KR20000035404A - Liquid Crystal Aligning Agent and Liquid Crystal Display Device - Google Patents

Abstract

This invention provides the liquid crystal aligning agent which was excellent in ejection stability, the performance stability of a liquid crystal aligning film, and the stability with respect to an inkjet apparatus.

Moreover, it is related with the liquid crystal aligning agent comprised from the block copolymer which contains the 1st polyimide block and the 2nd polyamic acid block in a molecule | numerator.

Description

Liquid crystal aligning agent and liquid crystal display device {Liquid Crystal Aligning Agent and Liquid Crystal Display Device}

This invention relates to the liquid crystal aligning agent suitable as a formation agent of a liquid crystal aligning film, and the liquid crystal display element using the same. More specifically, the present invention relates to a liquid crystal aligning agent exhibiting excellent coating stability and film thickness uniformity when applied to a substrate by an inkjet printing method by containing a block copolymer of a specific structure, and a liquid crystal display device using the same. .

At present, as a liquid crystal display element, the liquid crystal aligning film which consists of polyimide etc. is formed in the surface of the board | substrate with which the transparent conductive film is provided, it is set as a board | substrate for liquid crystal display elements, and the two sheets are mutually arrange | positioned, for example, positive dielectric TN having a so-called TN (Twisted Nematic) liquid crystal cell in which a nematic liquid crystal layer having anisotropy was formed to form a sandwich cell, and the long axis of the liquid crystal molecules was continuously twisted by 90 degrees from one substrate to the other substrate. Type liquid crystal display elements are known. The so-called TFT liquid crystal panel which operated this TN type liquid crystal display element by TFT drive is widely used instead of the conventional CRT monitor.

The liquid crystal aligning film is controlling the orientation of the liquid crystal in this liquid crystal element. The liquid crystal aligning film apply | coats and bakes the polyamic-acid solution which is a precursor of polyimide, and the polyimide solution soluble in a solvent to a board | substrate by the flexographic printing method.

However, in recent years, the flexographic printing method has a problem of complicated management in printing plate management, such as the need to replace a printing plate depending on a substrate, and the inkjet printing method has attracted attention. The inkjet method has advantages such as easy management of a printing plate, free setting of printing patterns, and a small amount of a liquid crystal aligning agent solution. The cost reduction and yield improvement of a liquid crystal panel are expected.

Although the inkjet printing method has the advantages as described above, a liquid crystal aligning agent suitable for this has not been proposed yet, and in the conventional polyimide and polyamic acid, damage of the inkjet printing machine according to the solvent used, polyimide, polyamic acid solution There was a problem in that it was not possible to maintain a stable printing state in view of the viscosity characteristics and the like.

(1) In the inkjet printing method, it is necessary to eject a liquid crystal aligning agent at a high speed from a fine nozzle, and the viscosity characteristic of a liquid crystal aligning agent becomes an important factor. That is, the resistance at the time of applying a strong external force to a solution is excellent, and fluidity is excellent. Moreover, some organic materials may be used for a nozzle member, and it is also important that a liquid crystal aligning agent does not invade this organic material, and it has strong solubility, such as N-methylpyrrolidone conventionally used as a solvent of a liquid crystal aligning agent. It is necessary to reduce the solvent content. In view of this, it is considered that polyamic acid-based materials having high solubility in various solvents are suitable.

(2) On the other hand, the required performance as a liquid crystal aligning film is becoming more advanced, and high voltage holding ratio, high pretilt angle, low residual DC, etc. could not be satisfied with a single material. As a means for satisfying all of these required performances, a technique is known in which a polyamic acid excellent in low residual DC and a polyimide excellent in high voltage retention and high pretilt angle are mixed.

From the situation of said (1), (2), it is anticipated that the polyamic acid and polyimide composite excellent in fluidity | liquidity and solubility are preferable for inkjet printing. However, studies by the present inventors have found that simply mixing polyamic acid and polyimide results in separation of both by shearing and heat during inkjet printing, resulting in lack of ejection stability and performance stability as a liquid crystal alignment film. lost. Therefore, in the present invention, by combining a polyamic acid and a polyimide containing a specific structure using a method called block copolymerization, the present invention succeeded in producing a liquid crystal aligning agent excellent in ejection stability, performance stability of the liquid crystal alignment film, and stability to an inkjet device. .

That is, an object of the present invention is to provide a novel liquid crystal aligning agent and a liquid crystal display element using the same.

Another object of the present invention is to provide a liquid crystal aligning agent comprising a block copolymer composed of a polyamic acid block and a polyimide block and a liquid crystal display element using the same.

Still another object of the present invention is to provide a liquid crystal aligning agent having excellent ejection stability, performance stability of a liquid crystal alignment film, and stability to an inkjet device, and a liquid crystal display element using the same.

Still other objects and advantages of the present invention will be apparent from the following description.

According to the present invention, the object and the advantages of the present invention is a block copolymer comprising a first polyimide block and a second polyamic acid block in a molecule, wherein the first polyimide block is a repeating unit represented by the following formula (1) And one or more repeating units selected from the group consisting of repeating units represented by the following formula (2), wherein the second polyamic acid block is a repeating unit represented by the following formula (3) and a repeat represented by the following formula (4) It is achieved by the liquid crystal aligning agent characterized by containing the block copolymer which consists of 1 or more types of repeating units chosen from the group which consists of units.

Where

R ¹ , R ⁴ , R ⁶ represent a hydrogen atom or an alkyl group,

R ² , R ³ , R ⁵ , and R ⁷ represent a divalent organic group,

l represents an integer of 1 to 4,

m, n, p and q are positive numbers indicating the number of repeat units.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

The liquid crystal aligning agent of this invention is a agent which has the 1st polyimide block which has a repeating unit represented by the said Formula (1) and / or Formula (2), and the repeating unit represented by the said Formula (3) and / or Formula (4) combined with It consists of the block copolymer which consists of 2 polyamic-acid blocks.

In Formula 1, R ¹ is a hydrogen atom or an alkyl group. An alkyl group may be linear or branched, Preferably, a C1-C30 alkyl group is mentioned. R ² is a divalent organic group, preferably a divalent alicyclic group or a divalent aromatic group. As a bivalent alicyclic group or a bivalent aromatic group, the bivalent residue remove | excluding the amino group from the alicyclic diamine or aromatic diamine mentioned later is mentioned, for example. The repeating unit number n is preferably 3 to 2,000, more preferably 3 to 100.

