KR101759753B1 - Liquid crystal-aligning agent, liquid crystal alignment film, and liquid crystal display element using same - Google Patents

Abstract

(식 [1] 중, X₁ 은 -O-, -NH-, -N(CH₃)-, -CONH-, -NHCO-, -CH₂O-, -COO-, -OCO-, -CON(CH₃)-, 또는 -N(CH₃)CO- 이고, X₂ 는 단결합, 탄소수 1 ∼ 20 의 지방족 탄화수소기, 비방향족 고리형 탄화수소기, 또는 방향족 탄화수소기이며, X₃ 은 단결합, -O-, -NH-, -N(CH₃)-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH₃)-, -N(CH₃)CO-, 또는 -O(CH₂)_m- (m 은 1 ∼ 5 의 정수이다) 이고, X₄ 는 탄소수 1 ∼ 20 의 유기기를 나타내고, n 은 1 ∼ 4 의 정수이다) At least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component containing a diamine compound represented by the formula [1] with a tetracarboxylic acid dianhydride and a polyimide obtained by dehydrocondylating the polyamic acid And the liquid crystal alignment treatment agent.
[Chemical Formula 1]

(Wherein X ₁ represents -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃₎ -, or -N (CH ₃₎ CO-, and, X ₂ represents a single bond, a carbon number of from 1 to 20 aliphatic hydrocarbon group, non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group, X ₃ is a single bond , -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N (CH ₃ ) CO-, Or -O (CH ₂ ) _m - (m is an integer of 1 to 5), X ₄ is an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 4)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment layer, and a liquid crystal display element using the same. BACKGROUND ART [0002] Liquid crystal alignment agents, liquid crystal alignment films, and liquid crystal display elements,

The present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film and a liquid crystal display element used for a liquid crystal display element.

In a liquid crystal display element, a liquid crystal alignment film plays a role of aligning the liquid crystal in a certain direction. Presently, the main liquid crystal alignment film used industrially is formed by coating a substrate with a polyimide-based liquid crystal alignment treatment agent comprising a polyamic acid (also referred to as polyamic acid) or a solution of polyimide as a polyimide precursor to form a film do. When the liquid crystal is aligned in a parallel or tilted orientation with respect to the substrate surface, surface roughening treatment is further performed by rubbing after the film is formed. As an alternative to the rubbing treatment, a method of using anisotropic photochemical reaction by polarized ultraviolet irradiation or the like has been proposed. Recently, studies for industrialization have been made.

The liquid crystal alignment layer is also used to control the angle of the liquid crystal with respect to the substrate, that is, the control of the pretilt angle of the liquid crystal. While the liquid crystal display element has high performance and its use range is expanding year by year, Not only the quality but also the stability of the pretilt angle becomes more important.

From the standpoint of stability of the pretilt angle, in order to obtain a constant pretilt angle regardless of the rubbing condition in the production process of the liquid crystal alignment film, a compound having two or more epoxy groups in the molecule is added to a polyimide- (See, for example, Patent Document 1).

In the manufacturing process of a liquid crystal display element, in order to enhance the alignment uniformity of the liquid crystal, there is a case where the liquid crystal is enclosed and then heat-treated to make the liquid crystal isotropic once. However, when the stability of the pretilt angle is low, a problem arises in that a desired pretilt angle after the isotropic treatment is not obtained or a deviation occurs in the pretilt angle. Particularly, in a liquid crystal display element using a backlight having a large heating value to obtain a high luminance or a liquid crystal display element used in a vehicle application, for example, a car navigation system or a meter panel, have. In such a severe condition, when the pretilt angle is gradually changed, initial display characteristics are not obtained, or there arises a problem such as display unevenness.

In recent years, a liquid crystal display device having a large screen and a high definition has widely been put to practical use. Such a liquid crystal display device is generally used for a long period of time in a severe use environment A property that can withstand use is required. Therefore, the liquid crystal alignment film has been required to have higher reliability. In particular, when the voltage holding ratio, which is one of the electric characteristics, is lowered, line ghosting, which is a display failure of the liquid crystal display element, is liable to occur, and a liquid crystal display element with high reliability can not be obtained. For this reason, it is required that not only the initial characteristics are good but also that it is difficult to lower even after a long time exposure at a high temperature, for example.

Japanese Patent Application Laid-Open No. 7-234410

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a liquid crystal alignment film excellent in stability of a pretilt angle and suppressed in lowering of a voltage holding ratio even under a high temperature environment for a long time, a liquid crystal display device having the liquid crystal alignment film, And a liquid crystal alignment treatment agent for forming a liquid crystal alignment film.

As a result of intensive studies, the present inventors have found that a liquid crystal alignment treating agent containing a polyamic acid using a specific diamine compound and / or a polyimide obtained by imidizing the polyamic acid as a diamine component And the present invention has been accomplished. In addition, the specific diamine compound contains a novel compound that is not included in the literature.

That is, the present invention has the following points.

(1) a polyamic acid obtained by reacting a diamine component containing a diamine compound represented by the formula [1] with a tetracarboxylic acid dianhydride, and a polyimide obtained by subjecting the polyamic acid to dehydration ring closure, A liquid crystal alignment treatment agent containing a polymer of the species.

[Chemical Formula 1]

(Wherein X ₁ represents -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, X ₃ is a single bond, _{O-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3) -, -N (CH 3) CO- or -O (CH ₂ ) _m - (m is an integer of 1 to 5), X ₄ is an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 4)

(2) The liquid crystal alignment treating agent according to (1), wherein X ₂ in formula [1] is a single bond or an alkylene group having 1 to 5 carbon atoms.

(3) The liquid crystal alignment treatment agent according to (1) or (2), wherein X ₄ in the formula [1] is an alkyl group having 1 to 5 carbon atoms.

(4) The compound according to any one of (1) to (3), wherein X _{1 in the} formula [1] is -O-, -CONH- or -COO-, X ₃ is a single bond or -O- and n is 1 By weight of the liquid crystal alignment treatment agent.

(5) The liquid crystal alignment treatment agent according to any one of (1) to (4), wherein 5 to 80 mol% of the diamine component is a diamine compound represented by the formula [1].

(6) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of (1) to (5).

(7) A liquid crystal display element having the liquid crystal alignment film according to (6) above.

