than % of the ear is preferred. It is preferably 1.5 mol% or more. More preferably 2 mol% or more. Further, in order to obtain sufficient curing properties of the formed liquid crystal alignment film, it is preferably 30 mol% or less. It is preferably 25 mol% or less.

R ³ (hereinafter also referred to as a second specific organic group) of the alkoxysilane represented by the formula (2) is substituted with at least one selected from the group consisting of an acryloyl group, a methacryl group and an aromatic group. Alkyl group. The number of substituted hydrogen atoms is one or more, preferably one. The carbon number of the alkyl group is preferably from 1 to 30, preferably from 1 to 20. More preferably 1~10. The alkyl group may be linear or branched, and is preferably linear.

R ⁴ of the alkoxysilane represented by the formula (2) is an alkyl group having 1 to 5 carbon atoms, preferably a carbon number of 1 to 3, particularly preferably a carbon number of 1 to 2.

Specific examples of the alkoxydecane represented by the formula (2) are listed below, but are not limited thereto. For example, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, methacryloxymethyltrimethoxydecane, methacryloxoxime Methyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, propyleneoxyethyltrimethoxydecane, propylene oxime Base ethyl triethoxy decane, styrylethyl trimethoxy decane, benzene Vinylethyltriethoxydecane, 3-(N-styrylmethyl-2-amineethylamino)propyltrimethoxydecane.

In the production of the polyoxyalkylene (A), in addition to the alkoxysilane represented by the formulas (1) and (2), in order to improve the adhesion to the substrate and the affinity with the liquid crystal molecules, One or more alkoxysilanes represented by the following formula (5) may also be used on the premise that the effects of the present invention are impaired. The alkoxydecane represented by the formula (5) can impart various properties to the polyoxyalkylene, and therefore one or more kinds can be used depending on the necessary characteristics.

(R ⁸ ) _n Si(OR ⁹ ) _4-n (5)

In the formula (5), R ⁸ is a hydrogen atom or a hydrocarbon group which may be substituted with a hetero atom, a halogen atom, an amine group, a glycidyl ether group, a mercapto group, an isocyanate group or a urea group and has a carbon number of 1 to 10. R ⁹ is an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3). n is an integer from 0 to 3 (preferably 0 to 2).

R ⁸ of the alkoxysilane represented by the formula (5) is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (hereinafter also referred to as a third specific organic group).

Examples of the third specific organic group, for example, an aliphatic hydrocarbon group; a hydrocarbon group having an aliphatic ring, an aromatic ring, and a heterocyclic ring structure; a hydrocarbon group having an unsaturated bond; and a hetero atom which may contain an oxygen atom, a nitrogen atom, a sulfur atom or the like The atom or the like may have a branched structure and a hydrocarbon group having 1 to 6 carbon atoms. The third specific organic group may also be substituted with a halogen atom, an amine group, a glycidyl ether group, a thiol group, an isocyanate group, a urea group or the like.

Specific examples of the alkoxysilane represented by the formula (5) are listed below, but are not limited thereto. 3. 3-(2-Aminoethylaminopropyl)trimethoxynonane, 3-(2-Aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethoxydecane, 2-(2-aminoethylthioethyl)triethoxydecane , 3-mercaptopropyltriethoxydecane, mercaptomethyltrimethoxydecane, vinyltriethoxydecane, 3-isocyanatepropyltriethoxydecane,trifluoropropyltrimethoxydecane,chloropropane Triethoxy decane, bromopropyltriethoxy decane, 3-mercaptopropyltrimethoxydecane, dimethyldiethoxydecane, dimethyldimethoxydecane, diethyldiethoxy Base decane, diethyl dimethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, 3-aminopropyl methyl diethoxy decane, 3-aminopropyl dimethyl Ethoxy decane, trimethyl ethoxy decane, trimethyl methoxy decane, γ-ureidopropyl triethoxy decane, γ-ureidopropyl trimethoxy decane and γ-ureidopropyl tripropyl Oxydecane, etc.

An alkoxydecane-based tetraalkoxyne wherein n is 0 in the alkoxydecane represented by the formula (5). Since the tetraalkane is easily condensed with the alkoxysilane represented by the formulae (1) to (4), the polyoxyalkylene (A) of the present invention can be obtained, which is suitable.

The alkoxy decane wherein n is 0 in the formula (5) is preferably tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane or tetrabutoxy decane, especially four. Oxydecane or tetraethoxydecane is preferred.

In the present invention, it is preferred that all of the alkoxysilanes used in the production of the polyoxyalkylene (A) contain the alkoxy decane represented by the formula (1) in an amount of from 1% to 20% by mole. 2 mol% to 20 mol%, and all alkoxydecane used in the manufacture of polyoxyalkylene (A) preferably contains 10 mole % of alkoxydecane represented by formula (2). 80% by mole, especially preferably 30% by mole to 80% by mole.

