KR101978655B1 - Liquid crystal aligning agent, liquid crystal alignment film, manufacturing method for the liquid crystal alignment film, and liquid crystal display device - Google Patents

Abstract

(PROBLEMS) To provide a liquid crystal aligning agent having good printability on a substrate, hardly swelling a printing plate, and good continuous printing property.
(A) at least one polymer (A) selected from the group consisting of polyamic acids, polyimides, polyamic acid esters and polyorganosiloxanes, and at least one polymer selected from the group consisting of N-ethyl-2-pyrrolidone, Imidazolidinone, and 3-methoxy-N, N-dimethylpropionamide, and at least one solvent selected from the group consisting of propylene glycol diacetate, diethylene glycol diethyl ether, diisopentyl ether, and diacetone Alcohol or the like is contained in the liquid crystal aligning agent.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film,

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a process for producing the liquid crystal alignment film and a liquid crystal display device, and more particularly to a liquid crystal aligning agent having excellent printability, a liquid crystal alignment film produced using the liquid crystal aligning agent, Device.

Conventionally, various types of driving methods have been developed as liquid crystal display devices with different electrode structures and physical properties of liquid crystal molecules used. For example, TN type, STN type, VA type, in-plane switching type (IPS type ), FFS type, and optical compensation bend type (OCB type) are known. These liquid crystal display devices have a liquid crystal alignment film for aligning liquid crystal molecules. As the material of the liquid crystal alignment film, polyamic acid, polyimide, polyorganosiloxane and the like are used in view of good heat resistance, mechanical strength, and various properties such as affinity with liquid crystals.

In the liquid crystal aligning agent, the polymer component is dissolved in a solvent, and the liquid crystal aligning agent is applied to the substrate and heated to form a liquid crystal alignment film. As a solvent for the liquid crystal aligning agent, non-protic polar solvents such as N-methyl-2-pyrrolidone and? -Butyrolactone are generally used for dissolving the polymer uniformly do. In addition to the aprotic polar solvent, the solvent may be a solvent such as butyl cellosolve or the like, for example, in order to improve the coatability (printability) of the liquid crystal aligning agent when the liquid crystal aligning agent is applied to the substrate. An organic solvent having a relatively low surface tension has been used in combination (see, for example, Patent Document 1 or Patent Document 2).

As a method of applying the liquid crystal aligning agent to the substrate, various methods such as a spin coating method, an offset printing method, and an ink jet method are applied. Among them, the offset printing method is generally performed by a transfer printing apparatus in which a liquid crystal aligning agent is applied to a printing plate made of resin such as APR (registered trademark) and the liquid crystal aligning agent is transferred onto a substrate by a printing plate ( See, for example, Patent Document 3).

Japanese Laid-Open Patent Publication No. 2010-97188 Japanese Laid-Open Patent Publication No. 2010-156934 Japanese Patent Application Laid-Open No. 2001-343649

However, butyl cellosolve, which is generally used for improving the coatability of a liquid crystal aligning agent to a substrate, is liable to swell the APR resin. For this reason, when a liquid crystal aligning agent containing butyl cellosolve is applied to a substrate by offset printing, the application of the liquid crystal aligning agent to the printing plate is repeatedly performed, whereby the printing plate is swelled, I am concerned. Further, as a solvent component of the liquid crystal aligning agent, it is required that the polymer is hardly precipitated on the printing machine even when the printing is continuously performed, and the printing property (continuous printing property) is good.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its main object to provide a liquid crystal aligning agent which is excellent in printability on a substrate, hardly swells a printing plate, and has good continuous printing property.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to achieve the problems of the prior art as described above, and as a result, they found that the above problems can be solved by using a specific organic solvent as a solvent, and have completed the present invention. Specifically, the following liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element are provided by the present invention.

The present invention provides, in one aspect, at least one polymer (A) selected from the group consisting of polyamic acid, polyimide, polyamic acid ester and polyorganosiloxane, a compound represented by the following formula (1) (2) and 1,3-dimethyl-2-imidazolidinone, a compound represented by the following formula (3), a compound represented by the following formula (4) And a second solvent which is at least one selected from the group consisting of compounds represented by the following formula (5):

(In the formula (1), R ¹ is a monovalent hydrocarbon group having 2 to 5 carbon atoms or a monovalent group having "-O-" between carbon-carbon bonds in the hydrocarbon group);

(In the formula (2), R ² and R ³ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent hydrocarbon group having "-O-" between carbon-carbon bonds of the hydrocarbon group R ² and R ³ may combine with each other to form a ring structure; R ⁴ is an alkyl group having 1 to 6 carbon atoms;

(In the formula (3), R ⁵ and R ⁷ are each independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, and R ⁶ is an alkanediyl group having 2 to 5 carbon atoms);

(In the formula (4), R ⁸ represents a monovalent group having one "-O-" among the carbon-carbon bonds of the linear or branched alkyl group having 3 to 5 carbon atoms, a linear or branched group having 3 to 5 carbon atoms Is a monovalent group formed by substituting at least one hydrogen atom of the alkyl group with a hydroxyl group or a branched alkyl group having 3 to 5 carbon atoms;

, X ¹ (wherein (5), -C (OH) R ^a - (However, R ^a is an alkyl group having 1 or 2), -CO-, or -COO - * (Note * is with R ⁹ And R ⁹ is an alkyl group having 1 to 4 carbon atoms).

By using a mixed solvent containing the first solvent and the second solvent as the solvent component of the liquid crystal aligning agent, it is possible to obtain a liquid crystal aligning agent which has good applicability to the substrate and is hard to swell the printing plate. In addition, even when continuous printing is performed, the polymer is hardly precipitated on the printing machine, and the printing property can be improved.

The present invention also provides, in one aspect, a liquid crystal alignment film formed by the liquid crystal aligning agent and a liquid crystal display element comprising the liquid crystal alignment film. Since the liquid crystal alignment film of the present invention is formed using the liquid crystal aligning agent, a uniform film is formed and the film quality is good. Further, when a liquid crystal display element is manufactured using such a liquid crystal alignment film, the printing defects can be reduced in the manufacturing process, and as a result, the yield of the product can be improved.

(Mode for carrying out the invention)

The liquid crystal aligning agent of the present invention comprises at least one polymer (A) selected from the group consisting of polyamic acid, polyimide, polyamic acid ester and polyorganosiloxane as the polymer component, and the polymer (A) Is dissolved in a solvent. Hereinafter, the liquid crystal aligning agent will be described.

≪ Polymer (A) >

[Polyamic acid]

The polyamic acid in the present invention can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine.

(Tetracarboxylic acid dianhydride)

Examples of the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid in the present invention include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides. As specific examples thereof,

Examples of the aliphatic tetracarboxylic acid dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and the like;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-2 anhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- , 5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride and the like;

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride and the like; The tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. The tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

The tetracarboxylic acid dianhydride used in the synthesis preferably contains an alicyclic tetracarboxylic acid dianhydride in view of transparency and solubility in a solvent. Among the alicyclic tetracarboxylic acid dianhydrides, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- 3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro- -2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane- 2: 4,6: 8-2 anhydride, and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and it is preferable that at least one selected from the group consisting of 2,3,5-tri Carboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, and 1,2,3,4-cyclobutane tetracarbon And at least one member selected from the group consisting of acid anhydrides.

As the tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6,8-2 Anhydride, and 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, the total content of these compounds is preferably at least one selected from the group consisting of tetracarboxylic acid Is preferably 10 mol% or more, more preferably 20 to 100 mol%, based on the total amount of the dianhydrides.

(Diamine)

Examples of the diamine used for synthesizing the polyamic acid in the present invention include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples of these diamines include aliphatic diamines such as meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

As aromatic diamines, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl Diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diamino Diphenyl ether, 1,3-bis (4-aminophenoxy) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- Bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) benzene, Biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, 3,6-diaminocarbazole, N- N, N'-bis (4-aminophenyl) benzene, N, N'-bis ) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 1- Aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 3,5-diaminobenzoic acid, Diaminobenzene, cholestenyloxy-2,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid lanostanyl, 3,6-bis (4-aminobenzoyloxy) cholestane, 4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) ) Cyclohexyl-3,5-diamino (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis , 4-heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4- Aminobenzylamine and 3-aminobenzylamine represented by the following formula (D-1): < EMI ID =

(In the formula (D-1), ^XI and ^XII each independently represent a single bond, -O-, * -COO-, * -OCO- or * -NH-CO- and also attached coupling hand is combined with a diamino-phenyl group), R and R ^{ⅰ ⅱ} are, each independently, an alkanediyl group having a carbon number of 1~3, a is 0 or 1, b is an integer from 0 to 2, c is an integer of 1 to 20, n is 0 or 1, m is 0 or 1, with the proviso that a and b are not 0 at the same time, and when X ^I is * -NH-CO-, 0)

And the like;

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in JP-A-2010-97188 can be used . These diamines may be used singly or in combination of two or more kinds.