In Formula 2, R ³ is a divalent organic group, preferably a divalent alicyclic group or a divalent aromatic group. As these specific examples, the same thing as the thing of said R <^2> can be mentioned. The number of repeating units m is preferably 3 to 2,000, more preferably 3 to 100.

In addition, in Formula 3, R ⁶ is a hydrogen atom or an alkyl group. An alkyl group may be linear or branched, Preferably, a C1-C30 alkyl group is mentioned.

R ⁷ is a divalent organic group, preferably a divalent alicyclic group or a divalent aromatic group. As a bivalent alicyclic group or bivalent aromatic group, the bivalent residue remove | excluding the amino group from the alicyclic diamine or aromatic diamine mentioned later is mentioned, for example. The number of repeating units q is preferably 2 to 1,000, more preferably 2 to 100.

In formula (4), R ⁴ is a hydrogen atom or an alkyl group. The alkyl group may be linear or branched, and preferably includes an alkyl group having 1 to 30 carbon atoms.

R ⁵ is a divalent organic group, preferably a divalent alicyclic group or a divalent aromatic group. As these specific examples, the same ones as those of the above R ⁷ may be mentioned. The repeating unit number p is preferably 2 to 1,000, and more preferably 2 to 100.

Further, the weight ratio ρ ₁ of the first polyimide block and the weight ratio ρ ₂ of the second polyamic acid block in the block copolymer is preferably ρ ₁ <ρ ₂ , and at ρ ₁ > ρ ₂ at a high shear. The viscosity of the film is excessive, which is not suitable for inkjet coating, and even in the usual flexographic printing method, the leveling is poor and the film thickness uniformity may be inferior.

<Method for Producing Block Copolymer>

Next, the manufacturing method of the block copolymer of this invention is demonstrated. The block copolymer of the present invention comprises: (1) "Step A" for producing a polyamic acid initial polymer (A) having an amino group at the molecular end, and 2) a polyimide initial polymer having a reactive group derived from tetracarboxylic acids at the molecular end ( It can manufacture by performing "process B" for manufacturing B) and "process C" which makes the said polyamic-acid initial polymer (A) and the said polyimide initial polymer (B) react. Moreover, although it is also possible to obtain the block copolymer of this invention from the polyamic-acid initial polymer of a tetracarboxylic-acid terminal and the polyimide initial polymer of an amino-group terminal, since the number of repeat units of an initial polymer tends to change with time, Process A, The method of B and C is preferable. Process A, B, and C are demonstrated below.

<Process A>

In this step A, tetracarboxylic acids having an organic group RA and a diamine having an organic group QA are reacted as shown in Scheme 1 below. The polyamic acid initial stage of the repeating unit number (beta) which has an amino group at the terminal of a molecule | numerator by using the diamine in excess in excess of molar amount with respect to the mole number of the tetracarboxylic acid used, for example, the mole number becomes 1.001-2 times. Polymer (A) is prepared.

Process B:

In this step B, tetracarboxylic acids having an organic group RB and a diamine having an organic group QB are reacted as shown in Scheme 2 below. Regarding the number of moles of diamine used, the polyamic acid having a reactive group derived from tetracarboxylic acids at the terminal of the molecule is used by using an excess amount exceeding the molar amount of tetracarboxylic acid such that the number of moles thereof is, for example, 1.001 to 2 times. To prepare. Next, the imidation process mentioned later is performed and the polyimide initial polymer (B) of repeating unit number (alpha) is obtained.

Process C:

In this step C, the terminal amino group of the polyamic acid initial polymer (A) obtained in step A and the reactive group derived from the terminal tetracarboxylic acid of the polyimide initial polymer (B) obtained in step B are the same as step A or step B. By reacting, the polyamic acid block (A) and the same nuclear atom group RB having repeating units of a bond with the organic group QA bonded to each other via a bivalent bonding group (-CO-NH-) in the nuclear atom group RA as shown in Scheme 3 below And a block copolymer in which a polyimide block (B) having a binder of an organic group QB as a repeating unit is bonded.

In addition, in the process C, the block copolymer obtained by the following method can also be made into the terminal modified block copolymer by which molecular weight was adjusted. This terminal modified block copolymer can be used for improvement of application characteristics, etc. Such terminal-modified forms can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound, or the like to the reaction system of Step C. Here, as an acid anhydride, maleic anhydride, a phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n- tetradecyl succinic anhydride, n-hexadecyl succinic anhydride, etc. are mentioned, for example. Can be. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine , n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n -Ecosilamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane , 3-ureidopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-amino Propyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, p- [N- (2-aminoethyl) aminomethyl] phenethyltrimethoxysilane, N, N-bis [3- (trimethoxysilyl) prop Phil] ethylenediamine, N-3-trimethoxysilylpropyl-m-phenylenediamine, etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, 3-isocyanate propyl triethoxysilane, etc. are mentioned, for example.

As tetracarboxylic acid and diamine used at a process A or a process B, it is possible to use together a some compound from the compound illustrated below. In addition, three or more blocks are included by reacting at least one of the polyamic acid initial polymer and / or the polyimide initial polymer prepared in the same manner as in Process A or Process B in Step C, or by reacting in the same manner as Step C. It is also possible to produce a block copolymer.

Specific examples of the tetracarboxylic dianhydride used in Step A include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxyl Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarb 1 or more types chosen from an acid dianhydride and a pyromellitic dianhydride can be used preferably.

Moreover, as a specific example of the tetracarboxylic dianhydride used at process B, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naph Earth [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro -2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl -5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexa Hydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4, 5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 , 3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (te Selected from trahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 2,3,5-tricarboxycyclopentylacetic dianhydride 1 or more types can be used preferably.

In addition, in step A and step B, these acid dianhydrides and tetracarboxylic dianhydrides to be described later are used in combination within a range that does not impair the characteristics of the present invention, preferably 20 mol% or less of all tetracarboxylic dianhydrides. Can be used.

Examples of the tetracarboxylic anhydride used in combination with Step A and / or Step B include alicyclic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides exemplified below. In addition, in step A, the tetracarboxylic dianhydride exemplified as used in step B, and in step B, the tetracarboxylic dianhydride exemplified as used in step A may also be used in an amount of up to 20 mol%. have.