<polyoxane (B)>

The polyoxyalkylene (B) is a polyoxyalkylene obtained by polycondensing alkoxysilane having 70 to 100% by weight of the alkoxysilane represented by the formula (3).

Si(OR ⁵ ) ₄ (3) In the formula (3), R ⁵ represents an alkyl group having 1 to 5 carbon atoms, preferably a carbon number of 1 or 2.

Specific examples of the alkoxydecane represented by the formula (3) are preferably tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane, especially tetramethoxy. Preferably, decane or tetraethoxy decane is preferred.

The polyoxyalkylene (B) may further be a polyoxyalkylene obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (2), in addition to the alkoxysilane represented by the formula (3).

The alkoxydecane represented by the formula (2) contained in the polyoxyalkylene (B) may be an alkoxydecane used in the production of the above polyoxyalkylene (A). The specific examples are also the same as described above.

The polyoxyalkylene (B) may further be a polyoxyalkylene obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (4), in addition to the alkoxysilane represented by the formula (3).

R ⁶ Si(OR ⁷ ) ₃ (4) In the formula (4), R ⁶ is an alkyl group having 1 to 5 carbon atoms, and R ⁷ represents an alkyl group having 1 to 5 carbon atoms. Formula (4) represents the Silane alkoxy of R ⁶ is alkyl of 1 to 5. The carbon number of the alkyl group is preferably from 1 to 4, more preferably from 1 to 3. R ⁷ of the alkoxysilane represented by the formula (4) is an alkyl group having 1 to 5 carbon atoms, preferably a carbon number of 1 to 3, particularly preferably a carbon number of 1 to 2.

Specific examples of the alkoxydecane represented by the formula (4) are listed below, but are not limited thereto. For example, methyl triethoxy decane, methyl trimethoxy decane, dimethyl trimethoxy decane, dimethyl triethoxy decane, n-propyl trimethoxy decane, n-propyl triethoxy decane.

In particular, the liquid crystal alignment agent further contains polyoxyalkylene (B) in addition to the alkoxysilane represented by the formula (3), and the polyoxyalkylene (B) is represented by the formula (4). It is obtained by polycondensation of an alkoxydecane alkoxy decane, which has a high vertical alignment force and is particularly suitable.

In order to increase the reaction speed of the liquid crystal display element by applying a voltage while applying a voltage to the liquid crystal to which the polymerizable compound is not added, the alkoxysilane represented by the formula (2) having the second specific organic group is used in order to It is preferred that all of the alkoxydecane used in the polyoxyalkylene (B) is 10 mol% or more. It is preferably 20 mol% or more. More preferably 30% by mole or more. Further, in order to sufficiently cure the formed liquid crystal alignment film, it is preferably 75 mol% or less.

In the production of the polyoxyalkylene (B), in addition to the alkoxydecane represented by the formula (2), the formula (3), and the formula (4), the adhesion of the substrate and the affinity with the liquid crystal molecules are improved. For the purpose, one or more alkoxysilanes represented by the following formula (5) may be used without impairing the effects of the present invention. The alkoxydecane represented by the formula (5) can impart various properties to the polyoxyalkylene, and therefore one or more kinds can be used depending on the necessary characteristics.

(R ⁸ ) _n Si(OR ⁹ ) _4-n (5) In the formula (5), the structures and suitable ranges of R ⁸ and R ⁹ and the alkoxydecane represented by the formula (5) are as described above, for example. .

<Method for producing polyoxyalkylene oxide>

The method for obtaining the polyoxyalkylene used in the present invention is not particularly limited. The polyoxyalkylene (A) of the present invention is obtained by polycondensation of an alkoxydecane having an essential component of the above formula (1) and formula (2) in an organic solvent; and polyoxyalkylene (B) is obtained by The above formula (3) is obtained by polycondensation of an alkoxysilane having an essential component in an organic solvent. Usually, polyoxyalkylene is obtained by polycondensing such an alkoxydecane and uniformly dissolving it in an organic solvent to prepare a solution.

The method of polycondensing the alkoxysilane is, for example, a method of hydrolyzing and condensing the alkoxysilane in a solvent such as an alcohol or a glycol. At this time, the hydrolysis and condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically possible to add 0.5 times moles of water of all alkoxy groups in the alkoxysilane, and it is usually preferred to add an excess of 0.5 times mole of water.

In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, and it is usually preferably 0.5 to 2 times the molar amount of all alkoxy groups in the alkoxysilane, and 1 to 2 moles. Double Moore is preferred.

