KR101049550B1 - Liquid crystal aligning agent, Liquid crystal aligning film containing this, Liquid crystal display containing this - Google Patents

Abstract

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment layer including the same, and a liquid crystal display device including the same, wherein the liquid crystal aligning agent is a first alkoxy silane compound represented by the following Chemical Formula 1 and a second alkoxy represented by the following Chemical Formula 2 A polysiloxane formed by polymerizing the first alkoxy silane compound and the second alkoxy silane compound in a molar ratio of 0.02 to 0.5 moles of the second alkoxy silane compound per mole of the first alkoxy silane compound, and a polysiloxane and a solvent. do.

[Formula 1]

(2)

(Definitions for R, R ₁ and R ₂ in Formulas 1 and 2 are as described in the detailed description of the specification).

The liquid crystal aligning agent of this invention can provide the alignment film which has stable vertical alignment force and the outstanding liquid-crystal orientation, heat resistance, and uniformity. In addition, the long-term reliability, high voltage holding ratio, and stable pretilt angle required for the liquid crystal aligning agent for large LCD TVs can be maintained, and an alignment film excellent in chemical resistance can be provided. Therefore, it is possible to provide an LCD product having a high display quality, and the alignment film properties are not degraded by other processes such as liquid crystal degradation and cleaning in the LCD panel manufacturing process, and in particular, the electrostatic eliminating properties generated during the process are excellent and removed. No additional annealing time is required to reduce production time.

Liquid crystal aligning film, liquid crystal aligning agent, silicon oligomer compound, polysiloxane, afterimage, pretilt angle, voltage holding ratio, orientation stability

Description

Liquid crystal aligning agent, a liquid crystal aligning film including the same, and a liquid crystal display device including the same TECHNICAL FIELD [0001] ALIGNMENT AGENT OF LIQUID CRYSTAL

The present invention relates to a liquid crystal aligning agent used in a liquid crystal display device, a liquid crystal alignment film including the same, and a liquid crystal display device including the same, and more particularly, to have a stable vertical alignment force, excellent liquid crystal alignment property, heat resistance and uniformity, A liquid crystal aligning agent having a high voltage holding ratio, a liquid crystal aligning film including the same, and a liquid crystal display including the same.

Current liquid crystal devices (LCDs) generally apply a liquid crystal aligning agent to a glass substrate on which a transparent indium-tin oxide (ITO) conductive film is deposited, and harden it with heat to form an alignment layer. Two board | substrates are bonded together in opposition, a liquid crystal is inject | poured, or a liquid crystal is dripped at one board | substrate, and a counter substrate is bonded together, and is completed. The liquid crystal dropping method is adopted in the 5th generation or larger line.

In general, a liquid crystal aligning agent is a solution in which a polymer resin, which is used to form an alignment film after application, is dissolved in a solvent. The polymer resin used here is a polyamic acid in which an aromatic acid is a polycondensation of an anhydride and an aromatic diamine, or dehydration and ring closure thereof. One polyimide is used.

However, when only aromatic acid dianhydride and diamine are used as described above, thermal stability, chemical resistance, mechanical properties, etc. are excellent, but transparency and solubility are degraded due to charge transfer complex, and electro-optic properties are deteriorated. have. In order to solve this problem, there has been an attempt to improve the problem by introducing an aliphatic cyclic acid dianhydride monomer or an aliphatic cyclic diamine (Japanese Patent Laid-Open No. 11-84391). In addition, functional diamines having side chains or functional acid dianhydrides having side chains and the like have been introduced for increasing the pretilt angle and stability of liquid crystals (Japanese Patent Laid-Open No. 06-136122).

In addition, the development of a vertical alignment layer that can be applied in a vertical alignment mode (VA mode) constituting the LCD panel by aligning the liquid crystal perpendicular to the surface (US Patent No. 5,420,233). The vertical alignment mode has a large viewing angle and does not require an alignment process such as a rubbing treatment, making it easy to enlarge the size. For large display devices of 40 inches or more, many panel makers adopt a vertical alignment mode (VA-mode).

However, as the vertical alignment type liquid crystal display device is enlarged, various problems that are difficult to solve with the conventional liquid crystal alignment agent have also occurred. In particular, in the case of the polyamic acid aligning agent is subjected to the printing process and curing step of about 200 ℃, in general, the imidization of the polyamic acid is completed at a high temperature of 300 ℃ or more, the imidation ratio is about 20 to 70%, A large amount of carboxyl groups not imidized exist on the alignment film surface. These uncured carboxyl groups are known to adsorb with the ionic impurities in the liquid crystal to lower the voltage holding ratio and promote the generation of afterimages.

Even in the case of using a polyimide aligning agent, since it is impossible to achieve 100% imidization in the dehydration ring closing process, there is a material problem in which afterimages eventually develop in long-term driving. In addition, functional diamine compounds having side chains are introduced into the polymer main chain to realize vertical alignment. Long-chain alkyl groups having 6 to 24 carbon atoms used as side chains of the functional diamines have flexible liquid chains. When the same physical shock is received, the pretilt angle decreases, causing a stain on the screen.

Therefore, research on inorganic alignment films has been continued for a long time in order to overcome the limitation of the organic polyimide alignment films. Inorganic alignment films have a large strength as next-generation alignment films because they have less change in physical properties of the organic alignment films and do not oxidize or generate ionic impurities even at high temperatures, and thus have fewer display problems such as afterimages and stains during long-term operation.

The inorganic alignment layer may be formed by an inorganic deposition method in which an inorganic layer is formed on an LCD substrate by a method such as chemical vapor deposition (CVD) of silicon oxide or silane monomer.

In addition, as described in Korean Patent Publication No. 1997-0062769, tetraalkoxy silane monomers are subjected to hydrocondensation polymerization to obtain a polysiloxane resin, which is dissolved in a suitable solvent to form an alignment solvent similar to an existing organic alignment layer, and then coating it on a substrate. And there is a wet method of curing at a temperature of 80 to 400 ℃ to form an inorganic film.

The inorganic deposition method has a disadvantage that it takes a long time to deposit and the process is expensive and difficult to apply as the substrate size increases, but the wet method is commercialized in that it can be applied to the same process as a conventional polyimide alignment layer. It's the best way.

However, in the case of forming a polysiloxane solvent by polymerizing a silane compound with the composition mentioned in Korean Patent Laid-Open Publication No. 1997-0062769 and coating and curing the same on an electrode substrate, the electro-optical properties, as well as low voltage preservation rate and poor printing, It has the same disadvantages.

It is an object of the present invention to provide a liquid crystal aligning agent having stable vertical alignment force, excellent liquid crystal alignment property, heat resistance and uniformity, and having high voltage holding ratio (VHR).

Another object of the present invention is to provide a liquid crystal aligning film containing the liquid crystal aligning agent.