Examples of the divalent group represented by "-X ^I - (R ^I -X ^II ) _n -" in the above formula (D-1) include an alkanediyl group having 1 to 3 carbon atoms, * -O-, * -COO- , * -OC ₂ H ₄ -O- or * -NH-CO- (provided that the bonding hand having "*" attached thereto is bonded to a diaminophenyl group).

Specific examples of the group "-C _c H _{2c +1} " include a methyl group, an ethyl group, a n-propyl group, an n-butyl group, an n-pentyl group, n-heptadecyl, n-heptadecyl, n-octadecyl, n-hexadecyl, n-hexadecyl, An n-nonadecyl group, and an n-eicosyl group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulas (D-1-1) to (D-1-4).

As the diamine, one of these compounds may be used alone or two or more of them may be used in combination.

The diamine used in the synthesis of the polyamic acid in the present invention preferably contains an aromatic diamine in an amount of 30 mol% or more, more preferably 50 mol% or more, and more preferably 80 mol% or more Is particularly preferable.

When a liquid crystal aligning agent for vertically aligned liquid crystal display elements is used, those having a pretilt component as a diamine may be used in order to give good vertical alignment properties. Specific examples of the diamine having such a pretilt component include dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene , Hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, Decanoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecaneoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, Diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, 3,5-diaminobenzoic acid cholestenyl, 3,5-diaminobenzoic acid cholestanyl, 3,5- (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'-trifluoromethoxybenzoyloxy) Cyclohexyl-3, 5-diaminobenzoate, 4- (4'- Bis (4- (aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4- (4 - ((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (Aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, and the diamine represented by the formula (A-1). The diamines having a pretilt component can be used singly or in combination of two or more.

The total amount of the diamines having a pretilt component is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total diamine.

When the liquid crystal aligning property is imparted to the coating film produced by using the liquid crystal aligning agent of the present invention by the photo alignment method, a part or the whole of the polymer (A) used for preparing the liquid crystal aligning agent of the present invention may be optically oriented Is preferably used. Here, the photo-alignment structure is a concept including both the photo-alignment group and the decomposition-type photo-alignment unit. Specific examples of the optically-oriented structure include various structures derived from compounds exhibiting photo-alignment properties by photoisomerization, photo-dimerization, photodegradation, and the like. For example, azobenzene or A chalcone-containing group containing as a basic skeleton a group having a cinnamic acid structure containing an azobenzene-containing group, cinnamic acid or a derivative thereof as a basic skeleton, a chalcone-containing group containing a derivative as a basic skeleton, Containing structure containing a benzophenone-containing group containing a derivative as a basic skeleton, a coumarin-containing group containing a coumarin or a derivative thereof as a basic skeleton, a polyimide or a derivative thereof as a basic skeleton, and the like.

When the polyamic acid as the polymer (A) has a photo-orientable group as a photo-orientable structure, the photo-orientable group is preferably a group having a cinnamic acid structure in that it has a high aligning ability. Such a polymer (A) is preferably a method of reacting the above-exemplified tetracarboxylic acid dianhydride with a diamine containing a diamine having a cinnamic acid structure, since it is easy to introduce the polymer (A) into a polymer. Specific examples of the diamine having a cinnamic acid structure include, for example, the following formulas (R1) to (R7):

(Wherein (R1) ~ (R5) of, ^Ⅰ R is a fluoroalkyl group of 3 to 12 carbon atoms or an alkyl group having a carbon number of 3-12, a is an integer of 1 to 6.)

And the like.

Examples of the alkyl group having 3 to 12 carbon atoms for R ¹ in the formulas (R1) to (R5) include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, A decyl group, and a dodecyl group. These groups may be either linear or branched, but are preferably linear. Examples of the fluoroalkyl group having 3 to 12 carbon atoms include groups obtained by substituting at least one hydrogen atom of the above-exemplified alkyl group with a fluorine atom. a is preferably an integer of 1 to 3, more preferably 1 or 2. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups.

In the case where the polyamic acid as the polymer (A) has a decomposition type photo-aligning moiety as the photo-orientable structure, preferred examples of the polymer (A) include polymers having a bicyclo [2.2.2] octene skeleton, A polymer having a backbone structure, and a polymer having a backbone structure represented by the following formula (b):

(Wherein, in the formula (b), X ² is a sulfur atom or an oxygen atom; "*" each represents a bond; provided that at least one of the two "*"

And a polymer having a structure represented by the following formula in its main chain.

The polymer having the decomposition type photo-aligning moiety can be obtained, for example, by reacting tetracarboxylic acid dianhydride with a diamine in the presence of at least a part of tetracarboxylic dianhydrides used in the reaction, for example, Tetracarboxylic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, or a tetracarboxylic acid dianhydride having the structure represented by the above formula (b); As at least a part of diamines used in the reaction, for example, the following formula (c):

(In the formula (c), A ¹ is a single bond or a divalent organic group, B ¹ is a divalent organic group, R ¹⁰ is a substituent and n 1 is an integer of 0 to 4)

A method using a compound having a cinnamic acid structure or a diamine having a structure represented by the above formula (b); And the like.

Examples of the tetracarboxylic acid dianhydride having the structure represented by the above formula (b) include the following formulas (b-1-1) to (b-1-6):

And the like.

Examples of the compound represented by the formula (c) include compounds represented by the following formulas (b-2-1) to (b-2-6):

And the like. Examples of the diamine having the structure represented by the above formula (b) include compounds represented by each of the above formulas (b-2-1) to (b-2-5), 4-aminophenyl- Aminophenyl-4'-aminobenzoate, 3,3 ', 5,5'-tetramethyl-4-aminophenyl-4'-aminobenzoate, 3-methyl Aminophenyl-4'-aminobenzoate, the following formulas (b-2-8) to (b-2-14):

And the like.

When the liquid crystal aligning ability is imparted to the coating film by the photo alignment method, the ratio of the polymer (A) having a photo-orientable structure is preferably set such that the proportion of the polymer (A) used in the synthesis of the polyamic acid of the present invention By weight, preferably 10% by weight or more, more preferably 30 to 100% by weight, and still more preferably 50 to 100% by weight.

[Molecular Weight Regulator]

In the synthesis of the polyamic acid, the endmodified polymer may be synthesized by using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and the diamine as described above. By using such a polymer having a terminal modification type, the coating property (printing property) of the liquid crystal aligning agent can be further improved without impairing the effect of the present invention.

Examples of the molecular weight regulator include acid anhydride, monoamine compound, monoisocyanate compound, and the like. Specific examples of such acid anhydrides include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n- ; As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and the like; Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and diamine to be used.

<Synthesis of polyamic acid>

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid in the present invention is such that the ratio of the acid anhydride group of the tetracarboxylic acid dianhydride to the equivalent of 0.2 to 2 equivalents , More preferably from 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature is preferably -20 ° C to 150 ° C, more preferably 0 ° C to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like.

Specific examples of these organic solvents include, but are not limited to, the aprotic polar solvents such as N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, Pyrrolidone, N-pentyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-methoxypropyl- N-dimethylacetamide, N, N-dimethylformamide, 3-butoxy-N, N-dimethylpropionamide, 3-methoxy- Butoxy-N-isopropyl-propionamide, dimethylsulfoxide, gamma -butyrolactone, tetrabutylammonium chloride, tetrabutylammonium chloride, Methyl urea, hexamethylphosphoric triamide and the like; As the phenolic solvent, for example, phenol, m-cresol, xylenol, halogenated phenol and the like;

Examples of the alcohol include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, diacetone alcohol and the like; Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetylacetone and the like; Examples of the esters include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, acetoacetic acid ethyl, methylmethoxypropionate, ethylethoxypropionate, diethyl oxalate, diethyl malonate, Isoamyl propionate, isoamyl isobutyrate, ethylene glycol diacetate, propylene glycol diacetate and the like;

Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether , Ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Tetrahydrofuran, diisopropyl ether, di-sec-butyl ether, di-sec-pentyl ether, diisopentyl ether and the like;

As the halogenated hydrocarbon, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like; Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene and the like; Respectively.

Among these organic solvents, at least one selected from the group consisting of an aprotic polar solvent and a phenol solvent (A solvent), or at least one selected from an A solvent and at least one selected from an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon And a hydrocarbon group (B solvent) are preferably used. In the latter case, the use ratio of the B solvent is preferably 50% by weight or less, more preferably 40% by weight or less, and further preferably 30% by weight or less, based on the total amount of the A solvent and the B solvent.