As alicyclic tetracarboxylic dianhydride, it is 1, 3- dichloro- 1, 2, 3, 4- cyclobutane tetracarboxylic dianhydride, 1,2,3, 4- cyclopentane tetracarboxylic acid, for example. Dianhydrides, 1,2,4,5-cyclohexanetetracarboxylic dianhydrides, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydrides, 3,5,6-tricarboxynorborne L-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1 , 2-dicarboxylic dianhydride, bicyclo [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride and a compound represented by the following formulas 5 and 6 Etc. can be mentioned.

In formula, R <_1> and R <_3> represents the divalent organic group which has an aromatic, R <_2> and R <_4> represents a hydrogen atom or an alkyl group, and _two or more R <_2> and R <_4> may be same or different, respectively.

As aromatic tetracarboxylic dianhydride, it is 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, for example. , 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic acid Dianhydrides, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3, 4-furantetetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) di Phenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3, 3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-r (Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid) -4,4 '-Diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitic acid), propylene glycol-bis (anhydrotrimellitic acid), 1,4-butanediol-bis (anhydrotrimellitic acid), 1,6 -Hexanediol-bis (anhydrotrimellitic acid), 1,8-octanediol-bis (anhydrotrimellitic acid), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitic acid And the compounds represented by the following formulas (7) to (10).

As a diamine compound used at the process A and / or the process B, an aliphatic diamine compound, an aromatic diamine compound, etc. are mentioned.

As an aliphatic diamine compound, for example, 1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4 Aliphatic diamines such as, 4-diaminoheptamethylenediamine; 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyl Diamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bisaminomethylcyclohexane, 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,6-bis (amino Alicyclic diamines such as methyl) bicyclo [2.2.1] heptane; And diamino organosiloxane represented by the following formula (11).

In the above formula, R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ^{9 's} may be the same or different, r is an integer of 1 to 3, and s is an integer of 1 to 20.

As an aromatic diamine compound, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl ethane, 4,4'- diamino diphenyl sulfide , 4,4'-diaminophenylsulfone, 4,4'-diaminodiphenylether, 3,5-diamibenzoic acid, 1-hexadecanooxy-2,4-diaminobenzene, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4 '-Diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3- Trimethylindan, 3,4'-diaminodiphenylether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [ 4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1 , 1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) Nil] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9- Bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline) , 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3 , 3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-dia Minobiphenyl, 4,4 '-(p-phenylenediisopropylidene) dianiline, 4,4'-(m-phenylenediisopropylidene) dianiline, 2,2'-bis [4- (4- Amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [(4 Aromatic diamines such as -amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5, 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-dia Mino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5- Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4-diaminopiperazine, 2, in a molecule such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine and the compounds represented by the following formulas (12) and (13) Of a diamine having a nitrogen atom other than the primary amino group and a primary amino group;

^Wherein R ¹⁰ represents a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X represents a divalent organic group.

In the above formula, R ¹ represents a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, X represents a divalent organic group, and a plurality of X May be the same or different.

Mono-substituted phenylenediamines represented by the following formula (14);

In the above formula, R ¹² represents a divalent organic group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -CO-, and R ¹³ represents a steroid skeleton, a trifluoromethyl group and a fluorine group. Monovalent organic group or group having 6 to 30 carbon atoms having a group selected from the group.

And compounds represented by the following formulas (15) to (27). These diamine compounds can be used individually or in combination of 2 or more types.

Wherein y is an integer from 2 to 12 and z is an integer from 1 to 5.

Among them, 1,4-diaminocyclohexane, isophoronediamine, 1-hexadecanoxy-2,4-diaminobenzene, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanyl Ethylenedimethylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), 1,3-bisaminomethylcyclohexane, 2,5-bis (amino Methyl) bicyclo [2.2.1] heptane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenyl Sulfone, 4,4'-diaminodiphenylether, 3,5-diaminobenzoic acid, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3- Aminophenoxy) bene Zen, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 3,3'-dimethoxy- 4,4'-diaminobiphenyl, 4,4 '-(p-phenylenediisopropylidene) dianiline, 4,4'-(m-phenylenediisopropylidene) dianiline, 1,1-methac Silylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine and the above formulas 15 to 27 The compound represented by is preferable.

These diamines can be used individually or in combination of 2 or more types.

The reaction in the step A, the step B and the step C is carried out in an organic solvent under temperature conditions of preferably 0 to 200 ° C, more preferably 0 to 100 ° C.

The organic solvent used for this reaction is not particularly limited as long as it can dissolve the polyamic acid produced. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylform Aprotic polar solvents such as amide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, and hexamethylphospholtriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, are mentioned. It is preferable that the usage-amount of an organic solvent is an amount whose total amount of tetracarboxylic acids and diamine becomes a ratio of 0.1-30 weight% with respect to the whole quantity of a reaction solution.

The organic solvent can be used in combination at a rate such that the polyamic acid initial polymer that produces alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons as poor solvents does not precipitate. As such a poor solvent, for example, ethyl alcohol, cyclohexanol, propylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, diethyl malonate, diethyl ether, ethylene glycol methyl Ether, ethylene glycol ethyl ether, ethylene glycol-propyl ether, ethylene glycol ethyl ether acetate, tetrahydrofuran, dichloroethane, chlorobenzene, hexane, heptane, toluene, xylene and the like.

The imidation reaction in process B is performed by the method of melt | dissolving the intermediate | middle product (polyamic acid) in Reaction Formula 2 in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as needed. In addition, by selecting the dehydration ring-closure reaction conditions in step B, a partially dehydrated ring-closure reaction polyimide can also be preferably used. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride can be used. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to these. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. Moreover, the organic solvent mentioned above is mentioned as an organic solvent used for dehydration ring-closure reaction. And the reaction temperature of a dehydration ring-closure reaction is 0-180 degreeC normally, Preferably it is 10-150 degreeC.

However, since these block copolymers are a combination of two or three or more kinds of polyimide-based blocks and polyamic acid-based blocks having different mutual structures, they have inherent properties as polyamic acids or polyimides. And the polyamic acid or polyimide homopolymer of each block. That is, for example, the first polyimide component and the second polyamic acid component coexist in a molecule as a block, whereby the first characteristics of the homopolymer of the polyimide constituting the first block and the second block It becomes what has the 2nd characteristic which the homopolymer of polyamic acid has simultaneously. Or it can be said that the characteristic of this block copolymer is a state denatured by the homopolymer characteristic of the polyamic acid which comprises the block from which the homopolymer characteristic of the polyimide which comprises a fixed block differs.