(8) A diamine compound represented by the following formula [1].

(2)

(Wherein X ₁ represents -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, X ₃ is a single bond, _{O-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3) -, -N (CH 3) CO- or -O (CH ₂ ) _m - (m is an integer of 1 to 5), X ₄ is an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 4)

(9) A polyamic acid obtained by reacting a diamine component containing a diamine compound represented by the formula (1) described in (8) above with a tetracarboxylic acid dianhydride or a polyamic acid obtained by subjecting the polyamic acid to dehydration ring closure.

The liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in the stability of the pretilt angle even under a high temperature environment for a long time and can suppress the decrease in voltage holding ratio. Therefore, the liquid crystal display element having the liquid crystal alignment film is excellent in reliability.

Further, according to the present invention, a novel diamine compound useful as a raw material for a liquid crystal alignment treatment agent and the like is provided.

In the liquid crystal alignment treatment agent of the present invention, a diamine compound having an oxetane group represented by the following formula [1] (hereinafter also referred to as a specific diamine compound) is used.

(3)

(Wherein X ₁ represents -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, X ₃ is a single bond, _{O-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3) -, -N (CH 3) CO- or -O (CH ₂ ) _m - (m is an integer of 1 to 5), X ₄ is an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 4)

In the present invention, a polyamide acid obtained by the reaction of a diamine component containing a specific diamine compound and a tetracarboxylic acid dianhydride and a polyimide obtained by dehydrocondylating the polyamide acid are collectively referred to as a polymer . The polymer obtained by using the specific diamine compound in the present invention has the side chain of the following formula [1a].

[Chemical Formula 4]

(In the formula [1a], X ₁ , X ₂ , X ₃ and X ₄ have the same meanings as defined in the formula [1]

The oxetane group present at the end of the side chain of the formula [1a] reacts with a carboxyl group and / or a hydroxyl group under heating. Further, two oxetanes are addition-polymerized with each other. These reactions form a crosslinked structure of a plurality of polymers. The oxetane group has higher nucleophilicity than the epoxy group, and thus the reaction efficiency is high. Therefore, a plurality of polymers having a side chain of the formula [1a] are more likely to be crosslinked, and a liquid crystal alignment film having a structure with a high crosslinking density tends to be formed. Since the oxetane group has a four-atom cyclic structure, when it is reacted with a carboxyl group and / or a hydroxyl group, it contains one methylene group at a bonding site in comparison with an epoxy group having a three-atom cyclic structure. Further, because of the oxetane group present at the end of the side chain of the formula [1a], a liquid crystal alignment film having a high crosslinking density and high elongation and toughness properties can be easily obtained. From this point, it is presumed that the stretchability of the polymer at the time of rubbing is difficult to be inhibited, and scratches and cutting are less likely to occur.

The oxetane group present at the end of the side chain of the formula [1a] can cause the crosslinking reaction to proceed efficiently, and when the crosslinking compound is added, the unreacted Of the crosslinkable compound.

In view of the above, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has improved stability against heat of the pretilt angle as compared with a liquid crystal alignment film containing no crosslinkable compound or a liquid crystal alignment film containing a crosslinkable compound , It is possible to suppress a decrease in the voltage holding ratio under a high temperature environment. Therefore, it is difficult for line ghosting, which is one of the display defects, to occur, so that a liquid crystal display element having excellent reliability can be obtained.

≪ Specific diamine compound &

The specific diamine compound of the present invention is a diamine compound having an oxetane group represented by the following formula [1].

[Chemical Formula 5]

In formula [1], X ₁ represents -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON CH ₃ ) -, -N (CH ₃ ) CO-. Among them, -O-, -NH-, -CONH-, -NHCO-, -CON (CH ₃ ) -, -CH ₂ O-, -COO- or -OCO- is preferable because a diamine compound is easy to synthesize . More preferably -O-, -CONH-, -CON (CH ₃ ) -, -CH ₂ O- or -COO-. More preferably -O-, -CONH- or -COO-, and particularly preferably -COO-.

In the formula [1], X ₂ is a single bond, an aliphatic hydrocarbon group of 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. It may also have an unsaturated bond.

Specific examples of the non-aromatic hydrocarbon group include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cyclododecane ring, cyclododecane ring, And examples thereof include a ring, a cyclotetradecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctadecane ring, a tricyclohexane ring, A decanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring and the like.

Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring and a phenalene ring.

Preferable examples of X ₂ include a single bond, an alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, More preferably a single bond, an alkyl group having a carbon number of 1 to 10, an unsaturated alkyl group having a carbon number of 1 to 10, a cyclohexane ring, a cyclohexane ring, a benzene ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring, A norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a fluorene ring or an anthracene ring, more preferably a single bond, an alkylene group having 1 to 5 carbon atoms or a benzene ring. Most preferably a single bond or an alkylene group of 1 to 5 carbon atoms.

In formula [1], X ₃ represents a single bond, -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N (CH ₃ ) CO-, -O (CH ₂ ) _m - (m is an integer of 1 to 5). -O-, -NH-, -CONH-, -NHCO-, -COO-, -OCO- or -O (CH ₂ ) _m - (wherein m is an integer of 1 to 5) More preferably a single bond, -O-, -NH-, -CONH-, -NHCO-, -COO-, -OCO- or -O (CH ₂ ) _m - (m is an integer of 1 to 5) , More preferably a single bond, -O-, -CONH- or -COO-, particularly preferably a single bond or -O-.

In the formula [1], X ₄ represents an organic group having 1 to 20 carbon atoms, and heteroatoms (N, O, S, Si) may be contained in the organic group. Preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

In the formula [1], n is an integer of 1 to 4. More preferably 1 to 3, and more preferably 1, from the viewpoint of reactivity with the tetracarboxylic acid dianhydride.

The bonding position of two amino groups (-NH ₂ ) in the formula [1] is not limited. Concretely, with respect to the coupler X ₁ of the side chain, positions 2 and 3 on the benzene ring, positions 2 and 4, positions 2 and 5, positions 2 and 6, positions 3 and 4, 5 < / RTI > Among them, from the viewpoint of reactivity in the synthesis of polyamic acid, positions 2 and 4, positions 2 and 5, and positions 3 and 5 are preferable. When the ease of synthesis of the diamine compound is also considered, positions 2 and 4 or positions 3 and 5 are more preferable.

