KR20140009375A - Silicon-based liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

Also in the liquid crystal display element of the system which processes similarly to a PSA system using the liquid crystal which does not add a polymeric compound, and improves the response speed after UV irradiation, the response speed after UV irradiation is improved, without reducing a perpendicular alignment force. The liquid crystal aligning agent which can form the liquid crystal aligning film which can be made, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and the liquid crystal display element which has this liquid crystal aligning film are provided.
Liquid crystal aligning agent containing following polysiloxane (A) and polysiloxane (B).
Polysiloxane (A): Polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (2).
R ¹ Si (OR ² ) ₃ (1)
(R ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom, and 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 substituted with an acryl group, methacryl group or an aryl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms.)
Polysiloxane (B): Polysiloxane obtained by polycondensing the alkoxysilane containing 70%-100% of the alkoxysilane represented by Formula (3).
Si (OR ⁵ ) ₄ (3)
(R ⁵ represents an alkyl group having 1 to 5 carbon atoms.)

Description

SILICON-BASED LIQUID CRYSTAL ALIGNMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM AND LIQUID CRYSTAL DISPLAY ELEMENT

This invention relates to the liquid crystal aligning agent containing the polysiloxane obtained by polycondensing an alkoxysilane, the liquid crystal aligning film obtained from the said liquid crystal aligning agent, and the liquid crystal display element which has this liquid crystal aligning film.

In recent years, the liquid crystal display element of the vertical (VA) system is widely used among the display system of a liquid crystal display element, such as a liquid crystal television of a large screen, high precision mobile use (display part of a digital camera or a mobile telephone).

In the VA method, the MVA method (Multi Vertical Alignment) in which projections for controlling the direction in which the liquid crystal falls down is formed on a TFT plate or a color filter substrate, or a slit is formed on the ITO electrode of the substrate to cause the liquid crystal to fall by an electric field. PVA (Patterned Vertical Alignment) method of controlling the losing direction is known.

As another orientation system, there is a PSA (Polymer sustained Alignment) system. Among the VA methods, the PSA method is a technology that has recently attracted attention. This system adds a photopolymerizable compound to a liquid crystal, and after manufacturing a liquid crystal panel, irradiates UV to a liquid crystal panel in the state which applied an electric field and fell liquid crystal. As a result, the orientation direction of a liquid crystal is fixed by photopolymerization of a polymeric compound, a pretilt arises, and a response speed improves. A slit is manufactured on one side electrode constituting the liquid crystal panel, and the electrode pattern on the opposite side can be operated even in a structure in which no projections such as MVA or a slit such as PVA are formed, thereby simplifying manufacturing and obtaining excellent panel transmittance. (Refer patent document 1).

An inorganic liquid crystal aligning film material is also known with organic liquid crystal aligning film materials, such as polyimide conventionally used. For example, an alignment agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid is proposed as a material of the coating inorganic alignment film, and the vertical alignment, heat resistance and uniformity on the electrode substrate of the liquid crystal display device are proposed. Forming this excellent liquid crystal aligning film is reported (refer patent document 2).

Moreover, the liquid crystal aligning agent composition containing the reaction product of tetraalkoxysilane, the specific trialkoxysilane, and water, and the specific glycol ether type solvent is proposed, and it prevents a display defect, and orients a liquid crystal with a good afterimage characteristic even after a long drive. It is reported to form the liquid crystal aligning film with little fall of the voltage retention with respect to light and heat, without reducing the ability to make it (refer patent document 3).

Japanese Unexamined Patent Publication No. 2004-302061 Japanese Patent Application Laid-Open No. 09-281502 Japanese Laid-Open Patent Publication 2005-250244

In the liquid crystal display element of a PSA system, there exists a problem that the solubility of the polymeric compound added to a liquid crystal is low, and when an addition amount is increased, it will precipitate at low temperature. On the other hand, when the addition amount of a polymeric compound is reduced, a favorable orientation state will no longer be obtained. Moreover, since the unreacted polymeric compound which remains in a liquid crystal becomes an impurity (contamination) in a liquid crystal, there exists a problem of reducing the reliability of a liquid crystal display element. About this problem, even if the liquid crystal which does not add a polymeric compound is used by introduce | transducing the side chain which superposes | polymerizes in an orientation film, the characteristic equivalent to a PSA system can be acquired.

In VA mode with vertical alignment, strong vertical alignment force is required for vertical alignment, but in this method without using a polymerizable compound, when the vertical alignment force is improved, the response speed after UV irradiation becomes slow, and after UV irradiation Increasing the response speed lowers the vertical alignment force. The improvement of the vertical alignment force and the response speed after UV irradiation is in a trade off relationship.

The subject of this invention uses the liquid crystal which does not add a polymeric compound, and processes it similarly to a PSA system, and also does not reduce a vertical orientation force also in the liquid crystal display element of the system which improves the response speed after UV irradiation, It is providing the liquid crystal display element which has the liquid crystal aligning agent which can form the liquid crystal aligning film which can improve the response speed after UV irradiation, and the liquid crystal aligning film obtained from this liquid crystal aligning agent.

This invention makes the following a summary.

[1] A liquid crystal aligning agent containing the following polysiloxane (A) and polysiloxane (B).

Polysiloxane (A): Polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (2).

R ¹ Si (OR ² ) ₃ (1)

(R ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom, and 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 with an acryl group, methacryl group or an aryl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms.)

Polysiloxane (B): Polysiloxane obtained by polycondensing the alkoxysilane containing 70%-100% of the alkoxysilane represented by Formula (3).

Si (OR ⁵ ) ₄ (3)

(R ⁵ represents an alkyl group having 1 to 5 carbon atoms.)