Further, in order to promote hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid; ammonia, methylamine, ethylamine, ethanolamine or triethylamine may be used. A catalyst such as a base; a metal salt such as hydrochloric acid, sulfuric acid or nitric acid. Further, in general, hydrolysis and condensation reactions can be further promoted by heating a solution in which an alkoxysilane is dissolved. At this time, the heating temperature and the heating time can be appropriately selected as desired. For example, a method of heating at 50 ° C, stirring for 24 hours, heating under reflux, stirring for 1 hour, or the like can be mentioned.

Further, as another method, for example, a method in which a mixture of alkoxysilane, a solvent, and oxalic acid is heated and condensed is condensed. Specifically, a method in which an oxalic acid alcohol solution is prepared by adding oxalic acid to an alcohol in advance, and then the solution is mixed with an alkoxysilane in a heated state. In this case, the amount of oxalic acid used is preferably 0.2 mol to 2 mol per mol of the total alkoxy group of the alkoxydecane, and is 0.5 mol to 1.5 mol. It is better. The heating in this method can be carried out at a liquid temperature of 50 ° C to 180 ° C. It should be a method of heating for several tens of minutes to ten hours under reflux in such a manner that liquid evaporation and volatilization do not occur.

In the case where a plurality of alkoxysilanes are used in the case of obtaining a polyoxyalkylene oxide, the alkoxysilane may be mixed in advance to prepare a mixture, or a plurality of alkoxysilanes may be sequentially mixed and used.

The solvent (hereinafter also referred to as a polymerization solvent) used in the polycondensation of the alkoxydecane is not particularly limited as long as it can dissolve the alkoxysilane. Further, in the case where the alkoxysilane is not dissolved, the alkoxydecane may be dissolved while being subjected to a polycondensation reaction. In general, an alcohol is produced by a polycondensation reaction of an alkoxysilane. Therefore, an alcohol, a glycol, a glycol ether, or an alcohol-soluble organic solvent can be used, and a glycol is particularly preferable.

Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexanediol, and 1,3-propanediol. 1,2-butanediol, 1,3-butane Alcohol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, Glycols such as 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and B Glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethyl Glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, Glycol ethers such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, dimethyl hydrazine, tetramethyl urea, trimethylamine hexamethyl phosphate, m-cresol, and the like. In the present invention, a plurality of the above polymerization solvents may also be used in combination.

The polymerization solution of the polyoxyalkylene obtained by the above method (hereinafter also referred to as a polymerization solution) is a concentration obtained by converting the ruthenium atom of all the alkoxysilanes charged as a raw material into SiO ₂ (hereinafter referred to as SiO _{2 ).} The concentration is preferably 20% by weight or less, and more preferably 5% by weight to 15% by weight. By selecting an arbitrary concentration in this concentration range, the generation of a colloid can be suppressed to obtain a homogeneous solution.

<Polyoxirane solution>

In the present invention, the polymerization solution obtained by the above method can be directly made into a solution of polyoxyalkylene. In addition, the solution obtained by the above method may be concentrated or added to a solvent to be diluted, or replaced with another solvent to form a polymer. A solution of oxoxane.

The solvent (hereinafter also referred to as an additive solvent) used at this time may be the same as the polymerization solvent, or may be another solvent. In the case where the polyoxyalkylene is uniformly dissolved, the solvent to be added is not particularly limited, and one or more may be arbitrarily selected and used.

Specific examples of such a solvent to be added include, in addition to the solvent exemplified as the above-mentioned polymerization solvent, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methyl acetate and ethyl acetate; An ester such as ethyl lactate.

These solvents can adjust the viscosity of the liquid crystal alignment agent or can improve the coatability when the liquid crystal alignment agent is applied onto the substrate by spin coating, offset printing, inkjet or the like.

<Other ingredients>

In the present invention, other components other than polysiloxane, such as inorganic fine particles, metal oxyalkylene oligomers, and metal oxyalkylenes, may be contained in the solution of polyoxyalkylene oxide without impairing the effects of the present invention. A component such as a polymer, a homogenizer, a further surfactant, or the like.

The inorganic fine particles are preferably fine particles such as cerium oxide fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles, and particularly preferably in the form of a colloidal solution. The colloidal solution may be a solution obtained by dispersing inorganic fine particles in a dispersion medium, or may be a colloidal solution of a commercially available product. In the present invention, by containing inorganic fine particles, the formed hardened film can be given a surface shape and other functions. The inorganic fine particles have an average particle diameter of It is preferably 0.001 μm to 0.2 μm, more preferably 0.001 μm to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the cured film formed by the prepared coating liquid may be used, and the transparency may be lowered.

Examples of the dispersion medium of the inorganic fine particles include water and an organic solvent. The pH or pKa of the colloidal solution is preferably adjusted to 1 to 10 from the viewpoint of the stability of the coating liquid for forming a film. It is preferably 2 to 7.