Such a property cannot be obtained by a simple mixture of the first polyimide and the second polyamic acid, and all tetracarboxylic acids and diamines used to obtain the first polyimide and the second polyamic acid may be exemplified. For example, even if the reaction is carried out in a batch.

That is, the block copolymer of this invention can be said to be a copolymer which has several favorable characteristic which cannot be obtained simultaneously by a normal means.

The characteristic of the block copolymer of this invention is determined by the structure of the repeating unit in each block which comprises it, the number of the repeating units, or its ratio. Therefore, by controlling these elements, it is possible to control the characteristic of the polyimide-type block copolymer finally obtained.

That is, if the kind of tetracarboxylic acid and diamine used for generation | occurrence | production of each block is selected, and the number of blocks, each kind, and their ratio which should comprise the block copolymer obtained by adjusting the usage amount or usage ratio are controlled, Thereby, it is possible to control the characteristic of the block copolymer finally obtained.

<Liquid crystal aligning agent>

Next, the liquid crystal aligning agent using the said block copolymer is demonstrated. Although the content rate of the block polymer in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it is 0.1-20 weight% with respect to the whole liquid crystal aligning agent, More preferably, it is 1-10 weight% Range. That is, the liquid crystal aligning agent which consists of a polymer solution is apply | coated to the surface of a board | substrate by the printing method, the spin coat method, etc., and then this film is dried and the film which is an oriented film material is formed, but when the content rate of a polymer is less than 0.1 weight%, When the film thickness is too thin, a good liquid crystal aligning film may not be obtained, and when it exceeds 20% by weight, the film thickness of the film is too thick, so that a good liquid crystal aligning film is difficult to obtain, and the viscosity of the liquid crystal aligning agent is increased, resulting in poor application characteristics. There may be a thing falling.

In addition, the liquid crystal aligning agent used in the present invention is characterized in that it comprises a block copolymer of a specific structure, it is also possible to use a mixture of polyamic acid and / or polyimide of another structure in a range that does not impair the effects of the present invention. have.

The organic solvent for dissolving the polymer is not particularly limited as long as it can dissolve the polymer, and examples thereof include solvents exemplified as those used in the synthesis reaction of polyamic acid and the dehydration ring closure reaction. Moreover, the poor solvent illustrated as what can be used together at the time of the synthesis reaction of a polyamic acid can also be selected suitably, and can be used together. Moreover, when apply | coating the liquid crystal aligning agent of this invention by the inkjet method, it is preferable to make content of N-methylpyrrolidone into 20 weight% or less of the total solvent quantity from a viewpoint of suppressing the damage of an apparatus member.

The liquid crystal aligning agent used for this invention may mix | blend a functional silane containing compound and an epoxy compound from a viewpoint of further improving the adhesiveness of a polymer and the surface of the board | substrate apply | coated. As such a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- ( 2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrier Methoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-tri Methoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl- 3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-ben Jyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltri Methoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned.

As the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3, 5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycid Dylaminomethyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltri Methoxysilane, 3- (N, N- diglycidyl) aminopropyltrimethoxysilane, etc. are mentioned as a preferable thing. Among these, compounds having a tertiary nitrogen atom in the molecule are preferable. The compounding ratio of these compounds is usually 40 parts by weight or less, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer.

<Liquid crystal display element>

The liquid crystal display element of this invention obtained using the liquid crystal aligning agent in this invention can be manufactured by the following method, for example.

(1) The liquid crystal aligning agent is apply | coated to the transparent conductive film side of the board | substrate with which the patterned transparent conductive film was installed, for example by methods, such as a roll coater method, a spinner method, and a printing method, and a film is formed by heating a coating surface then. As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass, plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used. As the transparent conductive film provided on one surface of the substrate, for example, an NESA film made of SnO ₂ , an ITO film made of In ₂ O ₃ -SnO ₂ , and the like can be used. The photoetching method, the method of using a mask beforehand, etc. are used for the patterning of these transparent conductive films.

In application | coating of a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate, a transparent conductive film, and a coating film further favorable, you may apply | coat a functional silane containing compound, titanate, etc. on a board | substrate and a transparent conductive film previously. Although the flexographic printing method has been the mainstream in the coating method conventionally, in the liquid crystal aligning agent of this invention, application | coating is possible not only the flexographic printing method but also the inkjet printing method. Moreover, the drying temperature of a coating film becomes like this. Preferably it is 80-250 degreeC, More preferably, it is 120-200 degreeC. The film thickness of the formed film is 0.001-1 micrometer normally, Preferably it is 0.005-0.5 micrometer.

The formed film is subjected to a rubbing treatment of rubbing the film surface in a predetermined direction with a roller wound around a film made of fibers such as nylon, rayon, cotton, etc., whereby the alignment ability of the liquid crystal molecules is imparted to the film, thereby forming a liquid crystal alignment film. Moreover, in order to remove the fine powder (foreign substance) which arises at the time of a rubbing process, and to make a film surface clean, it is preferable to wash the formed liquid crystal aligning film with isopropyl alcohol etc. Moreover, in addition to the method by a rubbing process, a film is obtained by irradiating polarizing ultraviolet-ray, an ion beam, an electron beam, etc. to the film surface, and providing an orientation capability, and obtaining a film by the uniaxial stretching method, the Langmuir Blodgett method, etc. By the method etc., a liquid crystal aligning film can also be formed.

Moreover, for example, Unexamined-Japanese-Patent No. 8-234207, No. 7-168187, No. 6-222366, or Japan Patent Publication ) A method of changing the pretilt angle by partially irradiating ultraviolet rays, ion beams, and electron beams disclosed in 6-281937, or the above-mentioned disclosed in Japanese Patent Laid-Open No. Hei 5-107544. By forming a resist film partially on the alignment-processed liquid crystal aligning film, performing an alignment process in a direction different from the preceding liquid crystal alignment direction, removing the said resist film and performing the process which changes the alignment capability of a liquid crystal aligning film It is possible to improve the clock characteristics of the liquid crystal display element.