The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50 wt% with respect to the total amount (a + b) of the reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid is purified, . When the polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution may be directly supplied to the dehydration ring-closing reaction. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring- May be purified and then subjected to a dehydration ring-closing reaction. The polyamic acid can be isolated and purified by a known method.

<Synthesis of polyimide and polyimide>

The polyimide contained in the liquid crystal aligning agent of the present invention can be obtained by imidizing the polyamic acid synthesized as described above by dehydration ring closure.

The polyimide may be a completely imidized product obtained by dehydrating and ring closure of all of the arboric acid structure possessed by the polyamic acid which is a precursor thereof and dehydrating and ring closure only a part of the arid acid structure to obtain a partial imide cargo . The imide ratio of the polyimide in the present invention is preferably 30% or more, more preferably 40 to 99%, and still more preferably 50 to 99%. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating the polyamic acid, or a method of dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and optionally heating . Of these, the latter method is preferable.

In the method of adding the dehydrating agent and the dehydrating ring-closing catalyst to the solution of the polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyimide is obtained. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent, or may be supplied to the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, Or may be added to the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. These purification operations can be carried out according to a known method.

<Polyamic acid ester>

The polyamic acid ester contained in the liquid crystal aligning agent of the present invention may be synthesized by, for example, a method of synthesizing [I] a polyamic acid obtained by the above-mentioned synthetic reaction by reacting a hydroxyl group-containing compound, a halide, Ⅱ] tetracarboxylic acid diester with diamine, and [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

Examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; Phenols such as phenol and cresol, and the like. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, and 1,1,1-trifluoro-2-iodoethane. Examples of the epoxy group- , For example, propylene oxide, and the like. The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring opening the tetracarboxylic acid dianhydride exemplified in the synthesis of the above polyamic acid by using the above-mentioned alcohols. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester thus obtained with a suitable chlorinating agent such as thionyl chloride. As the diamines used in the methods [II] and [III], diamines and the like exemplified for the synthesis of the polyamic acid can be used. In addition, the polyamic acid ester may have only an acid ester structure, or may be a partial ester ester in which an acid structure and an acid ester structure coexist.

&Lt; Solution viscosity and weight average molecular weight &gt;

The polyamic acid and the polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s and a solution viscosity of 15 to 500 mPa · s Do. The solution viscosity (mPa 占 퐏) of the polymer is preferably 10 weight% or less by weight, which is prepared by using a good solvent of the polymer (for example,? -Butyrolactone, N-methyl- % Of the polymer solution at 25 占 폚 using an E-type rotational viscometer.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyamic acid and polyimide contained in the liquid crystal aligning agent of the present invention is preferably 500 to 100,000, more preferably 1,000 to 50,000 desirable.

&Lt; Polyorganosiloxane &gt;

The polyorganosiloxane in the present invention can be obtained, for example, by hydrolyzing or hydrolyzing / condensing a hydrolyzable silane compound, preferably in the presence of an appropriate organic solvent, water and a catalyst.

Examples of the hydrolyzable silane compound used for the synthesis of the polyorganosiloxane include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, methyldichlorosilane , Methyldimethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Ethoxysilane, allyltrimethoxysilane, allyltriethoxysilane;

Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethyldimethylmethoxysilane, 4-glycidoxypropyldimethylethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, Glycidoxybutyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyldimethyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (Meth) acrylic acid (3-ethyloxetan-3-yl) methyl, (meth) acrylic acid (3-methyloxetan-3-yl) methyl;

Acrylates such as 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- Acrylates such as 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltrichlorosilane, 4- (meth) acryloxybutyltrimethoxysilane , 4- (meth) acryloxybutyltriethoxysilane, and the like. In addition, "(meth) acryloxy" is meant to include "acryloxy" and "methacryloxy".

Examples of the organic solvent that can be used in the synthesis of the polyorganosiloxane include hydrocarbons, ketones, esters, ethers, and alcohols. Examples of the hydrocarbons include toluene, xylene and the like; Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and the like; Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, it is preferable to use a water-insoluble organic solvent. These organic solvents may be used singly or in combination of two or more kinds.

The amount of the organic solvent used when synthesizing the polyorganosiloxane is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound. The amount of water used to produce the polyorganosiloxane is preferably 0.5 to 100 moles, more preferably 1 to 30 moles per 1 mole of the total silane compound to be used.

Examples of the catalyst that can be used in the synthesis of the polyorganosiloxane include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid and the like; Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like; Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole, triethylamine, tri-n-propylamine, tri- Tertiary organic amines such as butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, quaternary organic amines such as tetramethylammonium hydroxide, and the like; Respectively.

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used differs depending on the kind of the organic base, the reaction conditions such as the temperature and the like, and should be appropriately set. For example, it is preferably 0.01 to 3 moles per mole of the total silane compound, It is 1 mol.

The hydrolysis or hydrolysis / condensation reaction in the production of the polyorganosiloxane may be carried out by dissolving one or two or more kinds of hydrolyzable silane compounds in an organic solvent, mixing the resulting solution with an organic base and water, For example, by heating with an oil bath or the like.

In the hydrolysis and condensation reaction, the heating temperature is preferably 130 DEG C or lower, more preferably 40 DEG C to 100 DEG C, preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During the heating, the mixed solution may be stirred or refluxed.

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this washing, it is preferable that the cleaning is performed by using water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 wt%, from the viewpoint of facilitating the cleaning operation. The washing is carried out until the water layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain the objective polyorganosiloxane . As the polyorganosiloxane in the present invention, a commercially available product may be used.

As the polyorganosiloxane to be contained in the liquid crystal aligning agent of the present invention, the reactive polyorganosiloxane obtained by the condensation reaction is further reacted with a reactive compound having a specific structure, and the resulting polyorganosiloxane A polyorganosiloxane having a specific structure derived from a reactive compound in a side chain) may be used. Examples of the reactive polyorganosiloxane include a polyorganosiloxane having an epoxy group, an unsaturated double bond, a mercapto group, an amino group, and the like. Examples of the reactive compound include compounds having a structure in which a compound having a long-chain alkyl group, two or more rings (e.g., a benzene ring or a cyclohexane ring) are linked, a compound having a steroid skeleton, a compound having an unsaturated double bond , Compounds having photo-orientable groups, and the like.

The reaction of the reactive polyorganosiloxane with the reactive compound can be carried out according to a conventional method of organic chemistry. For example, by using a polyorganosiloxane having an epoxy group in its side chain as a reactive polyorganosiloxane and a carbonic acid having a specific structure as a reactive compound, a polyorganosiloxane having the specific structure in its side chain Can be obtained. Further, by using a polyorganosiloxane having an unsaturated double bond as a reactive polyorganosiloxane and a compound having a specific structure with a mercapto group or an amino group as a reactive compound, a polyorganosiloxane having a specific structure in the side chain To obtain a siloxane.

In the polyorganosiloxane of the present invention, the weight average molecular weight in terms of polystyrene measured by GPC is preferably 500 to 100,000, more preferably 1,000 to 30,000, and even more preferably 1,000 to 20,000 .

The liquid crystal aligning agent of the present invention can be obtained by polymerizing, as the polymer (A), a polymer selected from the group consisting of the above-mentioned polyamic acid, polyimide, polyamic acid ester and polyorganosiloxane either singly or in combination . The content ratio of each polymer to the total amount of the polymer (A) in the liquid crystal aligning agent can be appropriately selected depending on the use and the environment to be used, but from the viewpoint of obtaining the effect of the present invention more appropriately, It is preferable to include at least one of polyamic acid and polyimide. In this case, the total content of the polyamic acid and the polyimide is preferably 1 to 100 wt%, more preferably 5 to 100 wt% with respect to the total amount of the polymer (A) contained in the liquid crystal aligning agent .

<Solvent>

The liquid crystal aligning agent of the present invention is prepared as a liquid composition in which a polymer component and other components to be blended as required are dispersed or dissolved in an organic solvent. The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent which comprises, as a solvent component, at least one compound selected from the group consisting of the compound represented by the formula (1), the compound represented by the formula (2) and 1,3-dimethyl-2-imidazolidinone And a second solvent which is at least one selected from the group consisting of the compound represented by the formula (3), the compound represented by the formula (4) and the compound represented by the formula (5).

[First solvent]

(Compound represented by the formula (1)

As the monovalent hydrocarbon group of 2 to 5 carbon atoms for R ¹ in the first solvent, the compound represented by the formula (1) is preferably a chain hydrocarbon, and examples thereof include an alkyl group having 2 to 5 carbon atoms, an alkenyl group, And an alkynyl group. Examples of the monovalent group having "-O-" among the carbon-carbon bonds in the hydrocarbon group include an alkoxyalkyl group having 2 to 5 carbon atoms.