Examples of the organic solvent used in the dispersion medium of the colloidal solution include methanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol, and ethylene glycol. Alcohols such as propyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N a guanamine such as methylpyrrolidone; an ester such as ethyl acetate, butyl acetate or γ-butyrolactone; or an ether such as tetrahydrofuran or 1,4-dioxane. Among these, alcohols or ketones are preferred. These organic solvents may be used singly or in combination of two or more kinds as a dispersion medium.

As the metal oxyalkylene oligomer and the metal oxyalkylene polymer, a single or composite oxide precursor of ruthenium, titanium, aluminum, ruthenium, osmium, iridium, tin, indium, zinc or the like can be used. The metal oxyalkylene oligomer and the metal oxyalkylene polymer may be commercially available or may be a metal alkoxide, a nitrate, a hydrochloride, a carboxylate or the like, by a conventional method such as hydrolysis. The substance obtained.

Specific examples of commercially available metal oxyalkylene oligomers and metalloxane polymers include decyl oxides such as Methylsilicate 51, Methylsilicate 53A, Ethylsilicates 40, Ethylsilicates 48, EMS-485, and SS-101 manufactured by Colcoat. Oligomer or siloxane polymerization A titanyl oligomer such as a n-butoxytitanium tetramer manufactured by Kanto Chemical Co., Ltd. These may be used alone or in combination of two or more.

Further, a homogenizing agent, a surfactant, and the like can be used, and it is suitable for use in a commercially available product.

Further, the method of mixing the above other components in the polyoxyalkylene can be carried out simultaneously with or after the polyoxyalkylene, and is not particularly limited.

[Liquid alignment agent]

The liquid crystal alignment agent of the present invention contains the above polysiloxane, and a solution containing other components as necessary. In this case, as the solvent, a solvent selected from the group consisting of a polymerization solvent of the above polyoxyalkylene and a solvent may be used.

The content of the per-polysiloxane in the liquid crystal alignment agent is preferably from 0.5% by weight to 15% by weight, preferably from 1% by weight to 6% by weight, based on the SiO ₂ equivalent concentration. As long as such a concentration in terms of SiO ₂ is present, it is possible to easily obtain a desired film thickness in one application, and it is easy to obtain a sufficient pot life.

The liquid crystal alignment agent of the present invention contains polyoxyalkylene (A) and polyoxyalkylene (B) in a weight ratio of 10:90 to 50:50, preferably 20: in all polyoxyalkylene. 80~40:60.

Further, the weight ratio of the wholly polyoxyalkylene to the other components to be added in the liquid crystal alignment agent of the present invention is from 99:1 to 50:50, preferably from 98:2 to 70:30.

The method of preparing the liquid crystal alignment agent of the present invention is not particularly limited. The polyoxyalkylene used in the present invention is only required to be added as necessary. It can be divided into evenly mixed states. Usually, polyoxyalkylene is polycondensed in a solvent, so that a simple method is to directly use a solution of polyoxyalkylene or to add other components as necessary in a solution of polyoxyalkylene. Further, the method of directly using a polymerization solution of polyoxyalkylene is the easiest.

Further, when adjusting the content of the polyoxyalkylene in the liquid crystal alignment agent, a solvent selected from the group consisting of a polymerization solvent of the alkoxysilane and an additive solvent of polyoxyalkylene can be used.

[Liquid alignment film]

The liquid crystal alignment film of the present invention is obtained by using the liquid crystal alignment agent of the present invention. For example, the liquid crystal alignment agent of the present invention can be applied to a substrate, dried, and fired, and the obtained cured film can be directly used as a liquid crystal alignment film. Further, the cured film may be subjected to rubbing, irradiation of polarized light, light of a specific wavelength, or the like, or treatment with an ion beam or the like, or irradiation of UV in a state where a voltage is applied to the liquid crystal display element after liquid crystal filling.

The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it is a substrate having high transparency, and a substrate having a transparent electrode for driving the liquid crystal on the substrate is preferably formed.

Specific examples include glass plates, polycarbonates, poly(meth)acrylates, polyether oximes, polyarylates, polyurethanes, polybenzazoles, polyethers, polyetherketones, and top three. a transparent electrode formed of a plastic plate such as pentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triethylene fluorene cellulose, diethyl hydrazine cellulose, cellulose acetate butyrate or the like Substrate.

The coating method of the liquid crystal alignment agent includes a spin coating method and printing. A method, an inkjet method, a spray method, a roll coating method, and the like, and a transfer method widely used in the industry is also suitable for use in the present invention from the viewpoint of productivity.

After the liquid crystal alignment agent is applied, the drying step is not necessarily required, and the time from the application to the time when the firing is stopped varies with each substrate, or the case where the firing is not immediately performed after the coating is performed, good. This drying is not limited to the extent that the shape of the coating film is not deformed by the conveyance of the substrate or the like, and the solvent can be removed. The drying means is not particularly limited. For example, a method of drying for 0.5 minute to 30 minutes (preferably 1 minute to 5 minutes) on a hot plate at a temperature of 40 ° C to 150 ° C (preferably 60 ° C to 100 ° C) may be mentioned.