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

[3] The liquid crystal aligning agent according to the above [1], wherein the polysiloxane (B) is a polysiloxane obtained by further polycondensing an alkoxysilane containing an alkoxysilane represented by 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 above-mentioned [1] to [4], wherein at least one polysiloxane selected from polysiloxane (A) and polysiloxane (B) is a polysiloxane obtained by polycondensing an alkoxysilane containing an alkoxysilane represented by the following formula (5). 3] The liquid crystal aligning agent in any one of them.

(R ⁸ ) _n Si (OR ⁹ ) _4-n (5)

(R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group, and R ⁹ is a C1-5 carbon group) Is an alkyl group, n represents an integer of 0 to 3)

[5] The alkoxysilane represented by the formula (1) is contained in an amount of 1 mol% to 20 mol% in the total alkoxysilane used for the polysiloxane (A), and the alkoxysilane represented by the formula (2) is contained in the polysiloxane (A). The liquid crystal aligning agent in any one of said [1]-[3] contained in 10 mol%-80 mol% of all the alkoxysilanes used.

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

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

[8] A liquid crystal display device obtained by applying the liquid crystal aligning agent according to any one of the above [1] to [5] and irradiating UV in a state where voltage is applied to a liquid crystal cell in which a liquid crystal is sandwiched between two baked substrates. .

[9] A method for producing a liquid crystal display device wherein the liquid crystal aligning agent according to any one of the above [1] to [5] is applied, the liquid crystal is sandwiched between two baked substrates, and UV is applied in a state where a voltage is applied. .

ADVANTAGE OF THE INVENTION According to this invention, by irradiating UV like a PSA system using the liquid crystal which does not add a polymeric compound, the liquid crystal aligning film which can improve the response speed after UV irradiation can be formed, without reducing a perpendicular alignment force. The liquid crystal display element which has a liquid crystal aligning agent and the liquid crystal aligning film obtained from this liquid crystal aligning agent can be obtained.

<Polysiloxane (A)>

Polysiloxane (A) is polysiloxane obtained by polycondensing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (2).

R ¹ Si (OR ² ) ₃ (1)

In formula (1), R <^1> is a C8-30 hydrocarbon group which may be substituted by the fluorine atom, and R <^2> represents a C1-C5 alkyl group.

R ³ Si (OR ⁴ ) ₃ (2)

In formula (2), R <^3> is the alkyl group substituted by the acryl group, the methacryl group, or the aryl group, and R <^4> represents a C1-C5 alkyl group.

R ¹ (hereinafter also referred to as a specific organic group) of the alkoxysilane represented by the formula (1) is a hydrocarbon group having 8 to 30, preferably 8 to 22 carbon atoms which may be substituted with fluorine, and aligns the liquid crystal vertically. It will not specifically limit, if it has an effect to make.

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, the alkoxysilane whose R <^1> is an alkyl group or a fluoroalkyl group is preferable because it is comparatively cheap and it is easy to obtain as a commercial item. In the said fluoroalkyl group, the number of fluorine atoms is one or more, and all the hydrogen may be substituted by the fluorine atom.

In particular, the alkoxysilane whose R <^1> is an alkyl group is preferable. The polysiloxane (A) used for this invention may have two or more types of these specific organic groups.

R <^2> of the alkoxysilane represented by Formula (1) is C1-C5, Preferably it is an alkyl group of 1-3. More preferably, R ² is a methyl group or an ethyl group.

Although the specific example of the alkoxysilane represented by such Formula (1) is given, it is not limited to this.

For example, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexa Decyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyl Triethoxysilane, undecyltrimethoxysilane, 21-docosenyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane , Heptadecafluorodecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, m-styrylethyltrimethoxysilane, p-styrylethyltrimeth Oxysilane, (1-I Til) tree in the silane, (1-naphthyl) and the like can be mentioned trimethoxysilane. Among them, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyl Triethoxysilane, Heptadecyltrimethoxysilane, Heptadecyltriethoxysilane, Octadecyltrimethoxysilane, Octadecyltriethoxysilane, Nonadecyltrimethoxysilane, Nonadecyltriethoxysilane, Undecyltree Preference is given to ethoxysilane or undecyltrimethoxysilane.

In the alkoxysilane represented by Formula (1) which has the specific organic group mentioned above, in all the alkoxysilanes used in order to obtain polysiloxane (A), 1 mol% or more is preferable in order to acquire favorable liquid-crystal orientation. More preferably, it is 1.5 mol% or more. More preferably, it is 2 mol% or more. Moreover, in order to acquire sufficient hardening characteristic of the liquid crystal aligning film formed, 30 mol% or less is preferable. More preferably, it is 25 mol% or less.

R <^3> (henceforth 2nd specific organic group) of the alkoxysilane represented by Formula (2) is an alkyl group substituted by at least 1 chosen from the group which consists of an acryl group, a methacryl group, and an aryl group. The substituted hydrogen atom is one or more, Preferably it is one. As for carbon number of an alkyl group, 1-30 are preferable, More preferably, it is 1-20. More preferably, it is 1-10. Although an alkyl group may be linear or branched, a linear type is more preferable.

R <^4> of the alkoxysilane represented by Formula (2) is a C1-C5 alkyl group, Preferably it is C1-C3, Especially preferably, it is C1-C2.

Although the specific example of the alkoxysilane represented by Formula (2) is given, it is not limited to these. For example, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, methacryloxymethyl trimethoxysilane, methacryloxymethyl triethoxysilane, 3-acryloxypropyl tri Methoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, 3- (N -Styrylmethyl-2-aminoethylamino) propyltrimethoxysilane.

In addition to the alkoxysilane represented by Formula (1) and Formula (2), in manufacture of polysiloxane (A), unless the effect of this invention is impaired for the purpose of improving adhesiveness with a board | substrate, affinity with a liquid crystal molecule, etc. In the above, one or more kinds of alkoxysilanes represented by the following formula (5) may be used. Since the alkoxysilane represented by Formula (5) can give various characteristics to polysiloxane, 1 type or multiple types can be selected and used according to a required characteristic.