It is particularly preferable that X _{1 in the} formula [1] is -O-, -CONH- or -COO-, X ₃ is a single bond or -O-, and n is 1.

In the formula [1], X ₁ is -O-, -CONH- or -COO-, X ₂ is a single bond or an alkylene group having 1 to 5 carbon atoms, X ₃ is a single bond or -O-, X ₄ is an alkyl group having 1 to 5 carbon atoms, and n is particularly preferably 1.

Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ and n in the formula [1] are as shown in Table 1 below.

≪ Synthesis method of specific diamine compound >

The method for producing the specific diamine compound represented by the formula [1] of the present invention is not particularly limited, and preferred methods include the following methods.

The specific diamine compound of the present invention is obtained by synthesizing a dinitro compound represented by the following formula [2], further reducing the nitro group and converting it into an amino group.

[Chemical Formula 6]

(Equation _{[2] X 1, X 2} , X 3, X 4 and n have the same significance and X _1, X _2, the definition of X _3, X ₄ and n in the formula (1) in a)

The method for reducing the dinitro group is not particularly limited and a palladium catalyst such as palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon or the like is used as a catalyst and ethyl acetate, toluene, tetrahydrofuran, Dioxane, an alcohol-based solvent or the like using hydrogen gas, hydrazine, hydrogen chloride, or the like.

The dinitro compound represented by the formula [2] can be obtained by a method in which -X ₂ -X ₃ is bonded to dinitrobenzene via X ₁ .

X ₁ represents -O- (ether bond), -NH- (amino bond), -N (CH ₃ ) - (methylated amino bond), -CONH- (amide bond), -NHCO- CH ₂ O- (methylene ether bond), -COO- (ester bond), -OCO- (reverse ester _{bond), -CON (CH 3) -} (N- methylated amide linkages) and -N (CH ₃₎ CO- (N-methylated inverted amide bond), and these bond groups can be formed by a conventional organic synthetic method.

For example, when X ₁ is an ether or methylene ether bond, a method of reacting the corresponding dinitro group-containing halogen derivative with a hydroxyl group derivative containing X ₂ , X ₃ and X ₄ in the presence of an alkali or a method of reacting a dinitro group- Derivative and a halogen-substituted derivative containing an oxetane group having X ₂ , X ₃ and X ₄ are reacted in the presence of an alkali.

An amino group-containing derivative containing a corresponding dinitro group-containing halogen derivative and an oxetane group having X ₂ , X ₃ and X ₄ is reacted in the presence of an alkali.

In the amide bond, there can be mentioned a method in which an amino group substituent containing an oxetane group having a corresponding dinitro group-containing acid chloride group and X ₂ , X ₃ and X ₄ is reacted in the presence of an alkali.

In the case of a reverse amide bond, there can be mentioned a method of reacting an acid chloride substituent containing a corresponding dinitro group-containing amino group substituent and an oxetane group having X ₂ , X ₃ and X ₄ in the presence of an alkali.

In the case of an ester bond, there can be mentioned a method of reacting a corresponding dinitro group-containing acid chloride compound and a hydroxyl group-substituted derivative containing an oxetane group having X ₂ , X ₃ and X ₄ in the presence of an alkali.

In the case of a reverse ester bond, there can be mentioned a method in which an acid chloride containing a corresponding dinitro group-containing hydroxyl group derivative and an oxetane group having X ₂ , X ₃ and X ₄ is reacted in the presence of an alkali.

Specific examples of the dinitro group-containing halogen derivative and the dinitro group-containing derivative include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene, 3,5- Dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5-dinitrobenzoyl chloride, 2,4-dinitrobenzyl chloride, 3, Dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2, 5-dinitrophenol, 2,6-dinitrophenol, 2,4-dinitrophenylacetic acid, and the like. Considering the availability of raw materials and the reaction surface, one or more species can be selected and used.

≪ Other diamine compounds >

In the present invention, as long as the effect of the present invention is not impaired, other diamine compounds other than the specific diamine compound can be used in combination as the diamine component. Specific examples thereof are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- Diaminodiphenol, 3,5-diaminophenol, 3,5-diaminobenzyl, 2,4-diaminophenol, 3,5-diaminophenol, Alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diamino Biphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'- diaminobiphenyl, Diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diamino Phenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- bis (3-aminophenyl) silane, Aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 2,3-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, (2,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl Diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 ' - diaminobenzophenone, 2,3'-diaminobenzophenone, Diaminonaphthalene, 1,6-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,6-diaminonaphthalene, Bis (4-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) ) Propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1, (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, Phenylene bis (methylene)] dianiline, 4,4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ , 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, Phenylenebis [(3-amino)] phenanthrene [(4-aminophenyl) methanone] Phenylenemethanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [ Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate) Bis (3-aminophenyl) isophthalate, bis (4-aminophenyl) isophthalate, N, N ' Bis (4-aminobenzamide), N, N '- (1,4-phenylene) bis (3-aminobenzamide), N, N '- (1,3-phenylene) bis (3-aminobenzamide), N, N'- Bis (3-aminophenyl) terephthalamide, N, N'-bis (4- (4-aminophenoxy) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis [ Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, Bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis Butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, Heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) heptane, ) Octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) (Aminophenoxy) undecane, 1,12- (4-aminophenoxy) undecane, 1,11- (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane and the like, alicyclic diamines such as 1,3- Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diamine Aliphatic diamines such as nonanoyl, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

The diamine side chain may include an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a diamine having a substituent having a large-diameter substituent composed of the same. Specific examples include diamines represented by the following formulas [DA1] to [DA32] Diamine.

(7)

(In the formulas [DA1] to [DA5], R ₁ is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

[Chemical Formula 8]

(In the formulas [DA6] to [DA11], R ₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, R ₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group)

[Chemical Formula 9]

(Wherein R ₄ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ₅ represents a C 1 to C 22 An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

[Chemical formula 10]

(Wherein [DA14] ~ formula [DA16] of, R ₆ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH ₂ - or -CH ₂ -, and R ₇ is an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms)

(11)

(Wherein [DA17] and formula [DA18] of, R ₈ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH 2 -, -CH 2 OCO-, -CH 2 O-, -OCH ₂ -, -CH ₂ -, represents a -O- or -NH-, R ₉ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group )

[Chemical Formula 12]

(In the formulas [DA19] and [DA20], R ₁₀ is an alkyl group having 3 to 12 carbon atoms and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer, respectively.