Specific examples thereof include an alkyl group having 2 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group and a pentyl group; Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 3-butenyl group and the like; Examples of the alkynyl group having 2 to 5 carbon atoms include an ethynyl group, a 2-propynyl group, a 2-butynyl group and the like; Examples of the alkoxyalkyl group having 2 to 5 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, an ethoxymethyl group, and an ethoxyethyl group; And they may be linear or branched. R ¹ is preferably an alkyl group or an alkoxyalkyl group having 2 to 5 carbon atoms among the above.

Specific examples of the compound represented by the formula (1) include N-ethyl-2-pyrrolidone, N- (n-propyl) -2-pyrrolidone, N- Pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (t- Pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone and the like. Among them, preferred are N-ethyl-2-pyrrolidone, N- (n-pentyl) -2-pyrrolidone, N- (t- Rollidon can be particularly preferably used. The compounds represented by the above formula (1) can be used singly or in combination of two or more of these exemplified compounds.

(Compound represented by the formula (2)

Examples of the monovalent hydrocarbon group of 1 to 6 carbon atoms represented by R ² and R ³ in the first solvent include a straight chain hydrocarbon group of 1 to 6 carbon atoms and a straight chain hydrocarbon group of 3 to 6 carbon atoms, An alicyclic hydrocarbon group, and an aromatic hydrocarbon group having 5 or 6 carbon atoms. Examples of the monovalent group having "-O-" among the carbon-carbon bonds of the hydrocarbon group include an alkoxyalkyl group having 2 to 6 carbon atoms.

Specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl and the like, which may be linear or branched. Examples of the alicyclic hydrocarbon group having 3 to 6 carbon atoms include a cyclopentyl group, a cyclohexyl group and the like; Examples of the aromatic hydrocarbon group include a phenyl group and the like; Examples of the alkoxyalkyl group having 2 to 6 carbon atoms include a compound represented by R ¹ ; Respectively. R ² and R ³ in the formula (2) may be the same or different from each other. R ² and R ³ may be bonded to each other to form a ring together with the nitrogen atom to which R ² and R ³ bond. Examples of the ring formed by bonding R ² and R ³ to each other include a pyrrolidine ring and a piperidine ring, and these rings may be bonded with a monovalent chain hydrocarbon group such as a methyl group.

R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms for R ⁴ include the groups exemplified for the alkyl groups having 1 to 6 carbon atoms for R ² and R ³ above. Preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the compound represented by the formula (2) include 3-butoxy-N, N-dimethylpropionamide, 3-methoxy-N, N-dimethylpropionamide, 3-hexyloxy- Isopropyl-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and the like. The compounds represented by the formula (2) may be used singly or in combination of two or more.

The first solvent is preferably at least one compound selected from the group consisting of the compound represented by the formula (1) and the 1,3-dimethyl-2-imidazolidinone, and the compound represented by the formula (1) More preferably at least one member selected from the group consisting of a compound wherein R ¹ is an alkyl group or an alkoxyalkyl group having 2 to 5 carbon atoms and 1,3-dimethyl-2-imidazolidinone.

The amount of the first solvent to be used is preferably 5% by weight or more based on the total amount of the solvent contained in the liquid crystal aligning agent from the viewpoint of suitably suppressing the precipitation of the polymer component on the printing machine at the time of printing on the substrate , And more preferably 10 wt% or more. The upper limit of the amount to be used is not particularly limited, but is preferably 95% by weight or less, more preferably 90% by weight or less based on the total amount of the solvent contained in the liquid crystal aligning agent. As the first solvent, those described above may be used singly or in combination of two or more kinds.

The first solvent is soluble in the polymer (A) and has a boiling point of suitably high boiling point. Therefore, when the first solvent is used as the solvent component of the liquid crystal aligning agent, the volatilization of the solvent from the printing plate during printing on the substrate of the liquid crystal aligning agent is suppressed and the precipitation of the polymer component can be suppressed. As a result, (In particular, continuous printing property) can be improved. Further, since the boiling point of the solvent is not excessively high, the amount of the solvent remaining in the coating film after the preliminary heating can be reduced in the case of preheating (prebaking) after printing. As a result, it is possible to suppress the adhesion of dust to the surface of the coating film after the preheating, thereby making it possible to suppress the yield reduction of the product.

[Second solvent]

(Compound represented by the formula (3)

Examples of the hydrocarbon group having 1 to 3 carbon atoms in R ⁵ and R ⁷ with respect to the compound represented by the formula (3) in the second solvent include methyl, ethyl, n-propyl and isopropyl groups An alkyl group having 1 to 3 carbon atoms; A monovalent unsaturated hydrocarbon group having 2 or 3 carbon atoms such as a vinyl group and an allyl group; And the like. Among them, R ⁵ and R ⁷ are preferably a methyl group or an ethyl group. R ⁵ and R ⁷ may be the same or different.

Examples of the alkanediyl group having 2 to 5 carbon atoms for R ⁶ include an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,3-diyl group, A 4-diyl group, and a pentane-1,5-diyl group.

Preferable specific examples of the compound represented by the formula (3) include alkylene glycol diacetates such as ethylene glycol diacetate and propylene glycol diacetate. Of these, propylene glycol diacetate is preferably used. As the compound represented by the formula (3), the above-described compounds may be used singly or in combination of two or more.

(Compound represented by the formula (4)

The compound represented by the formula (4) has a structure in which two R &lt; ⁸ &gt; each are bonded to one oxygen atom. As such a compound, examples of the compound in which R ⁸ is a monovalent group having one "-O-" among the carbon-carbon bonds of the alkyl group having 3 to 5 carbon atoms include diethylene glycol dimethyl ether, diethylene glycol Diethyl ether and the like; As specific examples of the compound in which R ⁸ is a monovalent group in which the hydrogen atom of the alkyl group having 3 to 5 carbon atoms is substituted with a hydroxyl group, for example, dipropylene glycol and the like; Specific examples of the compound in which R ⁸ is a branched alkyl group include diisopropyl ether, diisopentyl ether, di-sec-butyl ether, di-sec-pentyl ether and the like; Respectively. Among the compounds represented by the formula (4), among them, at least one of diethylene glycol diethyl ether and diisopentyl ether is preferable. As the compound represented by the formula (4), the above-described compounds may be used singly or in combination of two or more.

(Compound represented by the formula (5)

In the above formula (5), X ¹ is preferably ^a group "-C (OH) R ^a -" and more preferably a group "-C (OH) (CH ₃ ) -". The alkyl group having 1 to 4 carbon atoms represented by R ⁹ may be linear or branched, and is preferably a methyl group or an ethyl group.

Specific preferred examples of the compound represented by the formula (5) include diacetone alcohol, acetylacetone, and ethyl acetoacetate, and diacetone alcohol is particularly preferably used. As the compound represented by the formula (5), the above-described compounds may be used singly or in combination of two or more.

The second solvent is more preferably at least one selected from the group consisting of the compound represented by the formula (3) and the compound represented by the formula (5), more preferably the compound represented by the formula (5) Do.

The amount of the second solvent to be used is preferably from 1 to 70% by weight, based on the total amount of the solvent contained in the liquid crystal aligning agent, from the standpoint of improving the coatability (printing property) to the substrate while suppressing the precipitation of the polymer , More preferably 3 to 60 wt%. As the second solvent, those described above can be used singly or in combination of two or more kinds.

The ratio of the first solvent to the second solvent is preferably 0.03 times (weight) or more in terms of the amount of the second solvent used relative to the amount of the first solvent used from the viewpoint of improving the applicability to the substrate , And 0.05 times (weight) or more. From the viewpoint of suppressing the precipitation of the polymer, it is preferably 2.5 times (weight) or less, more preferably 2.0 times (weight) or less.

Further, it is difficult for the second solvent to swell the APR (registered trademark, hereinafter the same) resin which is generally used as a printing plate of a printing machine used for applying a liquid crystal aligning agent on a substrate, It can be deduced that the printing property (particularly, the continuous printing property) can be improved by the difficulty of intrusion.

[Third solvent]

As the solvent contained in the liquid crystal aligning agent of the present invention, other solvents (third solvent) other than the above-mentioned first solvent and second solvent may be used. Examples of the third solvent include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, Methyl ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol mono (diethylene glycol monoethyl ether) Ethyl ether acetate, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, ethylene carbonate , Propylene carbonate, and the like. The above-mentioned third solvent may be used singly or in combination of two or more kinds.

The content of the third solvent is preferably 80% by weight or less, more preferably 70% by weight or less, further preferably 50% by weight or less based on the total amount of the solvent contained in the liquid crystal aligning agent, Particularly preferably 30% by weight or less.

<Other components>

The liquid crystal aligning agent of the present invention contains such a polymer and a solvent as described above, but may contain other components as required. Such other components include, for example, other polymers other than the above-mentioned polymer, a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), and a functional silane compound.