(R ⁸ ) _n Si (OR ⁹ ) _4-n (5)

In formula (5), R <^8> may be substituted by the hydrogen atom, the hetero atom, the halogen atom, the amino group, the glycidoxy group, the mercapto group, the isocyanate group, or the ureido group, and is a C1-C10 hydrocarbon group.

R <^9> is a C1-C5, Preferably it is an alkyl group of 1-3.

n is 0-3, Preferably it is an integer of 0-2.

R <^8> of the alkoxysilane represented by Formula (5) is a hydrogen atom or a C1-C10 hydrocarbon group (henceforth 3rd specific organic group).

As an example of a 3rd specific organic group, Aliphatic hydrocarbon group; Hydrocarbon groups having a ring structure such as aliphatic rings, aromatic rings and hetero rings; Hydrocarbon group having an unsaturated bond; It is a C1-C6 hydrocarbon group which may contain hetero atoms, such as an oxygen atom, a nitrogen atom, and a sulfur atom, and may have a branched structure. The third specific organic group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.

Although the specific example of the alkoxysilane represented by Formula (5) below is given, it is not limited to this. 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl Triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyl Triethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane , Diphenyl diethoxy silane, 3-aminopropyl methyl diethoxy silane, 3-amino propyl dimethyl ethoxy silane, trimethyl ethoxy silane, trimethyl methoxy silane, (gamma) -ureido propyl triethoxy silane, (gamma) -ureido propyl Trimethoxysilane And γ-ureidopropyltripropoxysilane.

In the alkoxysilane represented by Formula (5), the alkoxysilane whose n is 0 is tetraalkoxysilane. Since tetraalkoxysilane is easy to be condensed with the alkoxysilane represented by Formula (1)-(4), it is preferable in order to obtain the polysiloxane (A) of this invention.

In such formula (5), as alkoxysilane where n is 0, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is more preferable, and especially tetramethoxysilane or tetra Preferred are oxysilanes.

In the present invention, the alkoxysilane represented by the formula (1) is preferably 1 mol% to 20 mol%, particularly preferably 2 mol% to 20 mol%, of all the alkoxysilanes used for the production of the polysiloxane (A). Moreover, it is preferable that the alkoxysilane represented by Formula (2) contains 10 mol%-80 mol%, Especially preferably, 30 mol%-80 mol% in all the alkoxysilanes used for manufacture of polysiloxane (A).

&Lt; Polysiloxane (B) &gt;

Polysiloxane (B) is polysiloxane obtained by polycondensing the alkoxysilane containing 70 weight%-100 weight% of the alkoxysilane represented by Formula (3).

Si (OR ⁵ ) ₄ (3)

In formula (3), R <^5> represents a C1-C5 alkyl group and C1-C2 is preferable.

As a specific example of the alkoxysilane represented by such Formula (3), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, or tetrabutoxysilane is more preferable, especially tetramethoxysilane or tetraethoxysilane This is preferred.

In addition to the alkoxysilane represented by Formula (3), polysiloxane (B) may be polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (2) further.

As an alkoxysilane represented by Formula (2) contained in polysiloxane (B), the alkoxysilane used in manufacture of the said polysiloxane (A) can be used. The same applies to the specific examples.

Polysiloxane (B) may be polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (4) other than the alkoxysilane represented by Formula (3).

R ⁶ Si (OR ⁷ ) ₃ (4)

In formula (4), R <^6> is a C1-C5 alkyl group and R <^7> represents a C1-C5 alkyl group.

R <^6> of the alkoxysilane represented by Formula (4) is a C1-C5 alkyl group. As for carbon number of an alkyl group, 1-4 are preferable, More preferably, it is 1-3.

R <^7> of the alkoxysilane represented by Formula (4) is a C1-C5 alkyl group, Preferably it is C1-C3, Especially preferably, it is C1-C2.

Although the specific example of the alkoxysilane represented by Formula (4) is given, it is not limited to these. For example, they are methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxysilane.

In particular, the liquid crystal aligning agent containing the polysiloxane (B) obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (4) other than the alkoxysilane represented by Formula (3) is especially preferable because of high vertical alignment force. Do.

In order to improve the response speed of a liquid crystal display element by UV-irradiating, applying a voltage using the liquid crystal which does not add a polymeric compound, the alkoxysilane represented by Formula (2) which has a 2nd specific organic group is polysiloxane (B). 10 mol% or more is preferable in all the alkoxysilanes used in order to obtain the. More preferably, it is 20 mol% or more. More preferably, it is at least 30 mol%. Further, in order to sufficiently cure the liquid crystal alignment film to be formed, it is preferably 75 mol% or less.

In the production of polysiloxane (B), in addition to the alkoxysilane represented by the formula (2), formula (3) and formula (4), the effect of the present invention for the purpose of improving adhesion to the substrate, affinity with liquid crystal molecules, and the like. As long as it does not inhibit, the 1 type or multiple types of alkoxysilane represented by following formula (5) can also be used. Since the alkoxysilane represented by Formula (5) can give various characteristics to polysiloxane, 1 type or multiple types can be selected and used according to a required characteristic.

(R ⁸ ) _n Si (OR ⁹ ) _4-n (5)

In formula (5), the structure and preferable range of R <^8> and R <^9> and the specific example of the alkoxysilane represented by Formula (5) are as above-mentioned.

<Method for producing polysiloxane>

The method for obtaining the polysiloxane used in the present invention is not particularly limited. In the polysiloxane (A) of this invention, the alkoxysilane which makes said formula (1) and formula (2) an essential component is an alkoxysilane which makes said formula (3) an essential component in polysiloxane (B). It is obtained by polycondensation in an organic solvent. Usually, polysiloxane polycondenses such alkoxysilane and is obtained as a solution melt | dissolved uniformly in the organic solvent.