(3) Two board | substrates with a liquid crystal aligning film were produced as mentioned above, and two board | substrates were opposingly spaced so that the direction of the pretilt angle in each liquid crystal aligning film might be orthogonal or antiparallel. The two peripheral portions of the substrate are bonded together using a sealant, the liquid crystal is filled in the cell gap partitioned by the surface of the substrate and the sealant, and the filling hole is sealed to form a liquid crystal cell. And a liquid crystal display element is bonded to the outer surface of the liquid crystal cell, ie, the other surface side of each board | substrate which comprises a liquid crystal cell so that the polarizing direction may coincide with or perpendicular to the liquid crystal aligning direction of the liquid crystal aligning film formed in one surface of the said board | substrate. Can be obtained.

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

As said liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, for example. Especially, a nematic type liquid crystal is preferable, for example, a Schiff base type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenyl cyclohexane type liquid crystal, an ester type liquid crystal, a t-phenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a flute Midine type liquid crystals, dioxane type liquid crystals, bicyclooctane type liquid crystals, cuban type liquid crystals, etc. are used. In addition, these liquid crystals are, for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate, and product names "C-15" and "CB-15" (manufactured by Melk Co., Ltd.). The chiral agent sold etc. can also be added and used. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate called the H film which absorbed iodine while extending-stretching polyvinyl alcohol, the polarizing plate which sandwiched the cellulose acetate protective film, or the polarizing plate which consists of H film itself, etc. are mentioned.

<Example>

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The performance evaluation method at the time of using for the property of the liquid crystal aligning agent produced by the following example and the comparative example and a liquid crystal display element use is shown below.

[Solubility of Block Copolymer]

To 50 g of the liquid crystal aligning agent adjusted as a γ-butyrolactone solution having a solid content concentration of 4% by weight, butyl cellosolve serving as the poor solvent was added until precipitation occurred, and butyl cellosolve could be added to some extent. Presence was used as an indicator of solubility. The higher the amount added, the better the solubility.

[Inkjet coating property]

The liquid crystal aligning agent was apply | coated to the ITO board | substrate in the liquid amount which a dry film thickness becomes 800 Pa using the JET-CM continuous inkjet printer (made by Kishu Kikyo Kogyo Co., Ltd.) apparatus adjusted to solid content concentration 2 weight%. . Subsequently, it dried at 180 degreeC, the unevenness | corrugation of a dry film was measured with the stylus type film thickness meter, and the difference between the largest film thickness and the lowest film thickness was evaluated as film thickness uniformity. Moreover, the stability of printing was evaluated by comparing the film thickness uniformity at the time of start of inkjet coating and the time of continuous application for 5 hours, and it was considered that the case where the difference between the time of start and 5 hours after 50 kPa or less was favorable.

[Orientation of Liquid Crystal]

The presence or absence of the abnormal domain in the liquid crystal cell when the voltage was turned on and off in the liquid crystal display element was observed under a microscope, and it was judged as "good" that there was no abnormal domain.

[Pretilt Angle of Liquid Crystal Display Element]

It was measured by the crystal rotation method using He-Ne laser light according to the method described in T. J. Schffer, et. Al., J. Appl. Phys., Vol. 19, 2013 (1980).

[Voltage retention rate of liquid crystal display element]

After applying a voltage of 5 V to the liquid crystal display element with an application time of 60 microseconds and a span of 500 milliseconds, the voltage retention after 500 milliseconds from the release of the application was measured. The measurement apparatus was performed at 60 degreeC using VHR-1 by Toyo Technica Corporation.

Afterimage erasing time of liquid crystal display element

After applying DC voltage 20V to a liquid crystal display element for 24 hours, the time until the voltage was turned off and an afterimage was visually erased was measured.

<Synthesis example 1>

<Step A> Preparation of the polyamic acid initial polymer

64.14 g of pyromellitic dianhydride, 134.56 of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 198.27 g of 4,4'-diaminodiphenylmethane, 1600 g of N-methyl-2-pyrrolidone It dissolved in and reacted this solution at 20 degreeC for 6 hours. Subsequently, the obtained reaction solution was put in an excess of acetone to precipitate the reaction product, and the reaction product was precipitated, separated, washed, and dried to carry out a polyamic acid initial stage having an amino group at a molecular terminal having a logarithmic viscosity (ηln) of 1.8 d1 / g. 400.3 g of polymer (A-1) was obtained.

<Step B> Preparation of the polyimide initial polymer

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1 146.48 g of, 3-dione, 46.56 g of p-phenylenediamine and 6.96 g of the compound represented by the above formula (16) were dissolved in 800 g of N-methyl-2-pyrrolidone, and the solution was reacted at 20 ° C. for 26 hours. . The reaction solution obtained was then placed in excess acetone to precipitate the reaction product (polyamic acid initial polymer). 120.0 g of the obtained polyamic acid initial polymer was dissolved in 600 g of γ-butyrolactone, and 44 g of pyridine and 56 g of acetic anhydride were added and dehydrated and closed for 2 hours at 60 ° C. Subsequently, by precipitation, separation, washing and drying of the reaction product, 97.2 g of a polyimide initial polymer (B-1) having an acid anhydride group at a molecular terminal having a logarithmic viscosity (ηln) of 0.76 dl / g and an imidation ratio of 90%. Got.

<Step C> Preparation of the block copolymer

80 g of the polyamic acid initial polymer (A-1) obtained in step A and 20 g of the polyimide initial polymer (B-1) obtained in step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 17 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 20 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (1) was 1.64 d1 / g.

<Synthesis example 2>

<Step A> Preparation of the polyamic acid initial polymer

In the same manner as in Step A of Synthesis Example 1, a polyamic acid initial polymer (A-1) was obtained.

<Step B> Preparation of the polyimide initial polymer

The raw materials used in the synthesis were 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -c] Synthesis except for changing 132.31 g of furan-1,3-dione, 11.92 g of 4,4'-diaminodiphenylmethane, 30.35 g of p-phenylenediamine, and 25.4 g of the compound represented by the above formula (20). The reaction was carried out in the same manner as in Step B of Example 1, to obtain 25.3 g of a polyimide initial polymer (B-2) having an acid anhydride group at a molecular terminal having a logarithmic viscosity (? 1n) of 0.73 d1 / g and an imidation ratio of 94%.

<Step C> Preparation of the block copolymer

80 g of the polyamic acid initial polymer (A-1) obtained in step A and 20 g of the polyimide initial polymer (B-2) obtained in step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 17 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 20 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (2) was 1.65 d1 / g.