[Chemical Formula 13]

(Wherein [DA21] and formula [DA22] one, R ₁₁ is an alkyl group having a carbon number of less than 312, a cis-1,4-cyclohexylene-trans reason is respectively trans isomers)

[Chemical Formula 14]

[Chemical Formula 15]

Also, a diaminosiloxane represented by the following formula [DA33] may be mentioned.

[Chemical Formula 16]

(In the formula [DA33], p is an integer of 1 to 10)

Further, diamines of the following formula [DA34] can be mentioned.

[Chemical Formula 17]

(In the formula [DA34], A ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group, A ₂ is an oxygen atom or -COO- * (However, the number of bond attached to "*" is bonded and a _3), and, a ₁ is a bond and the number of bond attached to an oxygen atom or -COO- * (However, the "*" (CH ₂₎ a2 A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a 3 is an integer of 0 or 1)

The other diamine compounds may be used alone or in combination of two or more thereof, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

≪ Tetracarboxylic acid dianhydride >

The tetracarboxylic acid dianhydride used in the present invention is not particularly limited. Specific examples thereof are given below.

Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, Anthracene tetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4- Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4- Dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2- Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid, 2 , 6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid, oxydi Tetracarboxylic acid, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid , 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, Dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cycloheptane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetracarboxylic acid, Cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [ , 4,0] decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6>] undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butane Dicarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, bicyclo [ , 2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane- Tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxy norbornane-2 : 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like.

 The tetracarboxylic acid dianhydride can be used alone or in combination of two or more, depending on the properties such as liquid crystal aligning property, voltage holding property, and accumulated charge when the liquid crystal alignment film is used.

<Polymer>

As described above, the polymer of the present invention is a polyimide having a specific diamine compound as a raw material or a polyimide obtained by dehydration ring closure of the polyamic acid.

In the liquid crystal alignment film obtained from the polymer of the present invention, the more the content of the specific diamine compound in the diamine component is, the more the stability of the pretilt angle against heat is improved.

For the purpose of enhancing the above characteristics, it is preferable that 1 mol% or more of the diamine component is a specific diamine compound. Further, it is preferable that 5 mol% or more of the diamine component is a specific diamine compound, more preferably 10 mol% or more. From the viewpoint of the uniform coating property when the liquid crystal alignment treatment agent is applied, the specific diamine compound is preferably 80 mol% or less, more preferably 40 mol% or less of the diamine component, % Or less.

When the polyamic acid of the present invention is obtained by the reaction of the diamine component and the tetracarboxylic acid dianhydride, a known synthetic method can be used. Generally, the tetracarboxylic acid dianhydride and the diamine are reacted in an organic solvent. The reaction of the tetracarboxylic acid dianhydride with the diamine is advantageous in that it proceeds comparatively easily in an organic solvent and does not generate any by-products.

The organic solvent used for the reaction of the tetracarboxylic acid dianhydride and the diamine is not particularly limited as long as it dissolves the produced polyamic acid. Specific examples thereof are given below.

N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve, ethyl cellosolve, methyl cellosolve, But are not limited to, sorbose, methylcellosolve acetate, ethylcellosolve acetate, butylcarbitol, ethylcarbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate , Propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethyl Diethylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Propyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, N-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, propylene carbonate, propylene carbonate, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoacetate 3-methoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, propyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like. These may be used alone or in combination. Further, a solvent which does not dissolve the polyamic acid may be used in combination with the solvent within the range in which the produced polyamic acid is not precipitated. In addition, since moisture in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use an organic solvent which is dehydrated and dried.

When the tetracarboxylic acid dianhydride and the diamine component are reacted in an organic solvent, a method in which a solution in which a diamine is dispersed or dissolved in an organic solvent is stirred and a tetracarboxylic acid dianhydride is directly or dispersed or dissolved in an organic solvent and added , A method of adding a diamine to a solution in which a tetracarboxylic acid dianhydride is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride and a diamine, and the like. . When the tetracarboxylic acid dianhydride or diamine component is composed of a plurality of compounds, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, or the low molecular weight compounds reacted individually may be mixed and reacted, .

The temperature at which the tetracarboxylic acid dianhydride is reacted with the diamine component can be selected from any of -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C. If the concentration is excessively low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high and it becomes difficult to perform uniform stirring. Therefore, Is 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then an organic solvent may be added.

In the polymerization reaction of the polyamic acid, the ratio of the total number of moles of the tetracarboxylic acid dianhydride to the total number of the moles of the diamine component is preferably 0.8 to 1.2. As in the case of the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyamic acid.

The polyimide of the present invention is a polyimide obtained by dehydrocondylating the polyamic acid and is useful as a polymer for obtaining a liquid crystal alignment film.

In the polyimide of the present invention, the dehydration / removal rate (imidization rate) of the amidic acid group does not necessarily have to be 100%, but can be adjusted within a range of 45 to 85%, for example, depending on the purpose and purpose.

Examples of the method for imidizing a polyamic acid include thermal imidization in which a solution of a polyamic acid is heated as it is, and catalyst imidization in which a catalyst is added to a solution of a polyamic acid.

When the polyamic acid is thermally imidized in a solution, the temperature is preferably 100 ° C to 400 ° C, and more preferably 120 ° C to 250 ° C. It is preferable to carry out the removal while removing the water generated by the imidization reaction out of the system.

The catalyst imidation of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has a basicity suitable for proceeding the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

In the case of recovering the polyamic acid or polyimide produced from the reaction solution of polyamic acid or polyimide, the reaction solution may be put into a poor solvent and precipitated. Examples of poor solvents to be used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer introduced into the poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure or by heating. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the poor solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and it is preferable to use three or more poor solvents selected from these because the purification efficiency is further increased.

The molecular weight of the polyamic acid and the polyimide contained in the liquid crystal alignment treatment agent of the present invention is determined by GPC (Gel Permeation Chromatography) method in consideration of the strength of the coating film obtained therefrom, the workability in forming the coating film, The weight average molecular weight measured is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is a coating liquid for forming a liquid crystal alignment film and is a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing at least one kind of polymer selected from the above-mentioned polymers of the present invention. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.