As a method of polycondensing an alkoxysilane, the method of hydrolyzing and condensing an alkoxysilane in solvent, such as alcohol or glycol, is mentioned, for example. In that case, any of partial hydrolysis and complete hydrolysis may be sufficient as a hydrolysis-condensation reaction. In the case of complete hydrolysis, theoretically, 0.5 times mole of water of all the alkoxy groups in an alkoxysilane may be added, but it is preferable to add an excess amount of water more than 0.5 times mole normally.

In this invention, although the quantity of the water used for the said reaction can be suitably selected as desired, Usually, it is preferable that it is 0.5 times mole-2.5 times mole of all the alkoxy groups in an alkoxysilane, and 1 time mole-2 times mole are more preferable. .

Moreover, acids, such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid, and fumaric acid, for the purpose of generally promoting hydrolysis and condensation reaction; Alkali such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine and the like; Metal salts such as hydrochloric acid, sulfuric acid, and nitric acid; Catalysts are used. In addition, it is also common to accelerate hydrolysis and condensation reaction by heating the solution which the alkoxysilane melt | dissolved. At that time, the heating temperature and the heating time can be appropriately selected according to the desired one. For example, the method of heating and stirring at 50 degreeC for 24 hours, or heating and stirring for 1 hour under reflux is mentioned.

Moreover, as another method, the method of heating and polycondensing the mixture of an alkoxysilane, a solvent, and oxalic acid is mentioned, for example. Specifically, oxalic acid is added to the alcohol in advance to form an alcohol solution of oxalic acid, and then the alkoxysilane is mixed while the solution is heated. In that case, it is preferable to set it as 0.2 mol-2 mol with respect to 1 mol of all the alkoxy groups which an alkoxysilane has, and, as for the quantity of the oxalic acid to use, 0.5 mol-1.5 mol are more preferable. Heating in this method can be performed at liquid temperature of 50 degreeC-180 degreeC. Preferably, it is a method of heating for several tens of minutes to several tens of hours under reflux so that the liquid does not evaporate, volatilize, or the like.

When obtaining polysiloxane, when using multiple types of alkoxysilanes, an alkoxysilane may be mixed previously and may be used as a mixture, and may be used by mixing several types of alkoxysilanes one by one.

The solvent used for polycondensing the alkoxysilane (hereinafter also referred to as a polymerization solvent) is not particularly limited as long as it dissolves the alkoxysilane. In addition, even when the alkoxysilane is not dissolved, the alkoxysilane may be dissolved as the polycondensation reaction of the alkoxysilane proceeds. Generally, since alcohol is produced | generated by the polycondensation reaction of an alkoxysilane, the organic solvent which is compatible with alcohol, glycol, glycol ether, or alcohol is used, Especially preferably, glycol is used. .

As a specific example of such a polymerization solvent, Alcohol, such as methanol, ethanol, a propanol, butanol, diacetone alcohol; Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1 Glycols such as 2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, and 1,6-hexanediol Ryu; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene 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, diethylene 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, 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 dibu Glycol ethers such as tilether; N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol; And the like. In this invention, you may mix and use multiple types of the said polymerization solvent.

The polymerization solution (hereinafter also referred to as polymerization solution) of the polysiloxane obtained by the above method is preferably a concentration (hereinafter referred to as SiO ₂ conversion concentration) in which silicon atoms of all the alkoxysilanes added as raw materials are converted into SiO ₂ (hereinafter referred to as SiO ₂ concentration). It is more preferable to set it as 5 weight% or less, Furthermore, 5 weight%-15 weight%. By selecting an arbitrary concentration in this concentration range, formation of a gel can be suppressed to obtain a homogeneous solution.

&Lt; Solution of polysiloxane &gt;

In the present invention, the polymerization solution obtained by the above method may be used as a solution of polysiloxane as it is. If necessary, the solution obtained by the above method may be concentrated, diluted with the addition of a solvent, or substituted with another solvent to obtain a solution of polysiloxane.

In that case, the solvent (henceforth an addition solvent) to be used may be the same as a polymerization solvent, and may be another solvent. This addition solvent is not specifically limited as long as polysiloxane is melt | dissolving uniformly, One type or multiple types can be arbitrarily selected and used.

As a specific example of such an addition solvent, Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, in addition to the solvent mentioned as an example of the said polymerization solvent; And esters such as methyl acetate, ethyl acetate and ethyl lactate.

These solvents can improve the applicability | paintability at the time of apply | coating a liquid crystal aligning agent on a board | substrate by adjustment of the viscosity of a liquid crystal aligning agent, or spin coating, flexographic printing, an inkjet, etc.

&Lt; Other components &gt;

In the present invention, components other than polysiloxane, such as inorganic fine particles, metal siloxane oligomers, metal siloxane polymers, leveling agents, and surfactants, may be used as long as the effects of the present invention are not impaired. It may be contained in the solution of.

As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and in particular, the fine particles are preferably in a colloidal solution state. This colloidal solution may disperse | distribute an inorganic fine particle in a dispersion medium, and may be a colloidal solution of a commercial item. In the present invention, by containing the inorganic fine particles, the surface shape and other functions of the formed cured coating can be imparted. As inorganic fine particles, it is preferable that the average particle diameter is 0.001 micrometer-0.2 micrometer, More preferably, they are 0.001 micrometer-0.1 micrometer. When the average particle diameter of an inorganic fine particle exceeds 0.2 micrometer, transparency of the hardened film formed using the coating liquid prepared may fall.

Water and an organic solvent are mentioned as a dispersion medium of an inorganic fine particle. As the colloid solution, it is preferable that the pH or the pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating liquid for forming a film. And more preferably 2 to 7.

Examples of the organic solvent for use in the dispersion medium of the colloid solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexyleneglycol, diethylene glycol, dipropylene glycol and ethylene glycol monopropyl ether ; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Aromatic hydrocarbons such as toluene and xylene; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Ethers such as tetrahydrofuran and 1,4-dioxane; . Among these, alcohols or ketones are preferable. These organic solvents may be used alone or as a dispersion medium by mixing two or more kinds thereof.