[Other Polymers]

The other polymer may be used for improving solution characteristics and electrical properties. Examples of such other polymers include polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates. When the other polymer is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 50% by weight or less, more preferably 0.1 to 40% by weight, more preferably 0.1 to 30% by weight based on the total amount of the polymer in the composition. Is more preferable.

[Epoxy group-containing compound]

The epoxy group-containing compound can be used for improving the adhesion to the substrate surface and electric characteristics in the liquid crystal alignment film. Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Diallyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromonopentyl glycol di N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N-diglycidyl-cyclohexylamine, and the like.

When these epoxy compounds are added to the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight per 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent.

[Functional silane compound]

The functional silane compound can be used for the purpose of improving the printing property of the liquid crystal aligning agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxysilylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-tri Methoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, Trimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like, Can.

When these functional silane compounds are added to the liquid crystal aligning agent, the mixing ratio thereof is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight based on 100 parts by weight of the total of the polymers.

As other components contained in the liquid crystal aligning agent, a compound having at least one oxetanyl group in the molecule, an antioxidant, etc. may be used.

The solid concentration of the liquid crystal aligning agent of the present invention (the ratio of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent other than the solvent of the solvent) is appropriately selected in consideration of viscosity, volatility, etc., Is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and preferably is heated to form a coating film which becomes a liquid crystal alignment film or a liquid crystal alignment film. When the solid concentration is less than 1 wt% , The film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, so that a good liquid crystal alignment film can not be obtained and the viscosity of the liquid crystal aligning agent is increased and the coating property is poor.

A particularly preferable range of the solid concentration is different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5 wt%. In the case of the offset printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9 wt% and the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and the solution viscosity is in the range of 3 to 15 mPa · s. The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚.

<Liquid Crystal Alignment Film and Liquid Crystal Display Device>

The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent prepared as described above. Further, the liquid crystal display element of the present invention comprises a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention. The driving mode to which the liquid crystal display element of the present invention is applied is not particularly limited and can be applied to various driving modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type and the like.

The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3). In the step (1), the substrate to be used differs depending on the desired drive mode. Steps (2) and (3) are common to each drive mode.

[Process (1): Formation of coating film]

First, the liquid crystal aligning agent of the present invention is coated on a substrate, and then a coated film is formed on the substrate by heating the coated surface.

(1-1) In the case of producing a TN type, STN type, VA type or MVA type liquid crystal display device, two substrates on which a patterned transparent conductive film is formed are made into a pair, , The liquid crystal aligning agent of the present invention is preferably applied by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method, respectively. As the application method of the liquid crystal aligning agent, the liquid crystal aligning agent of the present invention is preferably applicable to the offset printing method among these because it has a property that makes it difficult to swell the APR plate. Examples of the substrate include glass such as float glass and soda glass; A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. As the transparent conductive film to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) . In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photoetching after forming a transparent conductive film without a pattern, a method of using a mask having a desired pattern in forming a transparent conductive film, have. When applying the liquid crystal aligning agent, a functional silane compound, a functional titanium compound or the like is preferably added to the surface of the substrate on which the coating film should be formed in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film The pre-treatment for pre-coating may be carried out.

After application of the liquid crystal aligning agent, preheating (prebaking) is preferably performed for the purpose of preventing the flow of the liquid of the applied aligning agent or the like. The prebaking temperature is preferably 30 to 200 캜, more preferably 40 to 150 캜, particularly preferably 40 to 100 캜. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, the solvent is completely removed, and a post-baking step is carried out for the purpose of thermally modifying the acid structure present in the polymer as required. The firing (post-baking) temperature is preferably 80 to 300 占 폚, more preferably 120 to 250 占 폚. The post baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. In this way, the film thickness of the film to be formed is preferably 0.001 to 1 占 퐉, and more preferably 0.005 to 0.5 占 퐉.

(1-2) In the case of manufacturing an IPS or FFS type liquid crystal display device, the electrode formed surface of the substrate on which the electrode is formed, which is made of the transparent conductive film or the metal film patterned in the comb shape, The liquid crystal aligning agent of the present invention is applied to one side of the substrate, and then each coated side is heated to form a coated film. The material, the coating method, the heating conditions after coating, the method of patterning the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferable film thickness of the coating film to be formed are the same as those in the above (1-1) . As the metal film, for example, a film made of a metal such as chromium can be used.

In any of the cases (1-1) and (1-2), a coating film to be an alignment film is formed by applying a liquid crystal aligning agent on a substrate and then removing the organic solvent. At this time, when the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid or an imidized polymer having an imidazole ring structure and an arboric acid structure, the dehydration ring-closure reaction is further advanced by further heating after forming the coating film, Or may be a coated film.

[Process (2): Orientation-imparting treatment]

Subsequently, a coating film formed on the substrate is subjected to rubbing treatment or light irradiation treatment, if necessary, to impart the liquid crystal aligning ability to the coating film.

First, when a TN type, an STN type, an IPS type or an FFS type liquid crystal display device is manufactured for the rubbing treatment, the coating film formed in the above step (1) is formed into a film made of a fiber such as nylon, rayon, Rubbing treatment is performed in which the cloth is wiped in a predetermined direction with a roll. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. On the other hand, in the case of producing a VA type or MVA type liquid crystal display device, the coating film formed in the above step (1) can be directly used as a liquid crystal alignment film, but the coating film may be rubbed.

In addition, it is also possible to treat the liquid crystal alignment film after the rubbing treatment by changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet rays or by forming a resist film on a part of the surface of the liquid crystal alignment film The rubbing treatment may be performed after removing the resist film after performing the rubbing treatment in a direction different from the rubbing treatment of the liquid crystal alignment film. In this case, it is possible to improve the visual field characteristic of the obtained liquid crystal display element.

In the case of the light irradiation treatment (photo alignment method), polarized or non-polarized radiation is irradiated to the coated film surface on the substrate after formation of the coated film to give the liquid crystal alignment capability to the coated film. As the radiation, for example, ultraviolet rays or visible rays including light having a wavelength of 150 to 800 nm can be used. Among them, ultraviolet rays including light having a wavelength of 300 nm to 400 nm are preferable. When the radiation to be used is polarized (linearly polarized light or partial polarized light), the light irradiation direction may be vertical to the coated film surface or may be oblique to give a pretilt angle. On the other hand, in the case of irradiating non-polarized radiation, it is necessary to conduct light irradiation from an oblique direction with respect to the coated film surface.

As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser can be used. The ultraviolet ray in the above-mentioned preferable wavelength range can be obtained by a means for using a light source in combination with, for example, a filter or a diffraction grating. The irradiation dose of the radiation is preferably 1 J / m 2 or more and less than 15,000 J / m 2, and more preferably 10 J / m 2 or more and 10,000 J / m 2 or less.

[Process (3): Construction of liquid crystal cell]

Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and the liquid crystal is arranged between the two substrates arranged opposite to each other to manufacture a liquid crystal cell. To produce a liquid crystal cell, for example, the following two methods can be mentioned.

The first method is a conventionally known method. First, two substrates are opposed to each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded to each other using a sealant. After the liquid crystal is filled and filled in the cell gap, the liquid crystal cell can be manufactured by sealing the injection port. The second method is a so-called ODF (One Drop FIll) method. For example, an ultraviolet curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and further liquid crystal is dropped to a predetermined number of places on the surface of the liquid crystal alignment film, The liquid crystal cell can be manufactured by joining the other substrate so that the alignment film is opposed to the substrate, spreading the liquid crystal on the entire surface of the substrate, and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealing agent. Regardless of the method, the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used is isotropic, and then gradually cooled to room temperature to remove the flow orientation at the time of filling the liquid crystal desirable.

As the sealing agent, for example, an epoxy resin containing a curing agent and an aluminum oxide sphere as a spacer can be used.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Of these, nematic liquid crystals are preferable, and examples thereof include a cypher base liquid crystal, an agar watch liquid crystal, a biphenyl liquid crystal, a phenyl cyclohexane liquid crystal, , Terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, quaternary type liquid crystals and the like. Further, to these liquid crystals, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate and cholesteryl carbonate; Chiral agents such as those sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate, or the like may be added and used.

The liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called an "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate comprising a H film itself have.

When the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other such that the rubbing directions of the coating films are at a predetermined angle, for example, orthogonal or anti-parallel to each other. When the coating film is irradiated with light, if the liquid crystal alignment film is horizontally oriented, the angle formed by the polarization direction of the irradiated linear polarized radiation and the angle between the respective substrates and the polarizing plate in the two substrates on which the liquid crystal alignment film is formed A liquid crystal display element having a TN type or STN type liquid crystal cell can be obtained. On the other hand, when the liquid crystal alignment film is vertically aligned, the cells are configured so that the directions of the easy axis in the two substrates on which the liquid crystal alignment film is formed are parallel, and the polarizing plate is polarized at 45 degrees So that a liquid crystal display element having a vertically aligned liquid crystal cell can be obtained.