In the present invention, all of the resin components may be a polymer used in the present invention, and other polymers may be mixed in the polymer of the present invention. At this time, the content of such another polymer in the resin component is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.

Such another polymer may be, for example, a polyamic acid or polyimide obtained by using a diamine other than a specific diamine compound as a diamine component to be reacted with a tetracarboxylic dianhydride.

The organic solvent used in the liquid crystal alignment treatment agent of the present invention is not particularly limited as long as it is an organic solvent dissolving the above-mentioned resin component.

The liquid crystal alignment treatment agent of the present invention may contain components other than those described above. Examples thereof include a solvent or a compound that improves film thickness uniformity and surface smoothness when the liquid crystal alignment treatment agent is applied, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

Specific examples of the solvent for improving the uniformity of the film thickness and the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopro Methyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid, methyl lactate, isobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ketone, methylcyclohexene, Ethyl acetate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methylethyl 3-ethoxypropionate, Methoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy- , 1-phenoxy Propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether- Ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, and lactic acid isoamyl ester.

The solvent for improving the uniformity of the film thickness or the surface smoothness may be one kind or a mixture of plural kinds may be used. When such a solvent is used, the amount of the solvent used is preferably from 5 to 80% by mass, more preferably from 20 to 60% by mass, based on the entire solvent contained in the liquid crystal alignment treatment agent.

Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

(For example, EF Top EF301, EF303 and EF352 manufactured by Tohchem Products), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC430 and FC431 SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Kagaku Co., Ltd.), and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl 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-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound which adheres to these substrates is used, the amount of the compound used is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent to be. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal alignment treatment agent of the present invention may be added with a dielectric substance or a conductive substance for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film, as long as the effect of the present invention is not impaired.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without rubbing treatment, light irradiation or the like, or without alignment treatment in a vertical alignment application, after coating and baking on a substrate. At this time, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. It is also preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed from the viewpoint of simplifying the process. In the reflection type liquid crystal display device, an opaque material such as a silicon wafer can be used only for a substrate on one side, and a material for reflecting light such as aluminum can be used as the electrode in this case.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. As other coating methods, there are dip, roll coater, slit coater, spinner and the like, and they may be used depending on the purpose.

The firing after coating the liquid crystal alignment treatment agent on the substrate can be carried out by evaporating the solvent at 50 to 300 deg. C, preferably 80 to 250 deg. C by a heating means such as a hot plate to form a coated film. The thickness of the coated film after firing is disadvantageous from the viewpoint of the power consumption of the liquid crystal display element if it is too thick, and the reliability of the liquid crystal display element is deteriorated when it is too thin. Therefore, the thickness is preferably 5 to 300 nm, more preferably 10 To 100 nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate having a liquid crystal alignment film attached thereto from the liquid crystal alignment treatment agent of the present invention is obtained by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is made inward, and the other substrate is bonded A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed, and then a substrate is bonded and sealed. At this time, the thickness of the spacer is preferably 1 to 30 mu m, more preferably 2 to 10 mu m.

As described above, the liquid crystal display device manufactured using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a liquid crystal television of a large screen and a large screen.

Example

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

&Quot; Synthesis of specific diamine compounds of the present invention &quot;

&Lt; Example 1 &gt;

Synthesis of diamine compound (4)

[Chemical Formula 18]

3-oxetane ethanol (2) (14.95 g, 146.4 mmol), triethylamine (16.29 g, 160.1 mmol) and tetrahydrofuran (150 ml) were added to a four-necked flask under nitrogen atmosphere at room temperature , A solution of 3,5-dinitrobenzoyl chloride (1) (33.70 g, 146.2 mmol) in tetrahydrofuran (40 ml) was added dropwise while maintaining the temperature at 15 ° C or lower. After completion of the reaction, the reaction solution was poured into 1 liter of pure water, and the obtained crystals were filtered and washed with pure water. The crystals were stirred in ethanol (200 ml) and then filtered and washed with ethanol to obtain Compound (3) (white crystals, 36.33 g, yield: 84%).

A mixture of compound (3) (30.00 g, 101 mmol) and 5% Pd-C (3 g) in tetrahydrofuran (300 mL) was stirred at room temperature in the presence of hydrogen. After completion of the reaction, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Hexane (200 ml) was added to the obtained crude product and stirred. After stirring, the crystal was filtered and washed with hexane. The obtained crystals were added to ethanol (100 ml) and stirred. The crystals were filtered and washed with ethanol to obtain a diamine compound (4) (white crystals, 21.45 g, yield 90%).

&Quot; Synthesis of polyamic acid and polyimide &quot;

In the following Examples 2 to 9 and Comparative Examples 1 to 4, synthetic examples of polyamic acid or polyimide are described. The meaning of the abbreviations used in the respective materials, the measurement of the molecular weight of the polyamic acid and the polyimide, The measurement of the rate of increase is as follows. The contents of polyamic acid and polyimide synthesized in Examples 2 to 9 and Comparative Examples 1 to 4 are shown in Tables 2 and 3, respectively.

(Tetracarboxylic acid dianhydride)

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride

[Chemical Formula 19]

(Specific diamine compound)

Diamine (4): The diamine compound synthesized in Example 1

[Chemical Formula 20]

(Other diamine compounds)

p-PDA: p-phenylenediamine

PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

PBCH5DAB: 1,3-Diamino-4- {trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

m-PBCH5DAB: 3,5-Diamino- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenyl} benzoate

[Chemical Formula 21]

(Crosslinkable compound)

KK1:

[Chemical Formula 22]

KK2:

(23)

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Measurement of molecular weight of polyamic acid and polyimide)

The molecular weights of the polyamic acid and the polyimide were measured using a room temperature gel permeation chromatography (GPC-101) manufactured by Showa Denko K.K. and a column (KD-803, KD-805) Respectively.