As the metal siloxane oligomer and the metal siloxane polymer, single or complex oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium and zinc are used. As a metal siloxane oligomer and a metal siloxane polymer, a commercial item may be sufficient and what was obtained by conventional methods, such as hydrolysis, from monomers, such as a metal alkoxide, a nitrate, a hydrochloride, and a carboxylate.

Specific examples of commercially available metal siloxane oligomers and metal siloxane polymers include siloxane oligomers or siloxane polymers such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colecott Corporation. And titanoxane oligomers such as titanium-n-butoxide tetramer manufactured by Canto Chemical Company. These may be used alone or in combination of two or more.

Moreover, a leveling agent, surfactant, etc. can use a well-known thing, Especially since a commercial item is easy to obtain, it is preferable.

In addition, the method of mixing the above-mentioned other components with polysiloxane may be simultaneous with polysiloxane, may be subsequent, and is not specifically limited.

[Liquid crystal aligning agent]

The liquid crystal aligning agent of this invention is a solution containing the above-mentioned polysiloxane and other components as needed. In that case, the solvent chosen from the group which consists of a polymerization solvent and addition solvent of the polysiloxane mentioned above is used as a solvent.

As for content of all the polysiloxane in a liquid crystal aligning agent, SiO ₂ conversion density | concentration becomes like this. Preferably it is 0.5 weight%-15 weight%, More preferably, they are 1 weight%-6 weight%. In a range of concentration in terms of SiO _2, the pot life (pot life) of a sufficient solution easily obtain a desired film thickness, with a single coating is liable to be obtained.

As the total polysiloxane, the liquid crystal aligning agent of the present invention contains polysiloxane (A) and polysiloxane (B) in a weight ratio of from 10 to 90 to 50 to 50, preferably from 20 to 80 to 40 to 60.

Moreover, the weight ratio of all polysiloxane in the liquid crystal aligning agent of this invention, and the other component added as needed is 99 to 1-50 to 50, Preferably it is 98 to 2 to 70 to 30.

The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. The polysiloxane used in the present invention and other components to be added as required may be uniformly mixed. Usually, since polysiloxane is polycondensed in a solvent, it is easy to use the solution of polysiloxane as it is, or to add another component as needed to the solution of polysiloxane. The most convenient method is to use the polymerization solution of polysiloxane as it is.

Moreover, when adjusting content of the polysiloxane in a liquid crystal aligning agent, the solvent chosen from the group which consists of the polymerization solvent of the alkoxysilane mentioned above, and the addition solvent of polysiloxane can be used.

[Liquid Crystal Alignment Layer]

The liquid crystal aligning film of this invention is obtained using the liquid crystal aligning agent of this invention. For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, the cured film obtained by performing drying and baking can also be used as a liquid crystal aligning film as it is. Moreover, this cured film can also irradiate UV in the state which rubbed, irradiated polarized light, the light of a specific wavelength, etc., processed an ion beam, etc., or applied voltage to the liquid crystal display element after liquid crystal charge.

The substrate to which the liquid crystal aligning agent is applied is not particularly limited as long as it is a substrate having high transparency, but a substrate having a transparent electrode for driving the liquid crystal on the substrate is preferable.

Specific examples thereof include glass plates, polycarbonates, poly (meth) acrylates, polyethersulfones, polyarylates, polyurethanes, polysulfones, polyethers, polyether ketones, trimethylpentens, polyolefins, polyethylene terephthalates, A substrate on which a transparent electrode is formed on a plastic plate such as acrylonitrile, triacetylcellulose, diacetylcellulose, and acetate butyrate cellulose.

As a method of applying the liquid crystal aligning agent, a spin coating method, a printing method, an inkjet method, a spraying method, a roll coating method, and the like can be mentioned. However, in terms of productivity, a transfer printing method is widely used industrially. Is preferably used.

Although the drying process after apply | coating a liquid crystal aligning agent is not necessarily required, when the time from application | coating to baking is not constant for every board | substrate, or is not baked immediately after application | coating, it is preferable to include a drying process. The solvent should just be removed to such an extent that a coating film shape does not deform | transform by conveyance of a board | substrate etc., and this drying is not specifically limited about the drying means. For example, the method of drying for 0.5 minutes-30 minutes, Preferably 1 minute-5 minutes is mentioned on the hotplate of temperature 40 degreeC-150 degreeC, Preferably 60 degreeC-100 degreeC.

The coating film formed by apply | coating a liquid crystal aligning agent by the said method can be baked, and it can be set as a cured film. In that case, although baking temperature can be performed at arbitrary temperature of 100 degreeC-350 degreeC, Preferably it is 140 degreeC-300 degreeC, More preferably, it is 150 degreeC-230 degreeC, More preferably, it is 160 degreeC-220 degreeC to be. Firing time can be baked in arbitrary time for 5 minutes-240 minutes. Preferably they are 10 minutes-90 minutes, More preferably, they are 20 minutes-80 minutes. The heating can use a conventionally well-known method, for example, a hot plate, a hot air circulation oven, an IR (infrared) oven, a belt furnace, etc.

Polycondensation of the polysiloxane in a liquid crystal aligning film advances in a baking process. However, in the present invention, it is not necessary to completely polycondense unless the effect of the present invention is impaired. However, it is preferable to perform the baking at a temperature higher by 10 ° C or more than the heat treatment temperature such as seal hardening required in the liquid crystal cell manufacturing process.

Although the thickness of this cured film can be selected as needed, Preferably it is 5 nm or more, More preferably, it is 10 nm or more, and since it is easy to acquire the reliability of a liquid crystal display element, it is preferable. Moreover, the thickness of a cured film becomes like this. Preferably it is 300 nm or less, More preferably, it is 150 nm or less, and since the power consumption of a liquid crystal display element does not become extremely large, it is preferable.