Still another object of the present invention is to provide a liquid crystal display device including the liquid crystal alignment layer.

The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by the average person from the following description.

According to one embodiment of the present invention, the first alkoxy silane compound represented by the following formula (1) and the second alkoxy silane compound represented by the formula (2) is 0.02 to 1 mol of the second alkoxy silane compound per mole of the first alkoxy silane compound Polysiloxane formed by polymerizing the first alkoxy silane compound and the second alkoxy silane compound in an amount of 0.5 molar ratio; And it provides a liquid crystal aligning agent comprising a solvent.

[Formula 1]

In Formula 1, R is an alkyl group having 1 to 6 carbon atoms, R ₁ is an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, n is an integer of 2 to 20.

[Formula 2]

In Formula 2, R is R is an alkyl group having 1 to 6 carbon atoms, R ₂ is an alkyl group having 1 to 20 carbon atoms or a fluorine alkyl group having 2 to 20 carbon atoms.

According to another embodiment of the present invention, a liquid crystal aligning film prepared by applying the liquid crystal aligning agent to a substrate is provided.

According to still another embodiment of the present invention, a liquid crystal display including the liquid crystal alignment layer is provided.

Other specific details of embodiments of the present invention are included in the following detailed description.

The liquid crystal aligning agent of the present invention can provide an alignment film having a stable vertical alignment force, excellent liquid crystal alignment property, heat resistance, low drop in voltage retention rate even in long-term driving, uniformity, and stripping in a reworkable solvent. can do. In addition, the long-term reliability, high voltage holding ratio, and stable pretilt angle required for the liquid crystal aligning agent for large LCD TVs can be maintained, and an alignment film excellent in chemical resistance can be provided. Therefore, it is possible to provide an LCD product having a high display quality, and the alignment film properties are not degraded by other processes such as liquid crystal degradation and cleaning in the LCD panel manufacturing process, and in particular, the electrostatic eliminating properties generated during the process are excellent and removed. No additional annealing time is required to reduce production time.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

According to one embodiment of the present invention, the first alkoxy silane compound represented by the following formula (1) and the second alkoxy silane compound represented by the formula (2) is 0.02 to 1 mol of the second alkoxy silane compound per mole of the first alkoxy silane compound Polysiloxane formed by polymerizing the first alkoxy silane compound and the second alkoxy silane compound in an amount of 0.5 molar ratio; And it provides a liquid crystal aligning agent comprising a solvent.

[Formula 1]

In Formula 1, R is an alkyl group having 1 to 6 carbon atoms, R ₁ is an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, n is an integer of 2 to 20.

[Formula 2]

In Formula 2, R is an alkyl group having 1 to 6 carbon atoms, R ₂ is an alkyl group having 1 to 20 carbon atoms or a fluorine alkyl group having 2 to 20 carbon atoms.

The liquid crystal aligning agent of the present invention has excellent advantages such as long-term reliability and high voltage retention (VHR), stable pretilt angle maintenance, excellent liquid crystal alignment and chemical resistance required for liquid crystal aligning agent for large LCD TVs, In addition to realizing the display quality, the alignment film characteristics are not degraded by other processes such as liquid crystal degradation and cleaning in the LCD panel manufacturing process, and in particular, the electrostatic elimination properties generated during the process are excellent, and thus no additional annealing time is required to remove the display film. The production time can be shortened.

In the liquid crystal aligning agent of the present invention, the polysiloxane may have a molar ratio of 0.02 to 0.5 moles of the first alkoxy silane compound of Formula 1 and the second alkoxy silane compound of Formula 2 of the second alkoxy silane compound per mole of the first alkoxy silane compound. When the alignment layer is manufactured from the liquid crystal aligning agent including the polysiloxane prepared as described above by polymerizing the first alkoxy silane compound and the second alkoxy silane compound, desired physical properties can be satisfactorily satisfied.

Polysiloxane prepared by polymerizing the first alkoxy silane compound of Formula 1 and the second alkoxy silane compound of Formula 2 has a weight average molecular weight of 3,000 to 30,000, and has a structure having a -Si-O-Si main chain. . Although the structure of the polysiloxane is not specifically described herein, the polysiloxane of the present invention may be obtained by polymerizing the first alkoxy silane compound of Formula 1 and the second alkoxy silane compound of Formula 2 according to a process described below. It is obvious that is easy for those in the field.

If the weight average molecular weight of the polysiloxane of the present invention is less than 3,000, the film thickness and chemical resistance is poor, the electro-optical properties are lowered, and if it exceeds 30,000, there may be a problem in printability due to the poor solubility in the solvent.

The content of polysiloxane in the liquid crystal aligning agent of the present invention is preferably 1 to 20% by weight, more preferably 3 to 8% by weight.

In the liquid crystal aligning agent of the present invention, a solvent selected from the group consisting of an alcohol first solvent, a second solvent, and a combination of the following Chemical Formula 3 may be preferably used.

(3)

In Chemical Formula 3,

R ₃ is a hydrogen atom, or a substituted or unsubstituted alkyl group, wherein carbon number is preferably 1 to 5.

Substituted herein, unless specified otherwise, a hydrogen atom is a halogen group, an alkyl group of 1 to 30 carbon atoms, a haloalkyl group of 1 to 30 carbon atoms, an aryl group of 6 to 30 carbon atoms, a heteroaryl group of 2 to 30 carbon atoms, carbon atoms It means substituted with any one substituent selected from the group consisting of 1 to 18 alkoxy groups, and combinations thereof.

Examples of the unsubstituted alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In addition, examples of the substituted alkyl group include hydroxymethyl, methoxymethyl, ethoxymethyl, hydroxyethyl, methoxyethyl or ethoxyethyl.

The second solvent is hexylene glycol, butyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl formamide, dimethyl sulfoxide, γ-butyrolactone, Methacresol, phenol, halogenated phenol, ethylene glycol, propylene glycol, triethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, malonic ester, diethyl ether, ethylene Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether, ethylene glycol phenyl methyl ether, ethylene glycol phenyl ethyl ether, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, diethylene glycol ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, die Tylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, 2-hydroxy ethyl propionate, 2- Ethyl hydroxy-2-methyl propionate, ethyl ethoxy acetate, ethyl hydroxy acetate, methyl 2-hydroxy-3-methyl butanoate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, 3-ethoxy propionic acid Ethyl, methyl 3-ethoxy propionate, methyl methoxy butanol, ethyl methoxy butanol, methyl ethoxy butanol, ethyl ethoxy butanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro butane, Trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and combinations thereof Can be mentioned.

Preferred examples of the alcohol of Formula 3 include methanol, ethanol, propanol, 1,4-butanediol, n-butanol or a combination thereof.