Column temperature: 50 ° C

30 mmol / l of lithium bromide-hydrate (LiBr.H ₂ O), 30 mmol / l of phosphoric acid-anhydrous crystals (o-phosphoric acid) as an additive, and 20 ml of tetrahydrofuran (THF ) &Lt; / RTI &gt; 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight about 900,000, 150,000, 100,000, 30,000) manufactured by Toso Corporation and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

(Measurement of imidization rate)

20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Scientific Co., Ltd.), 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) Was added to dissolve completely. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring device (JNW-ECA500) manufactured by Nippon Denshoku. The imidation rate is determined by using a proton originating from a structure that does not change before and after imidization as a reference proton and the proton peak integrated value derived from the NH group of the amide acid which appears in the vicinity of 9.5 to 10.0 ppm and the peak integrated value of this proton Was obtained by the following equation.

Imidization ratio (%) = (1 -? X / y) x 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH of the amide acid when the polyamic acid (imidization ratio is 0% The ratio of the number of reference protons to one protopertone.

&Lt; Example 2 &gt;

PODA (1.77 g, 16.4 mmol) and diamine (4) (1.10 g, 4.66 mmol) were mixed in NMP (14.4 g) After reacting at 80 ° C for 5 hours, CBDA (1.84 g, 9.38 mmol) and NMP (12.3 g) were added and reacted at 40 ° C for 6 hours to obtain a solution of polyamic acid (A) (concentration 25.4 mass%). This polyamic acid had a number average molecular weight of 23,900 and a weight average molecular weight of 59,500.

&Lt; Example 3 &gt;

NMP was added to the solution (20.0 g) of the polyamide acid (A) obtained in the same manner as in Example 2 to dilute the solution to a concentration of 6 mass%, acetic anhydride (2.48 g) and pyridine (1.90 g) And the mixture was reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a powder of polyimide (B). The polyimide had an imidization rate of 53%, a number average molecular weight of 21,300 and a weight average molecular weight of 51,200.

<Example 4>

PDA (1.63 g, 15.1 mmol) and diamine (4) (1.64 g, 6.94 mmol) were mixed in NMP (14.6 g) After reacting at 80 ° C for 5 hours, CBDA (1.82 g, 9.27 mmol) and NMP (12.7 g) were added and reacted at 40 ° C for 6 hours to obtain a solution of polyamic acid (C) (concentration 24.8 mass%). The polyamic acid had a number average molecular weight of 24,100 and a weight average molecular weight of 59,200.

&Lt; Example 5 &gt;

NMP was added to a solution (20.2 g) of the polyamide acid (C) obtained in the same manner as in Example 4 and diluted to 6 mass%. Acetic anhydride (2.50 g) and pyridine (1.95 g) And the mixture was reacted at 80 DEG C for 4 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a powder of polyimide (D). The imidization ratio of this polyimide was 55%, and the number average molecular weight was 22,400 and the weight average molecular weight was 52,500.

&Lt; Example 6 &gt;

PDA (1.01 g, 9.34 mmol) and diamine (4) (0.55 g, 2.33 mmol) were mixed in NMP (17.5 g) After reacting at 80 ° C for 5 hours, CBDA (1.83 g, 9.33 mmol) and NMP (15.9 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (concentration 25.3 mass%).

To the resulting polyamic acid solution (20.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.53 g) and pyridine (3.31 g) were added as an imidization catalyst and reacted at 90 ° C for 3 hours. The reaction solution was poured into methanol (310 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a powder of polyimide (E). The imidization ratio of the polyimide was 80%, the number average molecular weight was 16,300, and the weight average molecular weight was 45,400.

&Lt; Example 7 &gt;

PDA (1.89 g, 17.5 mmol) and diamine (4) (1.10 g, 4.66 mmol) were mixed in NMP (14.9 g) After reacting at 80 ° C for 5 hours, CBDA (1.83 g, 9.33 mmol) and NMP (12.3 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (concentration 24.5 mass%).

To the resulting polyamic acid solution (20.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (2.45 g) and pyridine (1.93 g) were added as imidation catalysts and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (280 mL), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide (F) powder. The imidization ratio of the polyimide was 55%, the number average molecular weight was 22,600, and the weight average molecular weight was 53,100.

&Lt; Example 8 &gt;

PDH (1.28 g, 11.8 mmol) and diamine (4) (1.12 g, 4.74 mmol) were mixed in NMP (16.5 g) After reacting at 80 ° C for 5 hours, CBDA (1.86 g, 9.48 mmol) and NMP (15.9 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (concentration 25.2 mass%).

To the resulting polyamic acid solution (20.5 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 90 ° C for 3 hours. The reaction solution was poured into methanol (330 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a powder of polyimide (G). The imidization ratio of the polyimide was 81%, the number average molecular weight was 16,100, and the weight average molecular weight was 44,800.

&Lt; Example 9 &gt;

PDA (1.26 g, 11.7 mmol) and diamine (4) (1.10 g, 4.66 mmol) were mixed in NMP (16.4 g) with stirring at room temperature for 30 minutes, BODA (3.50 g, 14.0 mmol), m-PBCH5DAB (3.12 g, 7.00 mmol) The mixture was allowed to react at 80 ° C for 5 hours and CBDA (1.83 g, 9.33 mmol) and NMP (15.3 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (concentration 25.4 mass%).

To the resulting polyamic acid solution (20.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (2.48 g) and pyridine (1.95 g) were added as an imidization catalyst and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a powder of polyimide (H). The imidization ratio of the polyimide was 55%, the number average molecular weight was 18,200, and the weight average molecular weight was 48,500.

&Lt; Comparative Example 1 &

PDA (2.29 g, 21.2 mmol) was mixed in NMP (13.1 g), reacted at 80 ° C for 5 hours, and then treated with CBDA (1.85 g, g, 9.43 mmol) and NMP (12.4 g) were added and reacted at 40 ° C for 6 hours to obtain a solution of polyamic acid (I) (concentration 25.0 mass%). This polyamic acid had a number average molecular weight of 25,400 and a weight average molecular weight of 63,300.

&Lt; Comparative Example 2 &

NMP was added to a solution (20.0 g) of the polyamide acid (I) obtained in the same manner as in Synthesis Example 1 and diluted to 6 mass%. Acetic anhydride (2.48 g) and pyridine (1.92 g) And the mixture was reacted at 80 DEG C for 4 hours. The reaction solution was poured into methanol (290 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a powder of polyimide (J). The imidization ratio of the polyimide was 55%, the number average molecular weight was 22,300, and the weight average molecular weight was 56,300.