<Liquid crystal display element>

After the liquid crystal aligning film is formed in a board | substrate by the said method, the liquid crystal display element of this invention can manufacture and obtain a liquid crystal cell by a well-known method.

As an example of liquid crystal cell manufacture, the method of fixing a pair of board | substrates with which the liquid crystal aligning film was formed with a sealing agent across a spacer, and injecting and sealing a liquid crystal is common. In that case, although the size of the spacer to be used is 1 micrometer-30 micrometers, Preferably it is 2 micrometers-10 micrometers.

The method for injecting the liquid crystal is not particularly limited, and the vacuum method for injecting the liquid crystal after the inside of the manufactured liquid crystal cell is reduced in pressure, the dropping method for sealing after dropping the liquid crystal, and the like.

By irradiating UV in the state which applied the voltage between the electrodes of the both board | substrates of the liquid crystal cell in which the liquid crystal was introduce | transduced, the acryl group, methacryl group, etc. in an orientation film polymerize and bridge | crosslink on the spot, and the response speed of a liquid crystal display becomes quick. Here, the voltage to be applied is 5 Vp-p to 50 Vp-p, but preferably 5 Vp-p to 30 Vp-p. UV irradiation amount to irradiate is 1 J (joule)-60 J, Preferably it is 40 J or less. It is preferable that the less the amount of UV radiation can reduce the reliability deterioration caused by the destruction of the members constituting the liquid crystal display, and further increase the manufacturing tact (operation amount) by reducing the UV irradiation time.

Although it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate used for a liquid crystal display element, Usually, it is a board | substrate with a transparent electrode for driving a liquid crystal on a board | substrate. Specific examples are the same as those of the substrate described in [Liquid Crystal Alignment Film]. A substrate having an electrode pattern or a projection pattern such as standard PVA or MVA can also be used.

As a board | substrate used for a liquid crystal display element, the structure which does not form a slit pattern or a projection pattern in the opposing board | substrate forms a 1 micrometer-10 micrometers line / slit electrode pattern in one side board | substrate similarly to a PSA system liquid crystal display. It is also possible to operate, and the liquid crystal display of this structure can simplify the process at the time of manufacture, and high transmittance | permeability can be obtained.

In a high-performance liquid crystal display element such as a TFT type liquid crystal display element, one in which a transistor element is formed on a substrate between an electrode for liquid crystal drive and a substrate is used.

In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, a material such as aluminum that reflects light only on one side substrate may be used, and an opacity such as a silicon wafer may be used. One substrate can also be used.

Example

Hereinafter, although an Example of this invention demonstrates more concretely, it is not limited to these and interpreted.

The abbreviation in the compound used by the present Example is as follows.

TEOS: tetraethoxysilane

C18: octadecyltriethoxysilane

ACPS: 3-acryloxypropyltrimethoxysilane

MPMS: 3-methacryloxypropyltrimethoxysilane

MTES: methyltriethoxysilane

HG: 2-methyl-2,4-pentanediol (alias hexylene glycol)

BCS: 2-butoxyethanol

UPS: 3-ureidopropyltriethoxysilane

&Lt; Synthesis Example 1 &

In a 200 mL four-necked 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 a solution of the alkoxysilane monomer. It prepared. A solution of 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 to the solution over 30 minutes at room temperature, followed by stirring at room temperature for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, 0.6 g of the methanol solution of 92 mass% of UPS content mixed previously, 0.3 g of HG, and 0.1 g of BCS were added. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixture of 20.0 g of the resulting polysiloxane solution 10.0 g and the BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (S1).

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 23.6 g of HG, 7.9 g of BCS, and 41.2 g of TEOS were mixed to prepare a solution of an alkoxysilane monomer. A solution of 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 to the solution over 30 minutes at room temperature, followed by stirring at room temperature for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, 0.6 g of the methanol solution of 92 mass% of UPS content mixed previously, 0.3 g of HG, and 0.1 g of BCS were added. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixture of 20.0 g of the resulting polysiloxane solution 10.0 g and the BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (U1). A liquid crystal aligning agent intermediate (S1) and the liquid crystal aligning agent intermediate (U1) obtained 3 (the same weight ratio, hereinafter), the ratio of 7 to a mixture, SiO ₂ in terms of the concentration of 4% by weight of the liquid crystal orientation to obtain a second [K1] .

&Lt; Synthesis Example 2 &

In a 200 mL four-necked 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 a solution of the alkoxysilane monomer. It prepared. A solution of 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 to the solution over 30 minutes at room temperature, followed by stirring at room temperature for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, 0.6 g of the methanol solution of 92 mass% of UPS content mixed previously, 0.3 g of HG, and 0.1 g of BCS were added. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixture of 20.0 g of the resulting polysiloxane solution 10.0 g and the BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (S2). A liquid crystal aligning agent intermediate (U1) obtained in the liquid crystal aligning agent intermediate (S2) of Synthetic Example 1, the obtained 3: a mixture in a ratio of 7, SiO ₂ in terms of the concentration to obtain the [K2] of 4% by weight of the liquid crystal alignment.

&Lt; Synthesis Example 3 &

In a 200 mL four-necked 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 an alkoxysilane monomer. A solution of 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 to the solution over 30 minutes at room temperature, followed by stirring at room temperature for 30 minutes. Then, after heating and refluxing for 30 minutes using an oil bath, 0.6 g of the methanol solution of 92 mass% of UPS content mixed previously, 0.3 g of HG, and 0.1 g of BCS were added. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixture of 20.0 g of the resulting polysiloxane solution 10.0 g and the BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (U2). An intermediate liquid crystal aligning agent (S1) and the liquid crystal aligning agent thus obtained intermediate (U2) obtained in Synthesis Example 13: a mixture in a ratio of 7, SiO ₂ in terms of the concentration to obtain a first [K3] is 4% by weight of the liquid crystal alignment.