The liquid crystal display element of the present invention can be effectively applied to various apparatuses and can be used for various applications such as a clock, a portable game, a word processor, a notebook PC, a car navigation system, a camcorder, a PDA, And can be used for display devices such as smart phones, various monitors, and liquid crystal televisions.

(Example)

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

The solution viscosity, the imidization ratio, the weight average molecular weight, and the epoxy equivalent of each polymer solution in the synthesis examples were measured by the following methods.

[Solution viscosity of polymer solution]

The solution viscosity (mPa 占 퐏) of the polymer solution was measured at 25 占 폚 using an E-type rotational viscometer with respect to the solution adjusted to a polymer concentration of 10% by weight by using a predetermined solvent.

[Imidization Rate of Polyimide]

The polyimide solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidization ratio [%] was determined by the following equation (x): &lt; EMI ID =

Imidization rate [%] = {(1-A ¹ ) / (A ² x?)} 100 ... (x)

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

[Weight average molecular weight of polymer, number average molecular weight]

The weight average molecular weight Mw and the number average molecular weight Mn are polystyrene reduced values measured by gel permeation chromatography under the following conditions.

Column: TSKgelGRCXLII, manufactured by Toso Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

[Epoxy equivalent]

The epoxy equivalent was measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

&Lt; Synthesis (1) of polymer (A) &gt;

Synthesis Example 1: Synthesis of polyimide (PI-1)

(0.1 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) as tetracarboxylic dianhydride, 8.6 g (0.08 mole) of p-phenylenediamine (PDA) (0.02 mole) of cholestanyl diaminobenzoic acid (HCDA) was dissolved in 166 g of N-methyl-2-pyrrolidone (NMP) and the reaction was carried out at 60 DEG C for 6 hours to obtain a polyamic acid solution containing 20 wt% Was obtained. A small amount of the obtained polyamic acid solution was collected, and NMP was added thereto to give a solution viscosity of 90 mPa · s as a solution having a polyamic acid concentration of 10% by weight.

Next, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 7 wt%, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new NMP (pyridine and anhydrous acetic acid used in the dehydration ring closure reaction were removed out of the system by this operation; 1) was obtained in an amount of 26% by weight. A small amount of the obtained polyimide solution was collected, and NMP was added thereto to give a solution viscosity of 45 mPa · s as a solution having a polyimide concentration of 10% by weight. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyimide (PI-1).

[Synthesis Example 2: Synthesis of polyimide (PI-2)] [

(0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, 5.2 g (0.01 mol) of HCDA and 4.0 g (0.02 mol) of 4,4'-diaminodiphenylmethane ) Was dissolved in 157 g of NMP, and the reaction was carried out at 60 DEG C for 6 hours to obtain a solution containing 20 wt% of polyamic acid. A small amount of the obtained polyamic acid solution was collected and NMP was added thereto, and the solution viscosity was measured as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 110 mPa · s.

Subsequently, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 7 wt%, and 16.6 g of pyridine and 21.4 g of acetic anhydride were added, followed by dehydration ring closure reaction at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a fresh NMP solvent to obtain a solution containing 26% by weight of polyimide (PI-2) having an imidization rate of about 82%. A small amount of the obtained polyimide solution was collected, and NMP was added thereto to give a solution viscosity of 62 mPa · s as a solution having a polyimide concentration of 10% by weight. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyimide (PI-2).

[Synthesis Example 3: Synthesis of polyimide (PI-3)] [

24.9 g (0.10 mol) of 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4, 6: 8-2 anhydride (BODA) as tetracarboxylic acid dianhydride, 8.6 g (0.08 mole) of HCDA and 10.4 g (0.02 mole) of HCDA were dissolved in 176 g of NMP and reacted at 60 占 폚 for 6 hours to obtain a solution containing 20 mass% of polyamic acid. A small amount of the obtained polyamic acid solution was collected, and NMP was added thereto to give a solution viscosity of 103 mPa · s as a solution having a polyamic acid concentration of 10% by weight.

Next, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 7 wt%, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a fresh NMP solvent to obtain a solution containing 26% by weight of polyimide (PI-3) having an imidization rate of about 71%. A small amount of the obtained polyimide solution was collected, and NMP was added thereto to give a solution viscosity of 57 mPa · s as a solution having a polyimide concentration of 10% by weight. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyimide (PI-3).

[Synthesis Example 4: Synthesis of polyimide (PI-4)] [

As the tetracarboxylic acid dianhydride, 110 g (0.50 mol) of TCA and 1, 3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3- ), 160 g (0.50 mole) of naphtho [1,2-c] furan-1,3-dione, 91 g (0.85 mol) of PDA and 25 g 25 g (0.040 mole) of 3,6-bis (4-aminobenzoyloxy) cholestane and 1.4 g (0.015 mole) of aniline as a monoamine were dissolved in 960 g of NMP and reacted at 60 DEG C for 6 hours To obtain a solution containing polyamic acid. A small amount of the obtained polyamic acid solution was collected and NMP was added thereto, and the solution viscosity was measured as a solution having a polyamic acid concentration of 10 wt%, and the solution viscosity was 60 mPa · s.

Next, 2,700 g of NMP was added to the obtained polyamic acid solution, 390 g of pyridine and 410 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a new? -Butyrolactone solvent to obtain about 2,500 g of a solution containing 15% by weight of polyimide (PI-4) having an imidization rate of about 95%. A small amount of this solution was collected and NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 70 mPa · s. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyimide (PI-4).

[Synthesis Example 5: Synthesis of polyimide (PI-5)] [

(0.1 mole) of TCA as tetracarboxylic dianhydride, 8.6 g (0.08 mole) of PDA as diamine, 2.0 g (0.01 mole) of 4,4'-diaminodiphenylmethane and 2,2'- (0.01 mol) of 4,4'-diaminobiphenyl were dissolved in 324 g of NMP and reacted at 60 ° C for 4 hours to obtain a solution containing 10% by weight of polyamic acid.

Subsequently, 360 g of NMP was added to the obtained polyamic acid solution, 39.5 g of pyridine and 30.6 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring closure reaction, the solvent in the system was replaced with a fresh NMP solvent to obtain a solution containing 10% by weight of polyimide (PI-5) having an imidization rate of about 93%. The solution viscosity of the obtained polyimide solution measured by taking a small amount of the polyimide solution was 30 mPa · s. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyimide (PI-5).

[Synthesis Example 6: Synthesis of polyimide (PI-6)] [

The diamine used was the same as in Synthesis Example 1 except that 0.08 mol of 3,5-diaminobenzoic acid (3,5-DAB) and 0.02 mol of cholestanyloxy-2,4-diaminobenzene (HCODA) Thereby obtaining a polyamic acid solution. A small amount of the obtained polyamic acid solution was collected, and the solution viscosity was measured as a solution having a polyamic acid concentration of 10% by weight by adding NMP, and the solution viscosity was 80 mPa · s.

Then, imidization was carried out in the same manner as in Synthesis Example 1 to obtain a solution containing 26% by weight of a polyimide (PI-6) having an imidization rate of about 65%. A small amount of the obtained polyimide solution was collected, and NMP was added thereto. The solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 40 mPa · s. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyimide (PI-6).

[Synthesis Example 7: Synthesis of polyamic acid (PA-1)] [

200 g (1.0 mole) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride (CB) as tetracarboxylic acid dianhydride, 210 g of 2,2'-dimethyl-4,4'-diaminobiphenyl 1.0 mol) was dissolved in a mixed solvent of 370 g of NMP and 3,300 g of? -Butyrolactone and reacted at 40 占 폚 for 3 hours to obtain a polyamic acid solution having a solid concentration of 10% by weight and a solution viscosity of 160 mPa 占 퐏. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyamic acid (PA-1).

[Synthesis Example 8: Synthesis of polyamic acid (PA-2)] [

Except that tetracarboxylic acid dianhydride to be used was changed to 0.9 mole of pyromellitic dianhydride (PMDA) and 0.1 mole of CB and the diamine was changed to 0.2 mole of PDA and 0.8 mole of 4,4'-diaminodiphenyl ether (DDE) A polyamic acid solution having a solid concentration of 10% by weight and a solution viscosity of 170 mPa · s was obtained in the same manner as in Synthesis Example 7. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain a polyamic acid (PA-2).