When hexylene glycol is used together with other solvents as the solvent, the amount of hexylene glycol is preferably used in an amount of 20 to 90% by weight based on 100% by weight of the total solvent. In addition, when butyl cellosolve is used together with another solvent as the solvent, the amount of butyl cellosolve is preferably used in an amount of 10 to 80% by weight based on 100% by weight of the total solvent. When the amount of hexylene glycol is included in the above range can be obtained excellent leveling properties, it is easy to cure, and when the amount of butyl cellosolve is included in the above range can be obtained excellent printability is preferred.

Hereinafter, the polysiloxane manufacturing process of the present invention will be described.

The first alkoxy silane compound of formula 1 and the second alkoxy silane compound of formula 2 are mixed. When the carbon number of the main chain is 1 to 3 in the compounds of Formula 1 and Formula 2, at least one compound of Formula 1 and at least one compound of Formula 2 may be used in combination.

[Formula 1]

In Formula 1, R is an alkyl group having 1 to 6 carbon atoms, R ₁ is an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, n is an integer of 2 to 20.

When n is used an oligomer corresponding to an integer of 2 to 20, the degree of crosslinking of the polymer to be produced becomes dense and stable, so that the reliability of the alignment film can be greatly improved, and if n is smaller than 2, Unstable optical characteristics, deterioration of afterimage characteristics such as low voltage holding ratio, and poor printing cause problems.

[Formula 2]

In Formula 2, R is an alkyl group having 1 to 6 carbon atoms, R ₂ is an alkyl group having 1 to 20 carbon atoms or a fluorine alkyl group having 2 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include hexyl, heptyl, octyl, dodecyl, hexadecyl or octadecyl. Examples of the fluoroalkyl group having 2 to 20 carbon atoms include trifluoropropyl and heptafluoropentyl. And fluoroalkyl groups such as heptafluoroisopentyl, tridecafluorooctyl and heptadecafluorodecyl.

Specific examples of the second alkoxy silane compound represented by Formula 2 include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane Unsubstituted alkyltrialkoxysilanes such as dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane ; Trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, heptafluoropentyltrimethoxysilane, heptafluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluoro Fluoroalkyltrialkoxysilanes such as octyltriethoxysilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.

In this case, the mixing ratio of the first alkoxy silane compound and the second alkoxy silane compound is preferably 0.02 mol or more and 0.5 mol or less, more preferably 0.02 to 0.4 mol, of the second alkoxy silane compound per mol of the first alkoxy silane compound. Do. If the amount of the second alkoxy silane compound exceeds 0.5 mole, a uniform polysiloxane solution may not be prepared. Moreover, when forming a liquid crystal aligning film using the polysiloxane manufactured using the said 2nd alkoxy silane compound in the quantity less than 0.02 mol, since the liquid crystal aligning film which shows a vertical alignment characteristic cannot be formed, it is unpreferable and liquid crystal aligning characteristic Since the amount of the first alkoxy silane compound which can be inhibited and is high in chemical resistance-solvent resistance becomes relatively excessive, the produced polysiloxane becomes insoluble in the stripper solvent. The disadvantage is that rework is not possible.

Subsequently, carboxylic acid and alcohol of the following formula (3) are added to the obtained mixture. As described above, since water is not used in the polysiloxane manufacturing process of the present invention, when the first alkoxy silane compound is present with water, a polymerization process may occur very vigorously to suppress a problem of gel or precipitation. Molecular weight adjustment is also preferable and it is preferable.

(3)

In Chemical Formula 3,

R3 is a hydrogen atom, or substituted or unsubstituted alkyl, wherein from 1 to 5 carbon atoms is preferable, and examples of the unsubstituted alkyl group include methyl, ethyl, propyl, butyl or pentyl. Moreover, hydroxymethyl, methoxymethyl, ethoxymethyl, hydroxyethyl, methoxyethyl or ethoxyethyl is mentioned as a substituted alkyl group.

Preferred examples of the alcohol represented by Formula 3 include methanol, ethanol, propanol, n-butanol, and 1,4-butanediol. In addition to these alcohols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or mixtures thereof You may use it in mixture of 2 or more types. However, the use of too many solvent types may complicate the polymerization reaction system, may be difficult in terms of reaction control or stabilization, and the solvent composition ratio may be difficult or unpredictable in preparing the polysiloxane alignment agent. . In the case of using a mixture of glycols, the amount of glycols can be appropriately adjusted. In addition, since the common silane compounds have an ethoxy group or a methoxy group, and condensation polymerization generates ethanol or methanol, it is preferable to use methanol or ethanol rather than using alcohol of too different properties. In addition, depending on the type of silane compound, ethanol is most preferable because the solubility in ethanol during polymerization is often not generated.

As the carboxylic acid, any of the carboxylic acids capable of reacting with alcohol to form an ester and generating water (H ₂ O) may be used, and a divalent dicarboxylic acid or formic acid such as oxalic acid may be used. Monovalent carboxylic acids such as acetic acid can be used.

When using a solid carboxylic acid, it is appropriate to dissolve in alcohol first. For example, the step of dissolving the solid carboxylic acid in alcohol can be carried out by adding carboxylic acid to the alcohol and heating at a temperature of 40 to 80 ° C for 10 minutes or more.

In addition, the step of adding a carboxylic acid and an alcohol to the mixture of the first alkoxy silane compound and the second alkoxy silane compound may include adding the carboxylic acid and alcohol to a dropping funnel to which a reflux capacitor is connected, and then adding the first alkoxy silane compound and the second alkoxy silane compound. It can carry out by the process of adding the mixture of an alkoxy silane compound and a 2nd alkoxy silane compound.

At this time, the molar ratio of the carboxylic acid and the alcohol is preferably 1: 1 to 1: 100, more preferably 1: 2 to 1: 20. When the molar ratio of carboxylic acid and alcohol is included in the above range, the reactivity is excellent and the side reactions can be easily removed, which is preferable.

In addition, the absolute amount of the carboxylic acid and the alcohol is appropriately increased in proportion to the input amount of the silane compound, and the carboxylic acid is 0.25 mol per mole of the alkoxy group in the total silane compound of the first alkoxy silane compound and the second alkoxy silane compound. To 1 mol is preferred. In the actual polysiloxane polymerization, 1 mole of carboxylic acid, for example oxalic acid, reacts with 2 moles of alcohol, for example ethanol, to produce 2 moles of water, and 2 moles of alkoxy group of the silane compound reacts with 1 mole of water to form Si-O. Since 1 mol and 2 mol of siloxane bonds of -Si produce alcohol, the actual equivalent of carboxylic acid is 0.25 mol relative to 1 mol of the total alkoxy groups of the silane compounds. However, considering the reactivity and the degree of polymerization, the polymerization rate is significantly lower than 0.25 mole, and the polymer may have a large amount of alkoxy group in itself when forming the polymer, which may act as a factor of lowering reliability when the alignment film is applied. In addition, when the carboxylic acid is used in an amount exceeding 1.0 mole, the polymerization rate is high, which makes it difficult to control the molecular weight and may form precipitates or gels. It is good to be.