<Synthesis example 3>

<Step A> Preparation of the polyamic acid initial polymer

In the same manner as in Step A of Synthesis Example 1, a polyamic acid initial polymer (A-1) was obtained.

<Step B> Preparation of the polyimide initial polymer

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1 267.16 g of 3,3-dione, 33.63 g of 2,3,5-tricarboxycyclopentylacetic dianhydride, 72.1 g of p-phenylenediamine, 47.21 g of 4,4'-diaminodiphenylmethane and represented by the above formula (16) 24.9 g of the compound was dissolved in 1800 g of N-methyl-2-pyrrolidone, and the solution was reacted at 20 ° C. for 26 hours. The reaction solution obtained was then placed in excess acetone to precipitate the reaction product (polyamic acid initial polymer). 30.0 g of the obtained polyamic acid initial polymer was dissolved in 150 g of γ-butyrolactone, and 11 g of pyridine and 14 g of acetic anhydride were added and dehydrated and closed for 2 hours at 60 ° C. Subsequently, by precipitation, separation, washing and drying of the reaction product, 29.3 g of a polyimide initial polymer (B-3) having an acid anhydride group at a molecular terminal having a logarithmic viscosity (η 1 n) of 0.66 dl / g and an imidation ratio of 90% Got.

<Step C> Preparation of the block copolymer

80 g of the polyamic acid initial polymer (A-1) obtained in step A and 20 g of the polyimide initial polymer (B-3) obtained in step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 16 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 20 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (3) was 1.61 d1 / g.

<Synthesis example 4>

<Step A> Preparation of the polyamic acid initial polymer

In the same manner as in Step A of Synthesis Example 1, a polyamic acid initial polymer (A-1) was obtained.

<Step B> Preparation of the polyimide initial polymer

224.2 g of 2,3,5-tricarboxycyclopentylacetic dianhydride, 92.7 g of p-phenylenediamine and 49.78 g of the compound represented by the above formula (16) were dissolved in 2000 g of N-methyl-2-pyrrolidone, The solution was reacted at 60 ° C. for 6 hours. The reaction solution obtained was then placed in excess acetone to precipitate the reaction product (polyamic acid initial polymer). 30.0 g of the obtained polyamic acid initial polymer was dissolved in 200 g of N-methyl-2-pyrrolidone, and 17 g of pyridine and 11 g of acetic anhydride were added to dehydrate and close the ring at 110 ° C for 4 hours. Subsequently, by precipitating, separating, washing and drying the reaction product, 28.3 g of a polyimide initial polymer (B-4) having an acid anhydride group at a molecular terminal having a logarithmic viscosity (η 1 n) of 0.5 dl / g and an imidation ratio of 80% Got.

<Step C> Preparation of the block copolymer

80 g of the polyamic acid initial polymer (A-1) obtained in Step A and 20 g of the polyimide initial polymer (B-4) obtained in Step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 15 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 18 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (4) was 1.60 d1 / g.

<Synthesis example 5>

<Step A> Preparation of the polyamic acid initial polymer

In the same manner as in Step A of Synthesis Example 1, a polyamic acid initial polymer (A-1) was obtained.

<Step B> Preparation of the polyimide initial polymer

In the same manner as in Step B of Synthesis Example 1, a polyimide initial polymer (B-1) was obtained.

<Step C> Preparation of the block copolymer

60 g of the polyamic acid initial polymer (A-1) obtained in step A and 40 g of the polyimide initial polymer (B-1) obtained in step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 18 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 23 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (5) was 1.70 d1 / g.

<Synthesis example 6>

<Step A> Preparation of the polyamic acid initial polymer

In the same manner as in Step A of Synthesis Example 1, a polyamic acid initial polymer (A-1) was obtained.

<Step B> Preparation of the polyimide initial polymer

In the same manner as in Step B of Synthesis Example 1, a polyimide initial polymer (B-1) was obtained.

<Step C> Preparation of the block copolymer

30 g of the polyamic acid initial polymer (A-1) obtained in step A and 70 g of the polyimide initial polymer (B-1) obtained in step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 16 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 22 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (6) was 1.60 d1 / g.

<Synthesis example 7>

<Step A> Preparation of the polyamic acid initial polymer

51.88 g of pyromellitic dianhydride and 48.12 g of 4,4'-diaminodiphenylmethane were dissolved in 600 g of N-methyl-2-pyrrolidone, and the solution was reacted at 20 ° C for 6 hours. Subsequently, the obtained reaction solution was put in an excess of acetone to precipitate the reaction product, and the reaction product was precipitated, separated, washed, and dried to obtain an initial polyamic acid having an amino group at the molecular end of logarithmic viscosity (ηln) of 1.4 dl / g. 95 g of polymer (A-2) was obtained.

<Step B> Preparation of the polyimide initial polymer

In the same manner as in Step B of Synthesis Example 1, a polyimide initial polymer (B-1) was obtained.

<Step C> Preparation of the block copolymer

80 g of the polyamic acid initial polymer (A-2) obtained in step A and 20 g of the polyimide initial polymer (B-1) obtained in step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 15 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 18 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (7) was 1.55 d1 / g.

<Synthesis example 8>

<Step A> Preparation of the polyamic acid initial polymer

In the same manner as in Step A of Synthesis Example 1, a polyamic acid initial polymer (A-1) was obtained.

<Step B-1> Preparation of the First Polyimide Initial Polymer

In the same manner as in Step B of Synthesis Example 1, a polyimide initial polymer (B-1) was obtained. <Step B-2> Preparation of the Second Polyimide Initial Polymer

In the same manner as in Process B of Synthesis Example 4, a polyimide initial polymer (B-4) was obtained.

<Step C> Preparation of the block copolymer

80 g of polyamic acid initial polymer (A-1) obtained in step A and 15 g of polyimide initial polymer (B-1) obtained in step B-1 and polyimide initial polymer (B-4) obtained in step B-2 5 g was dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of the solution was 16 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of a ternary block copolymer was obtained. The solution viscosity after reaction was 19 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (8) was 1.70 d1 / g.

<Synthesis example 9>

<Step A-1> Preparation of the first polyamic acid initial polymer

In the same manner as in Step A of Synthesis Example 1, a polyamic acid initial polymer (A-1) was obtained.