&Lt; Comparative Example 3 &

PDA (1.26 g, 11.7 mmol) was mixed in NMP (17.3 g) and reacted at 80 ° C for 5 hours. Then, CBDA (1.83 g, g, 9.33 mmol) and NMP (15.3 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (concentration 25.3 mass%).

To the resulting polyamic acid solution (20.1 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidization catalyst and reacted at 90 deg. C for 3 hours. The reaction solution was poured into methanol (320 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a powder of polyimide (K). The polyimide had an imidization rate of 80%, a number average molecular weight of 16,100 and a weight average molecular weight of 44,200.

&Lt; Comparative Example 4 &

PDA (1.77 g, 16.4 mmol) was mixed in NMP (16.2 g) and reacted at 80 ° C for 5 hours. Then, CBDA (1.83 g, g, 9.33 mmol) and NMP (15.0 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (concentration 24.5 mass%).

To the obtained polyamic acid solution (20.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (4.48 g) and pyridine (3.28 g) were added as imidation catalysts and reacted at 90 deg. C for 3 hours. The reaction solution was poured into methanol (320 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a powder of polyimide (L). The imidization ratio of the polyimide was 81%, the number average molecular weight was 19,500, and the weight average molecular weight was 49,400.

[Production of liquid crystal alignment treatment agent]

In Examples 10 to 17 and Comparative Examples 5 to 11 described below, production examples of liquid crystal alignment treatment agents are described. [Production of liquid crystal cell] used for evaluation of each liquid crystal alignment treatment agent, [liquid crystal orientation property and pretilt angle Evaluation &quot; and &quot; Evaluation of electrical characteristics &quot; The contents and properties of the respective liquid crystal alignment treatment agents obtained in Examples 10 to 17 and Comparative Examples 5 to 11 are summarized in Table 4 and Table 5, respectively.

[Production of liquid crystal cell]

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of the substrate having the 3 × 4 cm ITO electrode attached thereto and heat-treated on a hot plate at 80 ° C. for 5 minutes and at 210 ° C. for 30 minutes in a thermocycling type clean oven, Of a polyimide coating film was obtained. The coated film surface was subjected to rubbing treatment under the conditions of a roll diameter of 120 mm, a rayon cloth rubbing apparatus at a number of revolutions of 700 rpm, a moving speed of 40 mm / sec, and a press-in amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film attached thereto. Two substrates having the liquid crystal alignment film attached thereto were prepared, and the liquid crystal alignment film surface was placed inside the spacers with a spacing of 6 占 퐉 and the rubbing direction was reversed. Then, the periphery was bonded with a sealant, Respectively. Liquid crystal (ZLI-2293 manufactured by Merck Japan Co., Ltd.) was injected into this vacant cell by a reduced pressure injection method, and the injection port was sealed to obtain a nematic liquid crystal cell (hereinafter also referred to as a liquid crystal cell) in an anti-parallel orientation. In Example 14, Example 16, Example 17, and Comparative Examples 3 to 7, MLC-6608 (manufactured by Merck Japan Co., Ltd.) was used as a liquid crystal.

[Evaluation of Liquid Crystal Alignment Property and Pretilt Angle]

The liquid crystal cell obtained in the above [Preparation of liquid crystal cell] was subjected to heating treatment at 95 DEG C for 5 minutes (treatment 1 in Table 4) after heat injection of liquid crystals (initial treatment), heating treatment at 120 DEG C for 5 hours and heating at 95 DEG C for 5 minutes After the treatment (treatment 2 in Table 4), the pretilt angle was measured. The pretilt angles were measured at three points of the center of the liquid crystal cell and a point of 1 cm above and below the center thereof, and the average value thereof was defined as the value of the pretilt angle. At that time, the measurement was carried out at room temperature using a pretilt angle measuring apparatus (model PAS-301 manufactured by ELSICON).

The alignment uniformity of the liquid crystal was confirmed by observing the polarizing microscope of the liquid crystal cell after initial and each heating treatment. A state in which the liquid crystal was uniformly oriented was evaluated as &amp; cir &amp; and a state in which disturbance was observed in the alignment of the liquid crystal was evaluated as x.

[Evaluation of electric characteristics]

A voltage of 4 V was applied for 60 seconds at a temperature of 80 DEG C to the liquid crystal cell obtained in the above [Production of Liquid Crystal Cell], and the voltage after 16.67 ms and after 1667 ms was measured. (Initial voltage holding ratio in Table 5).

The liquid crystal cell after the measurement of the voltage holding ratio was left in a thermostatic chamber set at 100 DEG C for 21 days, and the voltage holding ratio (voltage holding ratio after being left at high temperature in Table 5) was measured in the same manner as described above.

[Evaluation of rubbing resistance]

The surface of the substrate on which the rubbed liquid crystal alignment film obtained in [Preparation of Liquid Crystal Cell] was adhered was observed with a confocal laser microscope, and the presence or absence of rubbing scratches was confirmed.

A sample in which no rubbing scratches were observed was rated as?, And a sample with rubbing scratches was evaluated as x.

&Lt; Example 10 &gt;

(10.2 g), NMP (9.71 g) and BCS (20.0 g) obtained in the same manner as in Example 2 were mixed at 25 占 폚 for 12 hours to obtain a liquid crystal alignment treating agent (1). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 11 &gt;

Powder (2.51 g), polyimide (24.5 g) and BCS (11.6 g) obtained in the same manner as in Example 3 were mixed at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treatment agent (2). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 12 &gt;

(10.5 g), NMP (11.6 g) and BCS (18.0 g) obtained in the same manner as in Example 4 were mixed at 25 占 폚 for 12 hours to obtain a liquid crystal alignment treating agent (3). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 13 &gt;

Powder (2.50 g), NMP (18.7 g) and BCS (17.3 g) of the polyimide (D) obtained in the same manner as in Example 5 were mixed at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treating agent (4). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 14 &gt;

(2.55 g), NMP (26.9 g) and BCS (9.81 g) obtained in the same manner as in Example 6 were mixed at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 15 &gt;

Powder of polyimide (F) (2.48 g), NMP (16.6 g) and BCS (19.2 g) obtained in the same manner as in Example 7 was mixed at 50 占 폚 for 15 hours to obtain liquid crystal alignment treatment agent (6). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 16 &gt;

(2.50 g), NMP (28.3 g) and BCS (7.69 g) obtained in the same manner as in Example 8 were mixed at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Example 17 &gt;

Powder (2.50 g), NMP (22.6 g) and BCS (13.4 g) of the polyimide (H) obtained in the same manner as in Example 9 were mixed at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treatment agent (8). No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the solution was a homogeneous solution.