The alcohol is preferably 1 to 100 moles per mole of alkoxy group in the total silane compounds of the first alkoxy silane compound and the second alkoxy silane compound. If the alcohol content is less than 1 mole per 1 mole of alcohol, the reaction is not performed as desired. If it exceeds 100 moles, side reactions occur and it is difficult to remove the side reaction products, which is not preferable.

The obtained mixed liquid is subjected to a polymerization step at a temperature of 50 to 180 ° C. In this case, when the solid carboxylic acid is used, it is heated to a temperature of 40 to 80 ℃ dissolves in alcohol, so that it may be carried out without performing a separate heating process, but the preparation of the mixed liquid at room temperature If so, the heating process must be carried out separately. Of course, even when using a solid carboxylic acid, if a higher temperature is required for polymerization, the heating step may be performed so that the temperature is 50 to 180 ℃. If the heating step is carried out at a temperature below 50 ° C., the mixed liquid becomes cloudy or contains a water insoluble substance, which causes problems in printing when used as an alignment agent, which is not preferable.

Therefore, the heating process is suitable to be carried out at a temperature of 50 ℃ or more can be terminated in a short time, it is appropriate, but it is sufficient to carry out at a temperature of up to 180 ℃, even if carried out at a temperature exceeding 180 ℃ does not show any additional effect It is not necessary to carry out at temperature higher than 180 degreeC. The heating time is not particularly limited. For example, it can be performed about 8 hours at 50 degreeC and 78 degreeC for 3 hours under reflux.

Typically, the heating process is stopped when the amount of remaining first and second alkoxy silane compounds is 5 mol% or less based on the total amount of the first and second alkoxy silane compounds. Based on the total amount of the first and second alkoxy silane compounds used, the polysiloxane-containing liquid having more than 5 mol% of the first and second alkoxy silane compounds remaining on the surface of the electrode substrate is then coated. When thermally cured at a temperature of 80 to 350 ° C., the coating film formed tends to have pinholes, or it is difficult to obtain a coating film having a suitable hardness, which is not preferable. Therefore, the amount of the first and second alkoxy silane compounds remaining in the polysiloxane-containing liquid obtained after the heating step is preferably at most 5 mol% or less, and the smaller is preferable, the lower limit need not be limited.

Since the reactor used in the said heating process should just use a normal reactor, it does not need to specifically limit.

According to the heating process, a polysiloxane-containing liquid comprising polysiloxane and alcohol is obtained. At this time, the polysiloxane is present in the state dissolved in alcohol or colloidal state, the weight average molecular weight is a polysiloxane having a main chain of SiO ₂ structure of about 3,000 to 30,000. The obtained polysiloxane-containing liquid is also in a transparent state and does not contain polysiloxane in the form of a gel. This is because the hydrolysis reaction does not occur because no water is used in the polysiloxane production process, so that a turbid liquid may be obtained which may be generated during the production of polysiloxane due to hydrolysis, or there is no problem in that a non-uniform polysiloxane is produced. The average molecular weight of the polysiloxane can be easily controlled by increasing or decreasing the reaction temperature, reaction time, silane monomer concentration, oxalic acid content, and the like.

In addition, according to the manufacturing process of the present invention, co-condensed polysiloxanes of the first and second alkoxy silane compounds having a suitable degree of polymerization and having a relatively uniform structure will be produced.

The obtained polysiloxane-containing liquid may be used directly as a coating fluid, ie, a liquid crystal aligning agent, coated on an ITO substrate or the like to form a liquid crystal alignment film, or may be concentrated or diluted. However, since the alcohol has a low boiling point, it is more preferable to replace the alcohol first solvent with another second solvent.

Substituting with another solvent is a method of adding a solvent such as hexane, toluene and benzene to the polysiloxane-containing liquid to obtain a solid precipitate, and then filtered and redissolved in the second solvent to be replaced, After adding a second solvent to the polysiloxane-containing liquid, there is a method of distilling off the alcohol first solvent. In addition, a second solvent to be substituted in this way may be added to the polysiloxane-containing liquid, and after distilling off the alcohol first, a second or more second solvent to be substituted may be further added.

The second solvent to be substituted is hexylene glycol, butyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl formamide, dimethyl sulfoxide, γ- Butyrolactone, metacresol, phenol, halogenated phenol, ethylene glycol, propylene glycol, triethylene glycol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, malonic ester, di Ethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether, ethylene glycol phenyl methyl ether, ethylene glycol phenyl ethyl ether, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, diethylene glycol ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, 2-hydroxy propionic acid Ethyl, 2-hydroxy-2-methyl propionate, ethoxy ethyl acetate, hydroxy ethyl acetate, 2-hydroxy-3-methyl butanoate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3 Ethyl ethoxy propionate, methyl 3-ethoxy propionate, methyl methoxy butanol, ethyl methoxy butanol, methyl ethoxy butanol, ethyl ethoxy butanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4 -Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and combinations thereof It is selected from may be used.

When used as a liquid crystal aligning agent for forming a liquid crystal aligning film, the solid content of polysiloxane is preferably 1 to 20% by weight, but more preferably 3 to 8% by weight of solid content in order to form a uniform film within 1000 kPa during coating.

Since the solid content of polysiloxane is composed of SiO ₂ , it is possible to infer it to some extent by calculating the number of Si moles of the initial silane monomer, but in polysiloxane polymerization, an alkoxy group is substituted with a hydrogen atom and becomes a hydroxyl group, which is then condensation polymerization. Dehydration forms Si-O-Si bonds, which may result in a difference of about 30 to 60% between the solids content before polymerization and the solids content after completion of polymerization, so that some of the prepared polysiloxane-containing liquids are subjected to 100 to 200 ° C convection oven. It is preferable to measure the residual amount of solid content obtained by drying for 20 to 60 minutes with a balance.

The process of forming a liquid crystal aligning film using the liquid crystal aligning agent containing polysiloxane of this invention can be formed by coating the said liquid crystal aligning agent on a board | substrate, and thermosetting.

The substrate may be used without any particular limitation as long as it is a substrate having high transparency, and a substrate on which an ITO electrode is formed, a glass substrate, an acrylic substrate, a polycarbonate substrate, or the like may be used. It is preferable from a viewpoint of simplicity.

The coating process may be carried out by conventional methods such as dipping, spinning coating, brush coating, roll coating or flexo printing.

Although the thermosetting may be performed immediately after the liquid crystal aligning agent is applied to the substrate, it is preferable to perform a drying step in order to increase the uniformity of the coating film before performing the thermosetting.