Synthesis Example 9: Synthesis of polyamic acid (PA-3)

7 g (0.031 mol) of TCA as a tetracarboxylic acid dianhydride and 13 g of a compound represented by the following formula (R-1) as a diamine (corresponding to 1 mol with respect to 1 mol of TCA) were dissolved in 80 g of NMP, The reaction was carried out for 4 hours to obtain a solution containing 20% by weight of polyamic acid (PA-3). The solution viscosity of this polyamic acid solution was 2,000 mPa · s. The compound represented by the following formula (R-1) was synthesized according to the description in JP-A-2011-100099. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyamic acid (PA-3).

Synthesis Example 10: Synthesis of polyorganosiloxane (APS-1)

100 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser tube And the mixture was mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out at 80 DEG C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with an aqueous 0.2 wt% ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a reactive polyorganosiloxane (EPS-1 ) As a viscous transparent liquid. As a result of ¹ H-NMR analysis of this reactive polyorganosiloxane, it was confirmed that a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm as the theoretical intensity, and no side reaction of the epoxy group occurred during the reaction . The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500 and the epoxy equivalent was 180 g / mol.

Then, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-dodecyloxybenzoic acid as a reactive compound, and 3 g of UCAT 18X Trade name, manufactured by San A Pro Co.) was added, and the reaction was carried out at 100 ° C for 48 hours with stirring. After completion of the reaction, ethyl acetate was added to the reaction mixture, which was then washed with water three times. The organic layer was dried over magnesium sulfate and then the solvent was distilled off to obtain 9.0 g of a liquid crystal aligning polyorganosiloxane (APS-1) . The weight-average molecular weight Mw of the obtained polymer was 9,900.

&Lt; Preparation of liquid crystal aligning agent (1) &gt;

[Example 1]

N-ethyl-2-pyrrolidone (NEP) and propylene glycol diacetate (PGDAc) were added as a solvent to polyimide (PI-1) as the polymer (A) : 50 (weight ratio), and a solid content concentration of 6.5 wt%. This solution was filtered using a filter having a pore diameter of 1 탆 to prepare a liquid crystal aligning agent (S-1). Further, the liquid crystal aligning agent (S-1) is mainly for the production of vertically aligned liquid crystal display elements.

&Lt; Evaluation of swelling property of printing plate &

The swelling easiness (swelling property) of the APR plate was evaluated using the liquid crystal aligning agent (S-1). The APR plate is a resin plate formed by a liquid photosensitive resin in which an ultraviolet ray irradiated portion is cured, and is generally used in a printing plate of a liquid crystal alignment film printing machine. When the liquid crystal aligning agent and the APR plate are brought into contact with each other, the APR plate is hardly swollen, meaning that the liquid crystal aligning agent hardly invades the APR plate during printing and the printing property is good. The swelling property was evaluated by immersing the APR plate in the liquid crystal aligning agent for one day and measuring the weight change of the APR plate before and after the immersion. At this time, when the increase amount of the weight of the APR plate was less than 4%, the APR plate was difficult to swell and the APR plate was easily swelled and evaluated as poor (x) when the increase amount was 4% or more. The evaluation results are shown in Table 1 below.

&Lt; Evaluation of printability &gt;

The printing properties (continuous printing property) in the case where the liquid crystal aligning agent prepared above was continuously printed on the substrate was evaluated. The evaluation was carried out as follows. First, the liquid crystal aligning agent (S-1) prepared was subjected to liquid crystal aligning with an anilox roll using a liquid crystal alignment film printing machine ("S40L-532" type, angstromer manufactured by Nihon Shinsengattsu Co., Ltd.) The dropping amount of the ITO film was printed on the transparent electrode surface of the glass substrate with a transparent electrode on the condition of 20 droplets (about 0.2 g) reciprocating. Printing onto the substrate was performed 20 times while using a new substrate at intervals of one minute.

Subsequently, a liquid crystal aligning agent was dispensed (one way) on the anilox roll at intervals of one minute, and an operation of contacting the anilox roll with the printing plate each time (hereinafter, referred to as ball operation) was repeated 10 times in total Printing on a glass substrate is not performed). In addition, this coarse operation is an operation performed so that the printing of the liquid crystal aligning agent is intentionally performed under a severe condition.

After ten times of operation, the printing was performed using a glass substrate. In this printing, five substrates were placed at intervals of 30 seconds after the blank operation, each substrate after printing was heated (prebaked) at 80 DEG C for 1 minute to remove the solvent, and then heated at 200 DEG C for 10 minutes ) To form a coating film having a film thickness of about 80 nm. The coating film was observed under a microscope with a magnification of 20 times to evaluate the printing property (continuous printing property). In the evaluation, when the precipitation of polymer was not observed from the first printing after the co-operation, the precipitation of the polymer was observed in the continuous printing property "good (O)" and the first printing after the printing operation, When the precipitation of the polymer was not observed during the execution, the continuous printing property &quot; Good &quot; (&quot; DELTA &quot;) and the case in which the precipitation of the polymer was observed even after the printing was repeated five times, . The evaluation results are shown in Table 1 below. In addition, it has been experimentally known that, in a liquid crystal aligning agent having good printability, precipitation of a polymer is lost (lost) while a substrate is continuously fed. Further, the printability of the liquid crystal aligning agent was evaluated in the same manner as above except that the number of times of the ball operation was changed 15 times, 20 times, and 25 times. The evaluation results are also shown in Table 1 below.

The symbols of the solvent composition in Tables 1 and 2 have the following meanings respectively.

a: N-ethyl-2-pyrrolidone

b: N-pentyl-2-pyrrolidone

c: 1,3-dimethyl-2-imidazolidinone

d: Propylene glycol diacetate

e: diacetone alcohol

f: diethylene glycol diethyl ether

g: diisopentyl ether

h:? -butyrolactone

i: propylene carbonate

j: N-methyl-2-pyrrolidone

m: butyl cellosolve

p: propylene glycol monomethyl ether acetate

[Examples 2 to 64 and Comparative Examples 1 to 5]

The liquid crystal aligning agents (S-2) to (S) were obtained in the same manner as in Example 1, except that the polymer (A) used and the kind and composition of the solvent were changed as described in Table 1 or Table 2, -64) and (SR-1) to (SR-5), respectively. In addition, for each of the liquid crystal aligning agents, the swelling property and the printing property of the printing plate were evaluated in the same manner as in Example 1 above. The results are shown in Tables 1 and 2 above. In Table 2, the use ratio (weight ratio) of each polymer with respect to the total amount of 100 parts by weight of the polymer used was also shown in the case of using two kinds of polymers as the polymer (A) (Examples 46 to 64). Of the respective liquid crystal aligning agents, (S-2) to (S-45), (SR-1) to (S-62) is mainly for the production of liquid crystal display devices of the IPS type, (S-64) is mainly for the production of vertically aligned liquid crystal display devices by the photo alignment method, and (S- Of the liquid crystal display device.

[Examples 65 to 70]

(S-65) to (S-70) were obtained in the same manner as in Example 1, except that the polymer (A) used and the kind and composition of the solvent were changed as described in Table 3, respectively Respectively. In addition, for each of the liquid crystal aligning agents, the swelling property and the printing property of the printing plate were evaluated in the same manner as in Example 1 above. The results are shown in Table 3 below. In Table 3, the use ratios (weight ratios) of the respective polymers to 100 parts by weight of the total amount of the polymers used were also shown for Examples 69 and 70 using two polymers as the polymer (A). Of the respective liquid crystal aligning agents, (S-65) to (S-68) are mainly in the vertical alignment type, (S-69) to be.

Among the symbols of the solvent composition in Table 3, the symbols other than those shown in Tables 1 and 2 have the following meanings, respectively.

k: 3-methoxy-N, N-dimethylpropionamide

l: 3-Butoxy-N, N-dimethylpropionamide

As shown in Table 1, Table 2 and Table 3, it was difficult to swell the APR plate in all of the examples. From this point of view, it can be said that the liquid crystal aligning agent of the embodiment can suppress the expansion of the printing plate at the time of printing and uniformly apply the liquid crystal aligning agent to the substrate. The continuous printing property was also good in all of Examples. On the other hand, the liquid crystal aligning agent of the comparative example had a lower continuous printing property than that of the examples. In addition, the degree of swelling of the APR plate was large in Comparative Examples 2, 4 and 5.

&Lt; Synthesis (2) of polymer (A) &gt;

[Synthesis Example 11: Synthesis of polyamic acid (PA-4)] [

2.24 g (0.01 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic acid dianhydride and 2.54 g (0.01 mole) of the compound represented by the above formula (b-2-1) -2-pyrrolidone (NMP), and the mixture was reacted at 40 占 폚 for 3 hours to obtain 31.8 g of a solution containing 15% by weight of polyamic acid (PA-4). The solution viscosity of this polyamic acid solution was 65 mPa · s. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 DEG C for 15 hours under reduced pressure to obtain polyamic acid (PA-4).