&Lt; Comparative Example 5 &

NMP (9.71 g) and BCS (20.2 g) were added to a solution (10.5 g) of the polyamic acid (I) obtained in Comparative Example 1 and stirred at 25 占 폚 for 12 hours to obtain a liquid crystal alignment treatment agent (9).

&Lt; Comparative Example 6 &gt;

Powder of polyimide (J) (2.45 g), NMP (24.0 g) and BCS (11.3 g) obtained in Comparative Example 2 were mixed at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treating agent (10).

&Lt; Comparative Example 7 &

(2.50 g), NMP (26.4 g) and BCS (9.62 g) of polyimide (K) obtained in Comparative Example 3 were mixed at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treatment agent (11).

&Lt; Comparative Example 8 &gt;

(2.45 g), the NMP (31.1 g), the BCS (11.3 g) and the crosslinkable compound KK1 (0.49 g) obtained in the same manner as in Comparative Example 3 were mixed at 50 占 폚 for 15 hours to obtain liquid crystals To obtain an orientation treatment agent (12).

&Lt; Comparative Example 9 &

(2.50 g), the NMP (31.7 g), the BCS (11.5 g) and the crosslinkable compound KK1 (0.50 g) obtained in Comparative Example 4 were mixed at 50 占 폚 for 15 hours to prepare a liquid crystal alignment treatment agent 13).

&Lt; Comparative Example 10 &

(2.48 g), the NMP (32.0 g), the BCS (11.1 g) and the crosslinkable compound KK2 (0.50 g) obtained in the same manner as in Comparative Example 3 were mixed at 50 占 폚 for 15 hours, To obtain an orientation treatment agent (14).

&Lt; Comparative Example 11 &

(2.52 g), NMP (31.8 g), BCS (11.4 g) and the crosslinkable compound KK2 (0.51 g) obtained in the same manner as in Comparative Example 4 were mixed at 50 占 폚 for 15 hours to obtain liquid crystals To obtain an orientation treatment agent (15).

As can be seen from the above results, the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Examples 10 to 17 exhibited uniform orientation and improved stability of the pretilt angle against heat. Even when exposed for a long time at a high temperature, Respectively. On the other hand, in the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Comparative Examples 5 to 7, alignment disorder of the liquid crystal, which is thought to be caused by rubbing scratches, was observed. In addition, the pretilt angle greatly decreased after the heat treatment at 120 ° C for 5 hours (heat treatment 2). On the other hand, in the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Comparative Examples 8 to 11, the voltage retention rate after the high temperature retention relative to the initial voltage retention rate was greatly decreased.

In addition, the comparison between Examples 10 and 12 and Comparative Example 5 and the comparison between Examples 11 and 13 to 17 and Comparative Examples 6 and 7 reveal that the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the Example has no cutting accompanied by the rubbing treatment , And the stability of the pretilt angle against heat was greatly improved. Thereby, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of these Examples can obtain a liquid crystal display element in which display unevenness does not occur even under extreme conditions in which the liquid crystal alignment film is used or left in a high temperature environment for a long time.

In comparison between Examples 10 and 12 and Comparative Example 9 and Examples 11 and 13 to 17 with Comparative Examples 6 and 7, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the Example exhibited a voltage when exposed for a long time at a high temperature The lowering of the retention rate was suppressed. As a result, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of these embodiments can provide a highly reliable liquid crystal display device that does not cause the ghosting, which is a display failure of the liquid crystal display element, even under extreme conditions.

On the other hand, in the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Comparative Examples 8 to 11, the voltage retention rate after the high temperature retention relative to the initial voltage retention rate was greatly decreased.

Industrial availability

The liquid crystal alignment treatment agent of the present invention is useful for a TN device, an STN device, a TFT liquid crystal device, and a vertically aligned liquid crystal display device, and can be preferably used for a liquid crystal television with a large screen and a large screen.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2009-295180 filed on December 25, 2009 are hereby incorporated herein by reference and the disclosure of the specification of the present invention.

Claims (10)

At least one polymer selected from the group consisting of a polyamic acid obtained by reacting a diamine component containing a diamine compound represented by the formula [1] with a tetracarboxylic acid dianhydride and a polyimide obtained by dehydrocondylating the polyamic acid And the liquid crystal alignment treatment agent.
[Chemical Formula 1]

(Wherein X ₁ represents -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or -N (CH ₃ ) CO-, X ₂ is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, X ₃ is a single bond, _{O-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH 3) -, -N (CH 3) CO- or -O (CH ₂ ) _m - (m is an integer of 1 to 5), X ₄ is an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 4) The method according to claim 1,
X ₂ in the formula [1] is a single bond or an alkylene group having 1 to 5 carbon atoms. The method according to claim 1,
X ₄ in the formula [1] is an alkyl group having 1 to 5 carbon atoms. The method according to claim 1,
X _{1 in the} formula [1] is -O-, -CONH- or -COO-, X ₃ is a single bond or -O-, and n is 1. The method according to claim 1,
5 to 80 mol% of the diamine component is a diamine compound represented by the formula [1]. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 5. A liquid crystal display element having the liquid crystal alignment film according to claim 6. A diamine compound represented by the following formula [1].
(2)

(Wherein X ₁ represents -O-, -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃₎ -, or -N (CH ₃₎ CO-, and, X ₂ represents a single bond, a carbon number of from 1 to 20 aliphatic hydrocarbon group, non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group, X ₃ is a single bond , -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N (CH ₃ ) CO-, Or -O (CH ₂ ) _m - (m is an integer of 1 to 5), X ₄ is an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 4) A polyamic acid obtained by reacting a diamine component containing a diamine compound represented by the formula [1] according to claim 8 with a tetracarboxylic acid dianhydride. A polyimide obtained by subjecting a polyamic acid obtained by the process of claim 9 to dehydration ring closure.