In the drying process, the temperature is preferably carried out for 1 to 60 minutes at room temperature to 80 ℃, preferably 50 to 80 ℃. By adjusting the volatilization degree of a liquid crystal aligning agent component through the said drying process, a uniform and uneven coating film can be obtained.

The thermosetting step after the drying step may be carried out at a temperature of 80 to 400 ℃, preferably 100 to 350 ℃. The thermosetting process may be carried out for 5 to 60 minutes.

When the temperature of the said thermosetting process is less than 80 degreeC, the hardness, chemical resistance, etc. of the formed coating film become unsuitable. In addition, thermal curing at more than 400 ° C. is not preferable because the vertical alignment property becomes poor. The thermosetting process can be carried out using conventional methods such as hotplates, ovens or belt furnaces.

The thickness of the liquid crystal aligning film formed by the said process has the preferable range of 100-2,000 kPa. When the thickness of the liquid crystal aligning film is thinner than 100 GPa, pinholes are likely to occur, and the liquid crystal device having the film tends to have disadvantages such as poor stability in conductivity or defects in the liquid crystal display. On the other hand, if it exceeds 2,000 GPa, the uniformity of the film surface becomes poor, or the film tends to be cracked, which is not preferable.

In addition, the liquid crystal alignment film formed according to the above process may be used in a liquid crystal display device without performing a uniaxial alignment treatment by polarized ultraviolet irradiation or in some applications such as a vertical alignment layer. The uniaxial alignment treatment may be performed by exposing the formed liquid crystal alignment layer at an energy of 10 mJ to 5000 mJ for 0.1 to 180 minutes.

According to still another embodiment of the present invention, a display device including the liquid crystal alignment layer formed of the liquid crystal alignment agent of the present invention is provided. It is preferable that the said display device is a liquid crystal display device.

1 is a cross-sectional view of a liquid crystal display according to an exemplary embodiment of the present invention.

Referring to FIG. 1, the liquid crystal display 1 according to the exemplary embodiment of the present invention includes a lower panel 100, an upper panel 200, and a liquid crystal layer 3.

The lower panel 100 includes a gate conductor including a plurality of gate lines (not shown) and a plurality of storage electrodes 133 on an upper surface of the first substrate 110. . On the gate conductor, a gate insulating layer 140, a plurality of semiconductors 154, a plurality of pairs of ohmic contacts 163 and 165, a plurality of source electrodes 173, And a plurality of drain electrodes 175 are formed in this order.

One gate electrode 124, one source electrode 173, and one drain electrode 175 together with the semiconductor 154 form one thin film transistor (TFT).

A passivation layer 180 is formed on the exposed portion of the semiconductor 154, the source electrode 173, the drain electrode 175, and the gate insulating layer 140. A plurality of pixel electrodes 191 are formed on the passivation layer 180.

Next, the upper panel 200 will be described.

In the upper panel 200, a light blocking member 220 is formed on the second substrate 210. A plurality of color filters 230 are formed on the second substrate 210 and the light blocking member 220, and an overcoat 250 is formed on the color filters 230. The overcoat 250 may prevent the color filter 230 from being exposed to the liquid crystal layer 3, and the overcoat 250 may be omitted.

The first liquid crystal alignment layer 12 and the second liquid crystal alignment layer 22 are formed on the pixel electrode 191 of the lower panel 100 and the common electrode 270 of the upper panel 200, respectively. The first liquid crystal alignment layer 12 and the second liquid crystal alignment layer 22 are manufactured by using the liquid crystal alignment agent according to the embodiment of the present invention.

In FIG. 1, the liquid crystal alignment layers 12 and 22 are formed on both the lower panel 100 and the upper panel 200. However, the liquid crystal alignment layers 12 and 22 may be the upper panel 200 or the lower panel. It may be formed only in any one of the (100).

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples.

Synthesis Example: Preparation of Polyamic Acid (PAA-1)

Synthesis Example 1

684.1 g of ethanol was added to a four-neck flask connected to a reflux condenser to dissolve 267.4 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. . Thereafter, a mixture of 267.42 g of an ethoxysilane oligomer having n = 2 and 7.49 g of octadecyltrimethoxysilane in Chemical Formula 1 was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, followed by 4 hours at a temperature of 60 ° C. For a while.

[Formula 1]

(In Formula 1, R ₁ is ethoxy, R is an ethyl group, n is 2)

Thereafter, the obtained product was cooled, 2000 g of hexylene glycol was charged and distilled, and ethanol was removed to obtain a 10% by weight polysiloxane solution having a weight average molecular weight of 16,000, which was named SA02-1. .

Synthesis Example 2

621.9 g of ethanol was dissolved in a four-neck flask connected to a reflux condenser, and dissolved 243.1 g of oxalic acid while stirring. The mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Then, in Formula 1 shown in Synthesis Example 1, a mixture of 273.6 g of ethoxysilane oligomer having n = 2 and 74.94 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

The resulting mixture was cooled, 2000 g of hexylene glycol was added and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 18,000, which was named SA02-2.

Synthesis Example 3

577.0 g of ethanol was added to a four-neck flask connected to a reflux condenser to dissolve 225.6 g of oxalic acid while stirring. Thereafter, a mixture of 229.14 g of an ethoxysilane oligomer having n = 2 and 123.64 g of octadecyltrimethoxysilane in Formula 1 shown in Synthesis Example 1 was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

Thereafter, the resultant mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a polysiloxane solution having a solid content of 10% by weight with a weight average molecular weight of 15,000, which was named SA02-3.

Synthesis Example 4

1587.1 g of ethanol was added to a four-neck flask connected to a reflux condenser to dissolve 620.4 g of oxalic acid while stirring. Thereafter, in Formula 1 shown in Synthesis Example 1, a mixture of 860.4 g of n = 6 ethoxysilane oligomer and 7.49 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 14,000, which was named SA02-4.

Synthesis Example 5

1359.1 g of ethanol was dissolved in a 4-neck flask connected to a reflux condenser, and 531.2 g of oxalic acid was dissolved while stirring. Thereafter, in Formula 1 shown in Synthesis Example 1, a mixture of 702.4 g of ethoxysilane oligomer having n = 6 and 74.9 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 12000, which was named SA02-5.

Synthesis Example 6

6.94.4 g of ethanol was added to a four-neck flask connected to a reflux condenser to dissolve 466.9 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Thereafter, in Formula 1 shown in Synthesis Example 1, a mixture of 588.3 g of ethoxysilane oligomer having n = 6 and 123.6 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃. Thereafter, the mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution having a weight average molecular weight of 13000, which was named SA02-6.

Synthesis Example 7

2941.6 g of ethanol was added to a 4-neck flask connected to a reflux condenser to dissolve 1149.8 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Thereafter, in Formula 1 shown in Synthesis Example 1, a mixture of 1648.4 g of n = 12 ethoxysilane oligomer and 7.49 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 12000, which was named SA02-7.