<Step A-2> Preparation of the second polyamic acid initial polymer

224.17 g of 2,3,5-tricarboxycyclopentylacetic dianhydride and 432.5 g of bis [4- (4-aminophenoxy) phenyl] sulfone are dissolved in 6000 g of γ-butyrolactone, and the solution is heated at 60 ° C. The reaction was carried out for 6 hours. Subsequently, the obtained reaction solution was put in an excess of acetone to precipitate the reaction product, and the reaction product was precipitated, separated, washed, and dried to obtain an initial polyamic acid having an amino group at a molecular terminal having a logarithmic viscosity (η 1 n) of 1.5 d 1 / g. 650 g of a polymer (A-3) was obtained.

<Step B> Preparation of the polyimide initial polymer

In the same manner as in Step B of Synthesis Example 1, a polyimide initial polymer (B-1) was obtained. <Step C> Preparation of the block copolymer

60 g of polyamic acid initial polymer (A-1) obtained in step A-1 and 20 g of polyamic acid initial polymer (A-3) obtained in step A-2 and polyimide initial polymer (B-1) 20 obtained in step B 20 g was dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of the solution was 18 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of a ternary block copolymer was obtained. The solution viscosity after reaction was 20 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (9) was 1.63 d1 / g.

<Synthesis example 10>

<Step A> Preparation of the polyamic acid initial polymer

26.37 g of pyromellitic dianhydride, 23.71 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 49.92 g of 4,4'-diaminodiphenylether were added N-methyl-2-pyrrolidone 900 It dissolved in g and made this solution react at 20 degreeC for 6 hours. Subsequently, the obtained reaction solution was put in an excess of acetone to precipitate the reaction product, and the reaction product was precipitated, separated, washed, and dried to carry out a polyamic acid initial stage having an amino group at a molecular terminal having a logarithmic viscosity (η 1 n) of 1.6 dl / g. 96.3 g of polymer (A-4) was obtained.

<Step B> Preparation of the polyimide initial polymer

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1 52.778 g, 3-dione, 6.64 g 2,3,5-tricarboxycyclopentylacetic dianhydride, 12.44 g p-phenylenediamine, 23.13 g 4,4 '-(p-phenylenediisopropylidene) dianiline and 5.01 g of the compound represented by Chemical Formula 16 was dissolved in 800 g of N-methyl-2-pyrrolidone, and the solution was reacted at 20 ° C. for 26 hours. The reaction solution obtained was then placed in excess acetone to precipitate the reaction product (polyamic acid initial polymer). 100.0 g of the obtained polyamic acid initial polymer was dissolved in 900 g of γ-butyrolactone, and 62 g of pyridine and 141 g of acetic anhydride were added to dehydrate and close the ring for 2 hours at 60 ° C. Subsequently, by precipitating, separating, washing and drying the reaction product, 97.2 g of a polyimide initial polymer (B-5) having an acid anhydride group at a molecular terminal having a logarithmic viscosity (ηln) of 0.73 d1 / g and an imidation ratio of 90%. Got.

<Step C> Preparation of the block copolymer

75 g of the polyamic acid initial polymer (A-4) obtained in Step A and 25 g of the polyimide initial polymer (B-5) obtained in Step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 20 mPa · s. This was reacted at 30 degreeC for 48 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 27 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer 10 was 1.8 dl / g.

<Synthesis example 11>

<Step A> Preparation of the polyamic acid initial polymer

40.72 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 51.28 g of 4,4'-diaminodiphenyl ether are dissolved in 900 g of N-methyl-2-pyrrolidone, and the solution is The reaction was carried out at 20 ° C. for 6 hours. Subsequently, the obtained reaction solution was put in an excess of acetone to precipitate the reaction product, and the reaction product was precipitated, separated, washed, and dried to carry out a polyamic acid initial stage having an amino group at a molecular terminal having a logarithmic viscosity (η 1 n) of 1.6 dl / g. 93 g of polymer (A-5) was obtained.

<Step B> Preparation of the polyimide initial polymer

1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1 , 3-dione 59.19 g, 2,3,5-tricarboxycyclopentylacetic dianhydride 4.69 g, p-phenylenediamine 13.44 g, 2,2-bis (4-aminophenyl) -1,1,1,3 10.39 g of 3,3-hexafluoropropane, 9.04 g of 4,4'-diaminodiphenylmethane and 3.25 g of the compound represented by Formula 16 are dissolved in 300 g of N-methyl-2-pyrrolidone, This solution was reacted at 20 ° C for 26 hours. The reaction solution obtained was then placed in excess acetone to precipitate the reaction product (polyamic acid initial polymer). 100.0 g of the obtained polyamic acid initial polymer was dissolved in 900 g of γ-butyrolactone, and 65.2 g of pyridine and 84.2 g of acetic anhydride were added and dehydrated and closed for 2 hours at 60 ° C. Subsequently, by precipitation, separation, washing and drying of the reaction product, 94 g of a polyimide initial polymer (B-6) having an acid anhydride group at a molecular terminal having a logarithmic viscosity (η 1 n) of 0.58 dl / g and an imidation ratio of 95% Got.

<Step C> Preparation of the block copolymer

75 g of the polyamic acid initial polymer (A-5) obtained in step A and 25 g of the polyimide initial polymer (B-6) obtained in step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 14 mPa · s. This was reacted at 50 degreeC for 4 hours, and the solution of a block copolymer was obtained. The solution viscosity after reaction was 21 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer 11 was 1.6 dl / g.

<Comparative Synthesis Example 1>

1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione 34.7 g, 10.41 g of p-phenylenediamine, 3.84 g of 1-hexadecanoxy-2,4-diaminobenzene and 1.05 g of 3-aminopropylmethyldiethoxysilane, 200 g of N-methyl-2-pyrrolidone It dissolved in and reacted this solution at 20 degreeC for 24 hours. Subsequently, the obtained reaction solution was put into excess acetone to precipitate the reaction product. 50.0 g of the obtained polymer was dissolved in 450 g of γ-butyrolactone, and 5.0 g of pyridine and 10.8 g of acetic anhydride were added to dehydrate and close the ring for 3 hours at 50 ° C. Subsequently, 47 g of soluble polyimide polymers (b) having a logarithmic viscosity (ηln) of 0.72 d1 / g and an imidation ratio of 90% were obtained by precipitating, separating, washing, and drying the reaction product.