The coating film formed by coating the liquid crystal alignment agent by the above method can be fired to form a cured film. In this case, the firing temperature may be carried out at any temperature of from 100 ° C to 350 ° C, and is preferably from 140 ° C to 300 ° C, preferably from 150 ° C to 230 ° C, more preferably from 160 ° C to 220 ° C. The firing time can be fired at any time from 5 minutes to 240 minutes. It should be 10 minutes to 90 minutes, preferably 20 minutes to 80 minutes. For the heating, a well-known method such as a hot plate, a hot air circulation oven, an IR (infrared) oven, a belt furnace, or the like can be usually used.

The polyoxyalkylene oxide in the liquid crystal alignment film is subjected to polycondensation in the firing step. However, in the present invention, it is not necessary to completely condense the mixture without impairing the effects of the present invention. However, it is preferable to burn at a temperature higher than 10 ° C which is higher than the heat treatment temperature of the sealant hardening required for the liquid crystal cell manufacturing step.

The thickness of the cured film may be selected as necessary, and is preferably 5 nm or more, preferably 10 nm or more, since the liquid crystal display element can be easily obtained. Reliability, so it is suitable. Further, the thickness of the cured film is preferably 300 nm or less, preferably 150 nm or less, and is suitable because the power consumption of the liquid crystal display element does not become extremely large.

<Liquid crystal display element>

The liquid crystal display device of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by a method described above, and then forming a liquid crystal cell by a known method.

In an example of the production of the liquid crystal cell, there is generally a method in which a pair of substrates on which a liquid crystal alignment film is formed are sandwiched by a spacer, fixed by a sealant, and injected into a liquid crystal and sealed. At this time, the size of the spacer to be used is 1 μm to 30 μm, and preferably 2 μm to 10 μm.

The method of injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method in which a liquid crystal is decompressed in the liquid crystal cell to be formed, a liquid crystal method in which liquid crystal is injected, and a dropping method in which a liquid crystal is dropped after the liquid crystal is dropped.

When UV is applied to the electrodes of the substrates on both sides of the liquid crystal cell into which the liquid crystal is introduced, the acryl fluorenyl group, the methacryl fluorenyl group or the like in the alignment film is polymerized and crosslinked, and the liquid crystal is crosslinked. The response speed of the display becomes faster. Here, the applied voltage is 5Vp-p~50Vp-p, and is preferably 5Vp-p~30Vp-p. The amount of UV irradiation to be irradiated is 1 J (joules) to 60 J, and preferably 40 J or less. When the amount of UV irradiation is small, it is possible to suppress a decrease in reliability (characteristics that do not break the members constituting the liquid crystal display), reduce the UV irradiation time, and improve the production tact (work).

The substrate used in the liquid crystal display element is not particularly limited as long as it is a substrate having high transparency, and is usually formed on a substrate to be used. A substrate that drives a transparent electrode of a liquid crystal. The specific example is the same as the substrate described in [Liquid Crystal Alignment Film]. A standard so-called PVA or MVA substrate having an electrode pattern or a protrusion pattern can also be used.

In the same manner as the PSA liquid crystal display, the substrate used for the liquid crystal display device has a line width/slit electrode pattern of 1 μm to 10 μm on one side substrate, and no slit pattern or protrusion pattern is formed on the counter substrate. The structure can also be operated. With the liquid crystal display thus constructed, the program at the time of manufacture can be simplified, and high transmittance can be obtained.

Further, among the high-performance liquid crystal display elements such as the TFT type liquid crystal display element, a transistor element may be formed between the electrode for driving the liquid crystal and the substrate, and the transistor element may be formed on the substrate.

In the case of a transmissive liquid crystal display device, a substrate as described above is generally used, and in the reflective liquid crystal display device, a material such as aluminum which reflects light only on one side substrate may be used, or a germanium wafer or the like may be used. Opaque substrate.

[Examples]

The invention is further illustrated by the following examples, but the invention is not construed as being limited thereto.

Abbreviations for the compounds used in this example are as follows.

TEOS: tetraethoxy decane

C18: octadecyltriethoxydecane

ACPS: 3-propenyloxypropyltrimethoxydecane

MPMS: 3-methacryloxypropyltrimethoxydecane

MTES: methyl triethoxy decane

HG: 2-methyl-2,4-pentanediol (alias: hexanediol)

BCS: 2-butoxyethanol

UPS: 3-ureidopropyl triethoxy decane

<Synthesis Example 1>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 20.6 g of HG, 6.9 g of BCS, 18.3 g of TEOS, 4.2 g of C18, and 23.4 g of ACPS were mixed to prepare an alkoxysilane monomer. Solution. In this solution, a solution obtained by mixing 10.3 g of HG, 3.4 g of BCS, 10.8 g of water, and 1.4 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Then, the mixture was heated in an oil bath and refluxed for 30 minutes, and then a mixed liquid obtained by mixing 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxyalkylene solution having a concentration of SiO ₂ of 12% by weight.