Synthesis Example 8

2464.7 g of ethanol was added to a four-neck flask connected to a reflux condenser to dissolve 963.4 g of oxalic acid while stirring. Thereafter, in Formula 1 shown in Synthesis Example 1, a mixture of 1345.6 g of n = 12 ethoxysilane oligomer and 74.9 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 13000, which was named SA02-8.

Synthesis Example 9

2120.4 g of ethanol was dissolved in a four neck flask connected to a reflux condenser, and 828.8 g of oxalic acid was dissolved while stirring. The mixture was heated to 60 ° C. and maintained for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Thereafter, a mixture of 1126.9 g of ethoxysilane oligomer having n = 12 and 123.6 g of octadecyltrimethoxysilane in Formula 1 shown in Synthesis Example 1 was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, followed by 60 ° C. It was kept at a temperature of 4 hours. After cooling, 2000 g of hexylene glycol was added and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution having a weight average molecular weight of 11000, which was named SA02-9.

Comparative Synthesis Example 1

687.6 g of ethanol was added to a four-neck flask connected to a reflux condenser to dissolve 268.9 g of oxalic acid while stirring. Thereafter, in Formula 1 shown in Synthesis Example 1, a mixture of 338.6 g of ethoxysilane oligomer having n = 2 and 3.75 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 16,000, which was named SA04-1.

Comparative Synthesis Example 2

556.1 g of ethanol was added to a 4-neck flask connected to a reflux condenser to dissolve 216.1 g of oxalic acid while stirring. Thereafter, in Formula 1, a mixture of 205.2 g of ethoxysilane oligomer having n = 2 and 149.9 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, followed by 4 at a temperature of 60 ° C. Kept for hours.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a polysiloxane solution having a solid content of 10% by weight with a weight average molecular weight of 15000, which was named SA04-2.

Comparative Synthesis Example 3

1599.8 g of ethanol was added to a 4-neck flask connected to a reflux condenser to dissolve 625.3 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Thereafter, in Formula 1, a mixture of 869.2 g of ethoxysilane oligomer having n = 6 and 3.75 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, followed by 4 at a temperature of 60 ° C. Kept for hours.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol and to obtain a polysiloxane solution having a solid content of 10% by weight with a weight average molecular weight of 14,000, which was named SA04-3.

Comparative Synthesis Example 4

1105.7 g of ethanol was added to a 4-neck flask connected to a reflux condenser to dissolve 432.2 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Thereafter, in Formula 1 shown in Synthesis Example 1, a mixture of 526.8 g of ethoxysilane oligomer having n = 6 and 149.9 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 15000, which was named SA04-4.

Comparative Synthesis Example 5

2968.1 g of ethanol was dissolved in a four-neck flask connected to a reflux condenser to dissolve 1160.2 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Thereafter, a mixture of 1665.2 g of ethoxysilane oligomer and 3.75 g of octadecyltrimethoxysilane in Formula 1 shown in Synthesis Example 1 was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, followed by 60 ° C. It was kept at a temperature of 4 hours.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 13000, which was named SA04-5.

Comparative Synthesis Example 6

1964.9 g of ethanol was added to a four-neck flask connected to a reflux condenser to dissolve 756.3 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Thereafter, a mixture of 1009.2 g of ethoxysilane oligomer having n = 12 and 149.9 g of octadecyltrimethoxysilane in Formula 1 shown in Synthesis Example 1 was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 It was kept for 4 hours at a temperature of ℃.

The resulting mixture was cooled to add 2000 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 12000, which was named SA04-6.

Comparative Synthesis Example 7

204.7 g of ethanol was added to a 4-neck flask connected to a reflux condenser to dissolve 80.0 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Subsequently, in Formula 1 shown in Synthesis Example 1, a mixture of 89.1 g of n = 1 ethoxysilane and 8.49 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, and then 60 ° C. It was kept at a temperature of 4 hours.

The resulting mixture was cooled to add 250 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a weight average molecular weight of 12000, which was named SA04-7.

Comparative Synthesis Example 8

200.0 g of ethanol was added to a four-neck flask connected to a reflux condenser to dissolve 78.0 g of oxalic acid while stirring, and the mixture was heated to 60 ° C. and held for 30 minutes to confirm that oxalic acid was sufficiently dissolved in ethanol. Thereafter, in Formula 1 shown in Synthesis Example 1, a mixture of 79.7 g of ethoxysilane having n = 1 and 25.3 g of octadecyltrimethoxysilane was slowly added dropwise to the oxalic acid / ethanol solution over 1 hour, followed by 60 ° C. It was kept at a temperature of 4 hours.

The resulting mixture was cooled to add 250 g of hexylene glycol and distilled to remove ethanol to obtain a 10% by weight polysiloxane solution with a solid content having a weight average molecular weight of 12000, which was named SA04-8.

[Example]

Example 1

To 100 g of the SA02-1 solution having a solid content of 10.0 wt% obtained in Synthesis Example 1, 50 g of butyl cellulose was added thereto, stirred well, and filtered through a 0.2 μm filter to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02-). 1).

The liquid crystal aligning agent prepared by the above method was applied on a glass substrate having a 10 cm × 10 cm sized ITO electrode, coated on an ITO surface, made uniformly to a thickness of 0.1 μm under certain conditions, and then dried at 80 ° C. on a hot plate. An alignment film sample was prepared through a process and a thermosetting process at 210 ° C.

Using the prepared alignment film sample, the spreading property and the curling property of the prepared sample were observed through the naked eye and an optical microscope to evaluate the printability of the alignment film solution. The printability evaluation results are shown in Table 1 below.

In addition, samples prepared in the same manner as those used in the printing evaluation for evaluating rework, ie, stripping properties by solvent, were prepared at 70 ° C. in TS-204, an alignment film reworking solvent of Korea Polyol Co., Ltd. It was measured by immersion in the alignment film is completely removed, the results are shown in Table 1 below.

In order to evaluate the liquid crystal alignment, pretilt angle and electro-optical characteristics of the alignment film solution, a liquid crystal cell was prepared and used in the following manner. The photolithography process was performed to remove other portions of ITO, leaving only 1.5 cm × 1.5 cm square ITO shapes and electrode ITO shapes for voltage application on glass substrates on which standard sized ITO electrodes were formed. After applying the liquid crystal aligning agent prepared in Example 1 to the patterned ITO surface substrate and spin-coated to 0.1 ㎛ thickness, an alignment film sample was prepared through a 80 ℃ desolvent process and 210 ℃ thermosetting process. .