Synthesis Example 12: Synthesis of polyamic acid (PA-5)

4.845 g (0.0106 mol) of the compound represented by the above formula (b-1-1) as a tetracarboxylic acid dianhydride and 1.155 g (0.0107 mol) of p-phenylenediamine as a diamine were dissolved in 54 g of NMP, Lt; / RTI &gt; Thus, 59 g of a polyamic acid solution having a solid concentration of 10% and a solution viscosity of 130 mPa · s was obtained. The polyamic acid solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain a polyamic acid (PA-5).

[Synthesis Example 13: Synthesis of polyamic acid (PA-6)] [

19.6 g (0.10 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as tetracarboxylic acid dianhydride and 10.8 g (0.10 mol) of p-phenylenediamine as a diamine were dissolved in 369.6 g of NMP, For 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyamic acid (PA-6).

[Synthesis Example 14: Synthesis of polyimide (PI-7)] [

5.94 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic anhydride, 1.65 g of 3,5-diaminobenzoic acid as a diamine, 1.35 g of cholestanyloxy-2,4-diaminobenzene, 2.51 g of the compound represented by the above formula (D-1-4) and 2.54 g of the compound represented by the following formula (d-1) were dissolved in 56 g of NMP and reacted at 60 ° C for 6 hours to obtain a polyamic acid % Solution. A small amount of this solution was collected and NMP was added to obtain a solution having a polyamic acid concentration of 10% by weight, and the solution viscosity measured at 25 占 폚 was 60 mPa 占 퐏.

Subsequently, 70 g of NMP was added to the obtained polyamic acid solution, 3.15 g of pyridine and 4.06 g of acetic anhydride were added, and the dehydration ring-closure reaction was carried out at 110 DEG C for 4 hours. After the dehydration ring-closure reaction, the solvent in the system was replaced with a fresh NMP solvent to obtain a solution containing 20% by weight of polyimide (PI-7) having an imidization rate of 74%. A small amount of this solution was collected and NMP was added to obtain a solution having a polyimide concentration of 10% by weight. The viscosity of the solution measured at 25 캜 was 55 mPa.. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain polyimide (PI-7).

[Synthesis Example 15: Synthesis of polyamic acid ester (PAE-1)] [

2.68 g (9.50 mmol) of the compound represented by the following formula (t-1) was introduced into a 100 mL four-necked flask equipped with a stirrer, 69.9 g of NMP was added and dissolved by stirring. Then, 0.506 g (5.00 mmol) of triethylamine and 2.58 g (10.0 mmol) of the compound represented by the following formula (d-2) were added and dissolved by stirring. (DMT-MM (15 ± 2 wt% hydrate)) was added to the solution while stirring the solution, (36.0 mmol) of NMP, 12.5 g of NMP was further added, and the mixture was stirred at room temperature for 4 hours to obtain a solution containing polyamic acid ester (PAE-1). The solution viscosity of this polyamic acid ester solution at 25 캜 was 30.9 mPa.. Subsequently, this polyamic acid ester solution was poured into methanol (589 g), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C to obtain a powder of polyamic acid ester (PAE-1). The number average molecular weight of the polyamic acid ester (PAE-1) was Mn = 17,800 and the weight average molecular weight was Mw = 39,700.

[Examples 71 to 75]

(S-71) to (S-75) were obtained in the same manner as in Example 1, except that the polymer (A) used and the kind and composition of the solvent were changed as described in Table 4, respectively Respectively. In addition, for each of the liquid crystal aligning agents, the swelling property and the printing property of the printing plate were evaluated in the same manner as in Example 1 above. The results are shown in Table 4 below.

The symbols of the solvent composition in Table 4 are the same as those in Tables 1, 2 and 3 above.

As shown in Table 4, all of the liquid crystal aligning agents of Examples 71 to 75 were hard to swell the APR plate, and the continuous printing property was good. In addition, even when the number of times of the ball operation was set to 25, precipitation of the polymer was not observed from the first printing after the blank printing, and the continuous printing property was evaluated as &quot; good &quot;.

&Lt; Production of liquid crystal display element and evaluation of liquid crystal alignment property &

[Example 71A]

A glass substrate having a metal electrode made of chromium patterned in a comb shape on one side and an opposing glass substrate on which electrodes are not formed are formed as a pair and a surface having electrodes of the glass substrate and a surface of the opposing glass substrate , And the liquid crystal aligning agent (S-71) prepared in the above were applied using a spinner, respectively. Subsequently, pre-baking was performed on a hot plate at 80 DEG C for 1 minute, and then the coated film was heated at 200 DEG C for 1 hour (post baking) in an oven in which the inside of the tube was replaced with nitrogen to form a coating film having a thickness of 0.1 mu m. Subsequently, a pair of substrates having a liquid crystal alignment film was obtained by irradiating the surfaces of these coating films with a Hg-Xe lamp and a gantry prism, respectively, from a vertical direction of the substrate surface with a polarizing ultraviolet ray of 10,000 J / m 2.

Subsequently, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 占 퐉 was applied to the periphery of the surface having one liquid crystal alignment film among the pair of substrates by screen printing, and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, The substrates were superimposed on each other so that the directions of the substrates when polarized ultraviolet rays were irradiated were opposite to each other, and the adhesive was thermally cured at 150 DEG C for 1 hour. Subsequently, a liquid crystal "MLC-7028" manufactured by Merck Ltd. was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Further, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated at 150 占 폚 and slowly cooled to room temperature. Next, a polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other, and the optical axis of the polarized ultraviolet ray of the liquid crystal alignment film was orthogonal to the projection direction of the substrate surface.

<Evaluation of Liquid Crystal Alignment Property>

With respect to the liquid crystal display device manufactured as described above, the presence or absence of an abnormal (abnormal) domain in the change of light and dark when a voltage of 5 V was applied / released was observed by an optical microscope. In the evaluation, the case where the abnormal domain was not observed was referred to as &quot; good liquid crystal alignability &quot;, and the case where the abnormal domain was observed was regarded as &quot; poor &quot; As a result, an abnormal domain was not observed in this liquid crystal display element, and liquid crystal alignability was good.

[Example 72A]

A liquid crystal display device was produced in the same manner as in Example 71A except that the liquid crystal aligning agent used was changed to (S-72), and the liquid crystal alignability of the liquid crystal display device was evaluated. As a result, an abnormal domain was not observed in this liquid crystal display element, and liquid crystal alignability was good.

[Example 73A]

A liquid crystal display element was produced in the same manner as in Example 71A except that the liquid crystal aligning agent used was changed to (S-73), and the liquid crystal alignability of the liquid crystal display element was evaluated. As a result, an abnormal domain was not observed in this liquid crystal display element, and liquid crystal alignability was good.

Claims (7)

At least one polymer (A) selected from the group consisting of polyamic acid, polyimide, polyamic acid ester and polyorganosiloxane,
A first solvent which is at least one selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2) and 1,3-dimethyl-2-imidazolidinone,
A liquid crystal aligning agent containing a second solvent which is at least one selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (5)

(In the formula (1), R ¹ is a monovalent hydrocarbon group having 2 to 5 carbon atoms or a monovalent group having "-O-" between carbon-carbon bonds in the hydrocarbon group);

(In the formula (2), R ² and R ³ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a monovalent hydrocarbon group having "-O-" between carbon-carbon bonds of the hydrocarbon group R ² and R ³ may combine with each other to form a ring structure; R ⁴ is an alkyl group having 1 to 6 carbon atoms;

(In the formula (3), R ⁵ and R ⁷ are each independently a monovalent hydrocarbon group having 1 to 3 carbon atoms, and R ⁶ is an alkanediyl group having 2 to 5 carbon atoms);

, X ¹ (wherein (5), -C (OH) R ^a - (However, R ^a is an alkyl group having 1 or 2), -CO-, or -COO - * (Note * is with R ⁹ And R ⁹ is an alkyl group having 1 to 4 carbon atoms). The method according to claim 1,
Wherein the content of the second solvent is 1 to 70% by weight of the total solvent contained in the liquid crystal aligning agent. The method according to claim 1,
As the polymer (A), 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6,8-2 anhydride And 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and a diamine and a polyamic acid, a polyimide and a polyamic acid ester obtained by reacting a tetracarboxylic acid dianhydride containing at least one member selected from the group consisting of 1,2,3,4- Wherein the liquid crystal aligning agent comprises at least one member selected from the group consisting of a liquid crystal aligning agent and a liquid crystal aligning agent. The method according to claim 1,
Wherein the polymer (A) is a polymer having a photo-aligning structure. A step of applying the liquid crystal aligning agent according to claim 4 on a substrate to form a coating film,
And irradiating the coating film with light to form a liquid crystal alignment film. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 4. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6.