<Comparative Synthesis Example 2>

<Step A> Preparation of the polyamic acid initial polymer

In the same manner as in Step A-2 of Synthesis Example 10, a polyamic acid initial polymer (A-3) was obtained.

<Step B> Preparation of the polyimide initial polymer

In the same manner as in Step B of Synthesis Example 1, a polyimide initial polymer (B-1) was obtained.

<Step C> Preparation of the block copolymer

80 g of the polyamic acid initial polymer (A-3) obtained in step A and 20 g of the polyimide initial polymer (B-1) obtained in step B were dissolved in γ-butyrolactone to give a solution having a solid content of 4% by weight. The viscosity of was 15 mPa · s. This was reacted at 40 degreeC for 24 hours, and the solution of the block copolymer was obtained. The solution viscosity after reaction was 18 mPa * s, and the logarithmic viscosity ((eta) 1n) of the obtained block copolymer (i) was 1.50 d1 / g.

<Example 1>

The block copolymer (1) obtained in Synthesis Example 1 was dissolved in γ-butyrolactone to obtain a solution having a solid content of 4% by weight, and the solution was filtered through a filter having a pore diameter of 1 μm to prepare a liquid crystal aligning agent. Butyl cellosolve was added to 50 g of this liquid crystal aligning agent until precipitation occurred. The amount of butyl cellosolve that could be added was 20 g, and the resulting block copolymer was excellent in solubility.

Moreover, when the obtained liquid crystal aligning agent was diluted to 2 weight% of solid content concentration, and printed by the inkjet printing machine, the difference (film thickness uniformity) of the maximum film thickness and the minimum film thickness was 70 kPa, and was favorable. Subsequently, when the continuous inkjet printability was tested, application | coating defect was not seen and the film thickness uniformity difference (continuous printing property) at the time of printing start and end was also very stable at 30 kPa.

The liquid crystal aligning agent was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane using the printing machine for apply | coating a liquid crystal aligning film, and it dried on a heating plate of 180 degreeC for 10 minutes, and formed the film of 600 mm of dry average film thickness It was. By the rubbing machine which has the roller which wound the cloth made from rayon on this film, the rubbing process was performed by roll rotation speed 400rpm, the movement speed of a stage 3cm / sec, and hair indentation length 0.4mm. After immersing the said oriented film coating board | substrate in isopropyl alcohol for 1 minute, both board | substrates were dried for 5 minutes on the 100 degreeC heating plate.

Subsequently, after screen-printing and apply | coating the epoxy resin adhesive which has a 5.5-micrometer diameter aluminum oxide sphere to each outer edge which has a liquid crystal aligning film of a pair of opposing liquid crystal aligning substrate, a pair of liquid crystal aligning substrates may face a liquid crystal aligning film surface. Moreover, it crimped | bonded so that the rubbing direction might go straight, and hardened the adhesive agent. Subsequently, the nematic liquid crystal (MLC-5081, manufactured by Melk Co., Ltd.) was charged from the liquid crystal injection hole to the pair of substrates, and then the liquid crystal injection hole was sealed with an acrylic photocuring adhesive, and the polarizing directions of the polarizing plates were respectively placed on both sides of the substrate. It bonded together so that it might correspond to the liquid crystal aligning film rubbing direction of the board | substrate of, and produced the liquid crystal display element.

When the liquid crystal alignability, the pretilt angle, the voltage retention, and the afterimage erasing of the obtained liquid crystal display element were evaluated, the orientation of the liquid crystal was good, the afterimage erasing time was short at 1 minute, and the required characteristics as the liquid crystal alignment film were satisfied. These results are shown in Table 1 and Table 2.

<Examples 2 to 12, Comparative Examples 1 to 4>

According to the prescription shown in Table 1, it carried out except adjusting the liquid crystal aligning agent using the polymer obtained by the synthesis examples 2-11 and comparative synthesis examples 1-2, and an additive, and changing the liquid crystal to MLC-2012 in Example 4. An orientation treatment was performed in the same manner as in Example 1, and a liquid crystal display device was produced in the same manner as in Example 1. Each of the obtained liquid crystal display elements was evaluated for the orientation of liquid crystal, the afterimage erasing time, and the like. The results are shown in Table 1 and Table 2.

The following effects are recognized from Examples 1-12 and Comparative Examples 1-4.

That is, the liquid crystal aligning agent which uses a polyamic acid and polyimide as a monomer, or simply mixed, has problems, such as the coating defect at the time of inkjet printing, the print quality defect, the performance as a liquid crystal display element, etc. According to this, the inkjet printability and various characteristics as the liquid crystal display element can all be satisfied at a high level.

Therefore, according to the present invention, since it is suitable for inkjet printing in order to improve the yield of the liquid crystal panel and reduce the cost, and can satisfy the high level of pretilt angle, voltage retention, and afterimage characteristic required for the liquid crystal display device, In addition to being suitable for STN type liquid crystal display elements, by selecting the liquid crystal to be used, it can be suitably used for SH (Super Homeotropic) type, IPS (In-Plane Switching) type, ferroelectric and antiferroelectric liquid crystal display elements, and the like. have. In addition, the block copolymer 11 used in Example 12 is also excellent in transparency, and thus is suitable for reflective LCD and projector applications.

Moreover, the liquid crystal display element which has the liquid crystal aligning film manufactured by the method of this invention can be effectively used for various apparatuses, For example, a table calculator, a wristwatch, a table clock, a counting plate, a word processor, a personal computer, a liquid crystal television, etc. It can be used as a display device.

Claims (2)

A block copolymer containing a first polyimide block and a second polyamic acid block in a molecule, wherein the first polyimide block is a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2) At least one repeating unit selected from the group consisting of: wherein the second polyamic acid block comprises at least one repeating unit selected from the group consisting of repeating units represented by the following formula (3) and repeating units represented by the following formula (4): A unit is contained, The liquid crystal aligning agent characterized by the above-mentioned. <Formula 1> <Formula 2> <Formula 3> <Formula 4> Where R ¹ , R ⁴ , R ⁶ represent a hydrogen atom or an alkyl group, R ² , R ³ , R ⁵ and R ⁷ are divalent organic groups, l represents an integer of 1 to 4, m, n, p and q are positive numbers indicating the number of repeat units. It has a liquid crystal aligning film obtained using the liquid crystal aligning agent of Claim 1, The liquid crystal display element characterized by the above-mentioned.