After aligning the sample of the alignment film using a rubbing machine at a predetermined depth and at a constant speed, the rubbing directions are in opposite directions (for VA mode) / 90 degrees, and then maintain a square cell ITO of 4.75 μm. Cells were prepared by joining the shapes up and down consistently, and liquid crystal cells were prepared by filling liquid crystals in the cells made in this manner.

The prepared liquid crystal cell was observed for the liquid crystal alignment property using an orthogonally polarized optical microscope, and the results are shown in Table 1 below.

The pretilt angle of the liquid crystal of the prepared liquid crystal cell was measured using a crystal rotation method, and the results are shown in Table 1 below.

In addition, the voltage holding ratio (VHR) of the prepared liquid crystal cell was measured at room temperature (25 ° C.), and the results are shown in Table 1 below. In addition, in order to evaluate the reliability of the alignment layer during long-term driving, the degree of degradation of the voltage retention rate after applying a voltage at a high temperature (60 ° C.) for 500 hours or more was measured, and the results are shown in Table 1 below. The voltage holding ratio refers to the extent to which the liquid crystal layer in the floating state and the floating state of the liquid crystal layer in the active driving type TFT-LCD maintains the charged voltage during the non-selection period, and a value close to 100% is ideal.

In addition, the residual DC voltage (RDC) of the prepared liquid crystal cell was measured, and the results are shown in Table 1 below. The residual DC voltage refers to a voltage applied to the liquid crystal layer even when no impurities are applied from the ionized liquid crystal layer to the alignment layer. Residual DC voltage was measured using flicker among the method of using a flicker which is a common method and the method of using the capacitance change curve (C-V) of the liquid crystal layer according to the DC voltage. The results of the electro-optical characteristics of the alignment layer using the liquid crystal cell are shown in Table 1 below.

In addition, the voltage-transmittance curve of the prepared liquid crystal cell was measured, and the results are shown in Table 1 below. The voltage-transmittance curve is one of the important electrical and optical characteristics, which is one of the characteristics for determining the driving voltage of the liquid crystal display device. The curve is normalized with the amount of light in the state at 0%.

Example 2

50 g of butyl cellosolve was added to 100 g of the SA02-2 solution having a solid content of 10.0 wt% obtained in Synthesis Example 2, followed by stirring and filtering with a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02). -2). Using this liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C), voltage degradation rate, residual DC voltage, and voltage were measured. The transmittance was measured, and the results are shown in Table 1 below.

Example 3

50 g of butyl cellosolve was added to 100 g of the SA02-3 solution having a solid content of 10.0 wt% obtained in Synthesis Example 3, stirred, and filtered through a filter having a particle diameter of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02-). 3). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Example 4

50 g of butyl cellosolve was added to 100 g of the SA02-4 solution having a solid content of 10.0 wt% obtained in Synthesis Example 4, stirred, and filtered through a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02-). 4). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Example 5

50 g of butyl cellosolve was added to 100 g of the SA02-5 solution having a solid content of 10.0 wt% obtained in Synthesis Example 5, stirred, and filtered through a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02-). 5). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Example 6

50 g of butyl cellosolve was added to 100 g of the SA02-6 solution having a solid content of 10.0 wt% obtained in Synthesis Example 6, followed by stirring and filtering with a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02-). 6). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Example 7

50 g of butyl cellosolve was added to 100 g of the SA02-7 solution having a solid content of 10.0 wt% obtained in Synthesis Example 7, and stirred, followed by filtration with a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02-). 7). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage preservation ratio (25 ° C., reduction of voltage preservation rate, residual DC voltage, and voltage transmittance) were measured. The measurement results are shown in Table 1 below.

Example 8

50 g of butyl cellosolve was added to 100 g of the SA02-8 solution having a solid content of 10.0 wt% obtained in Synthesis Example 8, stirred, and filtered through a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02-). 8). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Example 9

50 g of butyl cellosolve was added to 100 g of the SA02-9 solution having a solid content of 10.0 wt% obtained in Synthesis Example 9, stirred, and filtered through a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA02-). 09). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Comparative Example 1

50 g of butyl cellosolve was added to 100 g of the SA04-1 solution having a solid content of 10.0% by weight in Comparative Synthesis Example 1, stirred, and filtered through a filter having a particle size of 0.1 µm to obtain a liquid crystal aligning agent having a solid content of 5.0% by weight (hereinafter PSA04). -1). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, voltage retention rate (25 ° C.), reduction of voltage retention rate, residual DC voltage, and voltage. The transmittance was measured, and the results are shown in Table 1 below.

Comparative Example 2

50 g of butyl cellosolve was added to 100 g of SA04-2 solution having a solid content of 10.0% by weight obtained in Comparative Synthesis Example 2, followed by stirring and filtering with a filter having a particle size of 0.1 µm to obtain a liquid crystal aligning agent having a solid content of 5.0% by weight (hereinafter PSA04). -2). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Comparative Example 3

50 g of butyl cellosolve was added to 100 g of the SA04-3 solution having a solid content of 10.0% by weight in Comparative Synthesis Example 3, stirred, and filtered through a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0% by weight (hereinafter PSA04). -3). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Comparative Example 4

50 g of butyl cellosolve was added to 100 g of the SA04-4 solution having a solid content of 10.0 wt% obtained in Comparative Synthesis Example 4, followed by stirring and filtering with a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA04). -4). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Comparative Example 5

50 g of butyl cellosolve was added to 100 g of the SA04-5 solution having a solid content of 10.0 wt% obtained in Comparative Synthesis Example 5, followed by stirring and filtering with a filter having a particle size of 0.1 μm to obtain a liquid crystal aligning agent having a solid content of 5.0 wt% (hereinafter PSA04). -5). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Comparative Example 6

50 g of butyl cellosolve was added to 100 g of the SA04-6 solution having a solid content of 10.0% by weight in Comparative Synthesis Example 6, followed by stirring and filtering with a filter having a particle size of 0.1 µm to obtain a liquid crystal aligning agent having a solid content of 5.0% by weight (hereinafter PSA04). -6). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Comparative Example 7

50 g of butyl cellosolve was added to 100 g of the SA04-7 solution having a solid content of 10.0% by weight in Comparative Synthesis Example 7, followed by stirring and filtering with a filter having a particle size of 0.1 µm to obtain a liquid crystal aligning agent having a solid content of 5.0% by weight (hereinafter PSA04). -67). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

Comparative Example 8

50 g of butyl cellosolve was added to 100 g of the SA04-8 solution having a solid content of 10.0% by weight in Comparative Synthesis Example 8, followed by stirring and filtering with a filter having a particle size of 0.1 µm to obtain a liquid crystal aligning agent having a solid content of 5.0% by weight (hereinafter PSA04). -8). Using the liquid crystal aligning agent, printability, reworkability, liquid crystal alignment, and pretilt angle were measured in the same manner as in Example 1, and voltage retention rate (25 ° C.), voltage degradation rate, residual DC voltage, and voltage transmittance were measured. Was measured, and the results are shown in Table 1 below.