10.0 g of the obtained polyoxyalkylene solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (S1) having a SiO ₂ conversion concentration of 4% by weight.

Further, 23.6 g of HG, 7.9 g of BCS, and 41.2 g of TEOS were mixed in a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube to prepare a solution of the alkoxysilane monomer. In this solution, a solution obtained by mixing 11.8 g of HG, 3.9 g of BCS, 10.8 g of water, and 0.2 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Then, the mixture was heated in an oil bath and refluxed for 30 minutes, and then a mixed liquid obtained by mixing 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxyalkylene solution having a concentration of SiO ₂ of 12% by weight.

10.0 g of the obtained polyaluminoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (U1) having a SiO ₂ conversion concentration of 4% by weight. The liquid crystal alignment agent intermediate (S1) and the liquid crystal alignment agent intermediate (U1) were mixed at a ratio of 3:7 (weight ratio, the same applies hereinafter) to obtain a liquid crystal alignment agent having a SiO ₂ conversion concentration of 4% by weight. [K1].

<Synthesis Example 2>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 19.9 g of HG, 6.6 g of BCS, 18.3 g of TEOS, 4.2 g of C18, and 24.8 g of MPMS were mixed to prepare an alkoxysilane monomer. Solution. In this solution, a solution obtained by mixing 10.0 g of HG, 3.3 g of BCS, 10.8 g of water, and 1.4 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Then, the mixture was heated in an oil bath and refluxed for 30 minutes, and then a mixed liquid obtained by mixing 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxyalkylene solution having a concentration of SiO ₂ of 12% by weight.

10.0 g of the obtained polyaluminoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (S2) having a SiO ₂ conversion concentration of 4% by weight. The obtained liquid crystal alignment agent intermediate (S2) and the liquid crystal alignment agent intermediate (U1) obtained in Synthesis Example 1 were mixed at a ratio of 3:7 to obtain a liquid crystal alignment agent having a SiO ₂ conversion concentration of 4% by weight. K2].

<Synthesis Example 3>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 23.3 g of HG, 7.8 g of BCS, 39.2 g of TEOS, and 2.5 g of MPMS were mixed to prepare a solution of alkoxysilane monomer. In this solution, a solution obtained by mixing 11.7 g of HG, 3.9 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Thereafter, the mixture was refluxed for 30 minutes using an oil bath, and then a mixed liquid obtained by mixing 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxyalkylene solution having a concentration of SiO ₂ of 12% by weight.

10.0 g of the obtained polyaluminoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (U2) having a SiO ₂ conversion concentration of 4% by weight. The liquid crystal alignment agent intermediate (U2) obtained by the liquid crystal alignment agent intermediate (S1) obtained in Synthesis Example 1 was mixed at a ratio of 3:7 to obtain a liquid crystal alignment agent having a SiO ₂ conversion concentration of 4% by weight [K3 ].

<Synthesis Example 4>

The liquid crystal alignment agent intermediate (S2) obtained in Synthesis Example 2 and the liquid crystal alignment agent intermediate (U2) obtained in Synthesis Example 3 were mixed at a ratio of 3:7 to obtain a liquid crystal having a SiO ₂ conversion concentration of 4% by weight. Orienting agent [K4].

<Synthesis Example 5>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 23.8 g of NG, 7.9 g of BCS, 37.1 g of TEOS, and 3.6 g of MTES were mixed to prepare a solution of the alkoxysilane monomer. In this solution, a solution obtained by mixing 11.9 g of HG, 4.0 g of BCS, 10.8 g of water, and 0.4 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Then, the mixture was heated in an oil bath and refluxed for 30 minutes, and then a mixed liquid obtained by mixing 0.6 g of a methanol solution having a UPS content of 92% by mass, 0.3 g of HG, and 0.1 g of BCS was added. Further, it was refluxed for 30 minutes and then allowed to cool to obtain a polyoxyalkylene solution having a concentration of SiO ₂ of 12% by weight.

10.0 g of the obtained polyaluminoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent intermediate (U3) having a SiO ₂ conversion concentration of 4% by weight. The liquid crystal alignment agent intermediate (S1) obtained in Synthesis Example 1 and the obtained liquid crystal alignment agent intermediate (U3) were mixed at a ratio of 3:7 to obtain a liquid crystal alignment agent having a SiO ₂ conversion concentration of 4% by weight. K5].