&Lt; Synthesis Example 4 &

A liquid crystal aligning agent intermediate (U2) obtained in the liquid crystal aligning agent intermediate (S2) of Synthetic Example 3 obtained in Synthesis Example 23: The mixed at a ratio of 7, SiO ₂ in terms of the concentration of liquid crystal alignment and 4% by weight [K4] Got.

&Lt; Synthesis Example 5 &

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 23.8 g of HG, 7.9 g of BCS, 37.1 g of TEOS, and 3.6 g of MTES were mixed to prepare a solution of an alkoxysilane monomer. A solution of 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 to the solution over 30 minutes at room temperature, followed by stirring at room temperature for 30 minutes. After heating and refluxing for 30 minutes using the oil bath, 0.6 g of the methanol solution of 92 mass% of UPS content mixed previously, 0.3 g of HG, and 0.1 g of BCS were added. The mixture was further refluxed for 30 minutes and allowed to stand to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixture of 20.0 g of the resulting polysiloxane solution 10.0 g and the BCS, SiO ₂ in terms of a concentration of 4% by weight of the liquid crystal orientation to obtain a second intermediate (U3). A liquid crystal aligning agent intermediate (S1) and the obtained liquid crystal aligning agent intermediate (U3) obtained in Synthesis Example 13: a mixture in a ratio of 7, SiO ₂ in terms of the concentration to obtain the [K5] 4% by weight of the liquid crystal alignment.

&Lt; Synthesis Example 6 &

A liquid crystal aligning agent intermediate (U3) obtained in the liquid crystal aligning agent intermediate (S2) of Synthetic Example 5 was obtained in Synthesis Example 23: The mixed at a ratio of 7, SiO ₂ in terms of the concentration of liquid crystal alignment and 4% by weight [K6] Got.

<Comparative Synthesis Example 1>

In a 200 mL four-necked 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 an alkoxysilane monomer. A solution of 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 to the solution over 30 minutes at room temperature, followed by stirring at room temperature for 30 minutes. Thereafter, the mixture was heated and refluxed for 1 hour using an oil bath, followed by cooling to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by weight.

Mixing the resulting polysiloxane solution, 20.0 g of 10.0 g and the BCS, SiO ₂ in terms of the concentration to obtain a first [L1] of 4% by weight of the liquid crystal alignment.

<Comparative Synthesis Example 2>

Liquid crystal aligning agent [L2] was obtained similarly to the liquid crystal aligning agent intermediate (S1) obtained in the synthesis example 1.

<Comparative Synthesis Example 3>

Liquid crystal aligning agent [L3] was obtained similarly to the liquid crystal aligning agent intermediate (S2) obtained in the synthesis example 2.

&Lt; Example 1 &gt;

The liquid-crystal aligning agent [K1] obtained by the synthesis example 1 was spin-coated to the ITO surface of the ITO electrode substrate in which the ITO electrode pattern whose pixel size is 100 micron x 300 microns and whose line / space is 5 microns, respectively is formed. After drying for 2 minutes on an 80 degreeC hotplate, baking was performed for 30 minutes in 200 degreeC or 220 degreeC hot-air circulation type oven, and the liquid crystal aligning film of 100-nm-thick film was formed. After spin-coating the liquid-crystal aligning agent [K1] obtained by the synthesis example 1 to the ITO surface in which the electrode pattern is not formed, and drying it for 2 minutes on an 80 degreeC hotplate, it carried out similarly to the said board | substrate of 200 degreeC or 220 degreeC It baked for 30 minutes in the hot-air circulation type oven, and formed the liquid crystal aligning film with a film thickness of 100 nm. These two board | substrates were prepared, after spread | dispersing a 6 micrometers bead spacer on the liquid crystal aligning film surface of one board | substrate, the sealing compound was printed from on. After bonding the other board | substrate with the liquid crystal aligning film surface inside, the sealing compound was hardened and the empty cell was produced. Liquid crystal MLC-6608 (Merck & Co., Ltd. brand name) was injected into the empty cell by the pressure reduction injection method, and the liquid crystal cell was produced.

The response speed characteristic of the obtained liquid crystal cell was measured by the method of mentioning later. Thereafter, UV (wavelength; using a 365 nm band pass filter) was irradiated with 20 J from the outside of the liquid crystal cell in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell. Then, the response speed characteristic was measured again and the response speed in UV irradiation back and front was compared. The results are shown in Table 1.

Moreover, the vertical orientation of the cell was also measured and evaluated by the method described later. The result was also shown in Table 1 together.

&Lt; Example 2 &gt;

Except having changed the liquid-crystal aligning agent [K1] into the liquid-crystal aligning agent [K2] obtained by the synthesis example 2, it carried out similarly to Example 1, and produced the liquid crystal cell, and measured the response speed. The results are shown in Table 1.

&Lt; Example 3 &gt;

Except having changed the liquid-crystal aligning agent [K1] into the liquid-crystal aligning agent [K3] obtained by the synthesis example 3, it carried out similarly to Example 1, and produced the liquid crystal cell, and measured the response speed. The results are shown in Table 1.

<Example 4>

Except having changed the liquid-crystal aligning agent [K1] into the liquid-crystal aligning agent [K4] obtained by the synthesis example 4, it carried out similarly to Example 1, and produced the liquid crystal cell, and measured the response speed. The results are shown in Table 1.

&Lt; Example 5 &gt;

Except having changed the liquid-crystal aligning agent [K1] into the liquid-crystal aligning agent [K5] obtained by the synthesis example 5, it carried out similarly to Example 1, and produced the liquid crystal cell, and measured the response speed. The results are shown in Table 1.

&Lt; Example 6 &gt;

Except having changed the liquid-crystal aligning agent [K1] into the liquid-crystal aligning agent [K6] obtained by the synthesis example 6, it carried out similarly to Example 1, and produced the liquid crystal cell, and measured the response speed. The results are shown in Table 1.