sample Printability Reworkability LCD
Orientation Pretilt
(˚) VHR (%) Voltage-Transmittance RDC
(mV) 25 ℃ 60 ℃ Example 1 PSA02-1 Good Good Good 89.6 99.5 99.2 Good 120 Example 2 PSA02-2 Good Good Good 89.7 99.5 99.1 Good 160 Example 3 PSA02-3 Good Good Good 89.6 99.6 99.1 Good 170 Example 4 PSA02-4 Good Good Good 89.5 99.5 99.1 Good 137 Example 5 PSA02-5 Good Good Good 89.8 99.4 99.0 Good 150 Example 6 PSA02-6 Good Good Good 89.5 99.5 99.1 Good 155 Example 7 PSA02-7 Good Good Good 89.6 99.6 99.2 Good 162 Example 8 PSA02-8 Good Good Good 89.7 99.5 99.2 Good 141 Example 9 PSA02-9 Good Good Good 89.7 99.6 99.1 Good 136 Comparative Example 1 PSA04-1 Good Good Good 89.6 98.5 97.9 Good 836 Comparative Example 2 PSA04-2 Good Good Good 89.5 97.6 97.1 Good 780 Comparative Example 3 PSA04-3 Good Good Good 89.7 98.3 97.8 Good 760 Comparative Example 4 PSA04-4 Good Good Good 89.7 98.1 97.6 Good 860 Comparative Example 5 PSA04-5 Good Good Good 89.7 97.9 97.4 Good 910 Comparative Example 6 PSA04-6 Good Good Good 89.6 98.3 97.9 Good 850 Comparative Example 7 PSA04-7 Good Good Good 89.5 98.4 97.9 Good 905 Comparative Example 8 PSA04-8 Good Good Good 89.6 98.5 98.1 Good 895

(Electrical and Optical Properties of Liquid Crystal Alignment Film)

Referring to Table 1, it can be seen that the liquid crystal navigators prepared in Examples 1 to 9 and Comparative Examples 1 to 8 have good printability, vertical alignment, and pretilt angle, and thus may be used as liquid crystal alignment layers.

However, as shown in Table 1, the liquid crystal aligning agents prepared in Examples 1 to 9 had a good voltage-transmittance, and the voltage holding ratios were all 99% or more, whereas the liquid crystal aligning agents prepared in Comparative Examples 1 to 8 had voltage It can be seen that the conservation rate is less than 99%.

In addition, it can be seen that the liquid crystal aligning agents prepared in Examples 1 to 9 had a low residual DC, whereas the liquid crystal aligning agents prepared in Comparative Examples 1 to 8 showed a very high residual DC.

The voltage holding ratio and the residual DC serve as a criterion for evaluating the afterimage characteristic of the liquid crystal alignment layer, and the higher the voltage holding ratio and the lower the residual DC, the better the afterimage characteristic. Therefore, it can be seen that the liquid crystal aligning agent prepared in Examples 1 to 9 is superior to the afterimage characteristic than the liquid crystal aligning agent prepared in Comparative Examples 1 to 8.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

1 is a cross-sectional view of a liquid crystal display according to an exemplary embodiment of the present invention.

<Explanation of symbols for the main parts of the drawings>

1: liquid crystal display device 3: liquid crystal layer

12: first liquid crystal alignment film 22: second liquid crystal alignment film

100: lower display panel 110: first substrate

175: drain electrode 191: pixel electrode

200: upper display panel 210: second substrate

230: color filter 270: common electrode

Claims (10)

The first alkoxy silane compound represented by the following formula (1) and the second alkoxy silane compound represented by the following formula (2), the second alkoxy silane compound per mole of the first alkoxy silane compound in an amount of 0.02 to 0.5 mol, Polysiloxanes formed by polymerization; And Liquid crystal aligning agent containing a solvent. [Formula 1]

(In Formula 1, R is an alkyl group having 1 to 6 carbon atoms, R ₁ is an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms, n is an integer of 2 to 20.) [Formula 2]

(In Formula 2, R is an alkyl group having 1 to 6 carbon atoms, and R ₂ is an alkyl group having 1 to 20 carbon atoms or a fluorine alkyl group having 2 to 20 carbon atoms.) The method of claim 1, The content of the polysiloxane is 1 to 20% by weight liquid crystal aligning agent. The method of claim 1, The content of the polysiloxane is 3 to 8% by weight of the liquid crystal aligning agent. The method of claim 1, The weight average molecular weight of the said polysiloxane is 3,000-30,000 liquid crystal aligning agents. The method of claim 1, The solvent is selected from the group consisting of an alcohol first solvent of Formula 3, a second solvent, and a combination thereof, the second solvent is hexylene glycol, butyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl formamide, dimethyl sulfoxide, γ-butyrolactone, metacresol, phenol, halogenated phenol, ethylene glycol, propylene glycol, triethylene glycol, acetone, methyl ethyl ketone, Cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, malonic ester, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol phenyl ether, ethylene glycol phenyl methyl ether, ethylene Glycol phenyl ethyl ether, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, diethylene glycol ether, diethylene glycol monomethyl ether, diethyl Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, 4-hydroxy 4-methyl-2-pentanone, 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl propionate, ethoxy ethyl acetate, hydroxy ethyl acetate, 2-hydroxy-3-methyl butanoate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy propionate ethyl, 3-ethoxy propionate methyl, methyl methoxy butanol, ethyl methoxy butanol, methyl ethoxy butanol, ethyl ethoxy butanol, tetrahydro Furan, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o- Chlorobenzene, hexane, and the liquid crystal alignment would heptane, octane, benzene, toluene, xylene, and is selected from the group consisting of. (3)

(In Chemical Formula 3) R ₃ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.) The method of claim 1, Wherein the solvent comprises hexylene glycol in an amount of 20 to 90 wt% with respect to 100 wt% of the total solvent. The method of claim 1, Wherein said solvent comprises butyl cellosolve in an amount of 10 to 80% by weight relative to 100% by weight of the total solvent. The method of claim 1, The polysiloxane is Mixing the first alkoxy silane compound and the second alkoxy silane compound in an amount of a molar ratio of 0.02 to 0.5 moles per mole of the first alkoxy silane compound; Preparing a reaction solution by adding a carboxylic acid and an alcohol of Formula 3 to the mixture; Liquid crystal aligning agent which is manufactured by the process of heating and polymerizing the said reaction liquid. (3)

(In Chemical Formula 3) R ₃ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.) The liquid crystal aligning film manufactured by apply | coating the liquid crystal aligning agent in any one of Claims 1-8 to a board | substrate. A liquid crystal display device comprising the liquid crystal alignment film of claim 9.

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