<Synthesis Example 6>

The liquid crystal alignment agent intermediate (S2) obtained in Synthesis Example 2 and the liquid crystal alignment agent intermediate (U3) obtained in Synthesis Example 5 were mixed at a ratio of 3:7 to obtain a liquid crystal having a SiO ₂ conversion concentration of 4% by weight. Orienting agent [K6].

<Comparative Synthesis Example 1>

In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 22.6 g of HG, 7.5 g of BCS, and 39.6 g of TEOS were mixed to prepare a solution of the alkoxysilane monomer. In this solution, a solution obtained by mixing 11.3 g of HG, 3.8 g of BCS, 10.8 g of water, and 0.2 g of oxalic acid as a catalyst was added dropwise at room temperature for 30 minutes, and further at room temperature. Stir for 30 minutes. Then, the mixture was heated in an oil bath, refluxed for 1 hour, and then allowed to cool to obtain a polyoxyalkylene solution having a SiO ₂ conversion concentration of 12% by weight. 10.0 g of the obtained polyaluminoxane solution and 20.0 g of BCS were mixed to obtain a liquid crystal alignment agent [L1] having a SiO ₂ conversion concentration of 4% by weight.

<Comparative Synthesis Example 2>

The liquid crystal alignment agent [L2] was obtained in the same manner as in the liquid crystal alignment agent intermediate (S1) obtained in Synthesis Example 1.

<Comparative Synthesis Example 3>

The liquid crystal alignment agent [L3] was obtained in the same manner as in the liquid crystal alignment agent intermediate (S2) obtained in Synthesis Example 2.

<Example 1>

The liquid crystal alignment treatment agent [K1] obtained in Synthesis Example 1 was spin-coated on The ITO surface of the ITO electrode substrate was formed with an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line width/pitch of 5 μm. After drying on a hot plate at 80 ° C for 2 minutes, the film was fired in a hot air circulating oven at 200 ° C or 220 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. The liquid crystal alignment treatment agent [K1] obtained in Synthesis Example 1 was spin-coated on an ITO surface on which no electrode pattern was formed, and dried on a hot plate at 80 ° C for 2 minutes, and then 200 ° C or 220 in the same manner as the above substrate. The hot air circulating oven at ° C was baked for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm. After preparing such two substrates, a 6 μm bead spacer was spread on the liquid crystal alignment film surface of one of the substrates, and then a sealant was printed thereon. After the other substrate is bonded to the inside of the liquid crystal alignment film surface, the sealant is cured to form an empty groove. Liquid crystal MLC-6608 (trade name, manufactured by Merck Co., Ltd.) was injected into an empty space by a pressure reduction injection method to prepare a liquid crystal cell.

The reaction rate characteristics of the obtained liquid crystal cell were measured by the method described later. Then, in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell, UV was applied to the outside of the liquid crystal cell (using a band pass filter having a wavelength of 365 nm) 20J. Then, the reaction rate characteristics were measured again, and the reaction rates before and after the UV irradiation were compared. The results are disclosed in Table 1.

Further, the vertical alignment of the grooves was also measured and evaluated by the method described later. The results are shown together in Table 1.

<Example 2>

Changed from the liquid crystal alignment treatment agent [K1] to the synthesis example 2 A liquid crystal cell was produced in the same manner as in Example 1 except for the liquid crystal alignment treatment agent [K2], and the reaction rate was measured. The results are disclosed in Table 1.

<Example 3>

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [K3] obtained in Synthesis Example 3, and the reaction rate was measured. The results are disclosed in Table 1.

<Example 4>

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [K4] obtained in Synthesis Example 4, and the reaction rate was measured. The results are disclosed in Table 1.

<Example 5>

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [K5] obtained in Synthesis Example 5, and the reaction rate was measured. The results are disclosed in Table 1.

<Example 6>

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment agent [K1] was changed to the liquid crystal alignment treatment agent [K6] obtained in Synthesis Example 6, and the reaction rate was measured. The results are disclosed in Table 1.

<Comparative Example 1>

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [L1] obtained in Comparative Synthesis Example 1, and the reaction rate was measured. The results are disclosed in Table 1.

<Comparative Example 2>

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [L2] obtained in Comparative Synthesis Example 2, and the reaction rate was measured. The results are disclosed in Table 1.

<Comparative Example 3>

A liquid crystal cell was produced in the same manner as in Example 1 except that the liquid crystal alignment treatment agent [K1] was changed to the liquid crystal alignment treatment agent [L3] obtained in Comparative Synthesis Example 2, and the reaction rate was measured. The results are disclosed in Table 1.

[Reaction speed characteristics]

When a square wave having a voltage of ±4 V and a frequency of 1 kHz is applied to a liquid crystal cell to which no voltage is applied, a change in luminance of the liquid crystal panel with time is recorded on an oscilloscope. The luminance when no voltage was applied was set to 0%, the luminance value of saturation when the voltage of ±4 V was applied was set to 100%, and the time when the luminance was changed from 10% to 90% was determined as the rising reaction rate.