&Lt; Comparative Example 1 &

The liquid crystal cell was produced like Example 1 except having changed the liquid-crystal aligning agent [K1] into the liquid-crystal aligning agent [L1] obtained by the comparative synthesis example 1, and response speed was measured. The results are shown in Table 1.

&Lt; Comparative Example 2 &

The liquid crystal cell was produced like Example 1 except having changed the liquid-crystal aligning agent [K1] into the liquid-crystal aligning agent [L2] obtained by the comparative synthesis example 2, and response speed was measured. The results are shown in Table 1.

&Lt; Comparative Example 3 &

Except having changed the liquid-crystal aligning agent [K1] into the liquid-crystal aligning agent [L3] obtained by the comparative synthesis example 2, it carried out similarly to Example 1, and produced the liquid crystal cell, and measured the response speed. The results are shown in Table 1.

Response speed characteristic

The time variation of the luminance of the liquid crystal panel when a square wave having a voltage of ± 4 V and a frequency of 1 Hz was applied to the liquid crystal cell to which no voltage was applied, was introduced into the oscilloscope. When the voltage was not applied and the luminance was 0% and a voltage of ± 4 V was applied, the value of the saturated luminance was made 100%, and the time for the luminance to change from 10% to 90% was used as the response speed of the rise.

[Vertical orientation]

About evaluation of the vertical orientation, the cell was arrange | positioned and observed between two polarizing plates arrange | positioned by cross nicol, and it judged whether or not black display was shown. Even if the firing temperature was increased, the more the vertical alignment property was, the higher the vertical alignment property was.

Before UV irradiation
Response speed
(ms) After UV irradiation
Response speed
(ms) Vertical orientation 200 ℃ firing 220 ℃ firing Example 1 ＞ 700 39 ○ ○ Example 2 ＞ 700 25 ○ ○ Example 3 ＞ 700 37 ○ ○ Example 4 ＞ 700 28 ○ ○ Example 5 ＞ 700 43 ○ ◎ Example 6 ＞ 700 29 ○ ◎ Comparative Example 1 ＞ 700 ＞ 700 ○ ○ Comparative Example 2 ＞ 700 41 ○ × Comparative Example 3 ＞ 700 26 ○ ×

X: does not show vertical orientation

(Circle): Vertical orientation in the baking of 200 degreeC or 220 degreeC 30 minutes is shown.

(Double-circle): Vertical orientation also shows in baking at 220 degreeC and 60 minutes.

As can be seen from Table 1, in the liquid crystal cell of the example, the vertical alignment was also exhibited even at the time of 220 degreeC baking, and the response speed improved after UV irradiation. In particular, the liquid crystal cell of Example 5 and Example 6 showed the vertical orientation also when the time of 220 degreeC baking was extended to 60 minutes. On the other hand, in the comparative example 1, although the vertical orientation was shown at 220 degreeC baking, the response speed did not improve after UV irradiation. In the comparative examples 2 and 3, although the response speed improved after UV irradiation, in the case of 220 degreeC baking, the vertical orientation did not show.

Industrial availability

The liquid crystal display element manufactured using the liquid crystal aligning agent of this invention is a liquid crystal display element which can acquire the characteristic equivalent to a PSA system also when using the liquid crystal which does not add a polymeric compound in the orientation system of a PSA system. It can provide and can be used as a TFT liquid crystal display element of a PSA system, a TN liquid crystal display element, a VA liquid crystal display element, etc.

In addition, all the content of the JP Patent application 2011-038413, the claim, and the abstract for which it applied on February 24, 2011 is referred here, and it takes in as an indication of the specification of this invention.

Claims (9)

The following polysiloxane (A) and polysiloxane (B) are contained, The liquid crystal aligning agent characterized by the above-mentioned.
Polysiloxane (A): Polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by Formula (1) and the alkoxysilane represented by Formula (2).
R ¹ Si (OR ² ) ₃ (1)
(R ¹ is a hydrocarbon group having 8 to 30 carbon atoms which may be substituted with a fluorine atom, and 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 with an acryl group, methacryl group or an aryl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms.)
Polysiloxane (B): Polysiloxane obtained by polycondensing the alkoxysilane containing 70%-100% of the alkoxysilane represented by Formula (3).
Si (OR ⁵ ) ₄ (3)
(R ⁵ represents an alkyl group having 1 to 5 carbon atoms.) The method of claim 1,
The liquid crystal aligning agent whose polysiloxane (B) is polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane further represented by Formula (2). The method of claim 1,
The liquid crystal aligning agent whose polysiloxane (B) is polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane further represented by 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 method according to any one of claims 1 to 3,
The liquid crystal aligning agent which is polysiloxane obtained by polycondensing the alkoxysilane containing the alkoxysilane represented by following formula (5) in which at least 1 sort (s) of polysiloxane chosen from polysiloxane (A) and polysiloxane (B) is further represented.
(R ⁸ ) _n Si (OR ⁹ ) _4-n (5)
(R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group, and R ⁹ is a C1-5 carbon group) Is an alkyl group, n represents an integer of 0 to 3) The method according to any one of claims 1 to 3,
All the alkoxysilane represented by the said Formula (1) is contained in 1 mol%-20 mol% of all the alkoxysilanes used for polysiloxane (A), and the alkoxysilane represented by the said Formula (2) is used for polysiloxane (A) The liquid crystal aligning agent contained 10 mol%-80 mol% in an alkoxysilane. The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent in any one of Claims 1-5 to a board | substrate, drying, and baking. The liquid crystal display element which has a liquid crystal aligning film of Claim 6. The liquid crystal display element obtained by apply | coating the liquid crystal aligning agent in any one of Claims 1-5, and irradiating UV in the state which applied the voltage to the liquid crystal cell in which the liquid crystal was clamped between two baked board | substrates. The manufacturing method of the liquid crystal display element which apply | coats the liquid crystal aligning agent in any one of Claims 1-5, clamps a liquid crystal between two baked board | substrates, and irradiates UV in the state which applied the voltage.