[vertical alignment]

Regarding the evaluation of the vertical alignment property, a groove body was placed between two polarizing plates arranged in orthogonal polarization, and observation was made to determine whether or not a black display was exhibited. Increasing the firing temperature, the more the vertical alignment property is exhibited, the higher the vertical alignment property.

As is clear from Table 1, in the case of the liquid crystal cell of the example, the vertical alignment was exhibited at the time of firing at 220 ° C, and the reaction speed after UV irradiation was increased. In particular, in the liquid crystal cells of Example 5 and Example 6, when the firing time at 220 ° C was extended to 60 minutes, vertical alignment was also exhibited. On the other hand, in the case of Comparative Example 1, when it was fired at 220 ° C, it showed a vertical alignment, and After UV irradiation, the reaction rate did not increase. In the case of Comparative Examples 2 and 3, the reaction speed was increased after the UV irradiation, but the vertical alignment was not exhibited at the time of firing at 220 °C.

Industrial availability

In the liquid crystal display device produced by using the liquid crystal alignment agent of the present invention, in the PSA type alignment method, even when a liquid crystal containing no polymerizable compound is used, a liquid crystal display having the same characteristics as the PSA type can be provided. As the element, a PSA type TFT liquid crystal display element, a TN liquid crystal display element, a VA liquid crystal display element, or the like can be used.

In addition, the entire contents of the specification, the patent application, and the abstract of the Japanese Patent Application No. 2011-38413, filed on Feb. 24, 2011, are hereby incorporated by reference.

Claims (9)

A liquid crystal alignment agent comprising the following polyoxyalkylene (A) and polyoxyalkylene (B): polyoxyalkylene (A): containing an alkoxysilane represented by the formula (1) and a formula (2) Polypyroxy olefin R ¹ Si(OR ² ) ₃ (1) obtained by polycondensation of alkoxy oxane of alkoxy decane (R ¹ is a hydrocarbon group which may be substituted by a fluorine atom and has a carbon number of 8 to 30) , R ² represents an alkyl group having 1 to 5 carbon atoms; R ³ Si(OR ⁴ ) ₃ (2) (R ³ is an alkyl group having 1 to 30 carbon atoms substituted by an acryl fluorenyl group, a methacryl fluorenyl group or an aryl group. a group, R ⁴ represents an alkyl group having 1 to 5 carbon atoms, and a polyoxane (B): a polyfluorene obtained by polycondensing an alkoxysilane having 70% to 100% of an alkoxysilane represented by the formula (3). Oxygenane Si(OR ⁵ ) ₄ (3) (R ⁵ represents an alkyl group having 1 to 5 carbon atoms). The liquid crystal alignment agent of the first aspect of the invention, wherein the polyoxyalkylene (B) is a polyoxyalkylene obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (2). The liquid crystal alignment agent of claim 1, wherein the polyoxyalkylene (B) is a polyoxyalkylene obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the formula (4), R ⁶ Si(OR ⁷ ) ₃ (4) (R ⁶ is an alkyl group having 1 to 5 carbon atoms, and R ⁷ represents an alkyl group having 1 to 5 carbon atoms). The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polyoxyalkylene selected from the group consisting of polyoxyalkylene (A) and polyoxyalkylene (B) further comprises the following a polyadenine obtained by polycondensation of an alkoxysilane of an alkoxydecane represented by the formula (5), (R ⁸ ) _n Si(OR ⁹ ) _4-n (5) (R ⁸ is a hydrogen atom or may be a hetero atom, a halogen atom, an amine group, a glycidyl ether group, a fluorenyl group, an isocyanate group or a ureido group substituted with a hydrocarbon group having 1 to 12 carbon atoms, R ⁹ is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3 ). The liquid crystal alignment agent according to any one of the above-mentioned items (1), wherein the alkoxy decane represented by the above formula (1) is contained in the entire alkoxysilane used in the polyoxyalkylene (A). The molar % is 20% by mole, and the alkoxy decane represented by the above formula (2) contains 10% by mole to 80% by mole of the alkoxy decane represented by the above formula (2). A liquid crystal alignment film obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 5 to a substrate, drying it, and baking it. A liquid crystal display element having a liquid crystal alignment film according to item 6 of the patent application. A liquid crystal display device which is irradiated with a voltage applied to a liquid crystal cell in which liquid crystal is sandwiched between two substrates which are fired by the liquid crystal alignment agent according to any one of claims 1 to 5 UV is obtained. A method for producing a liquid crystal display device, which is obtained by coating a liquid crystal alignment agent according to any one of claims 1 to 5 and firing it. The two substrates sandwich the liquid crystal and irradiate the UV with a voltage applied thereto.