TW201137037A - Liquid crystal-aligning agent, liquid crystal alignment film, and liquid crystal display element using same - Google Patents

Abstract

A liquid crystal-aligning agent comprising at least one kind of a polymer selected from the group consisting of a polyamic acid, which is obtained by reacting a diamine component containing a diamine compound represented by formula [1] with a tetracarboxylic dianhydride, and a polyimide obtained by the dewatering cyclization of said polyamic acid. In formula [1], X1 represents -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-; X2 represents a single bond or an aliphatic hydrocarbon group, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, each group having 1 to 20 carbon atoms; X3 represents a single bond, -O-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH3)-, -N(CH3)CO- or -O(CH2)m- (wherein m is an integer of 1 to 5); X4 represents an organic group having 1 to 20 carbon atoms; and n is an integer of 1 to 4.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element used in a liquid crystal display element. [Prior Art] In the liquid crystal display device, the liquid crystal alignment film has an effect of aligning the liquid crystals in a certain direction. Nowadays, the main liquid crystal alignment film used in the industry is a polyamido acid (also known as polylysine) or a polyamidene solution formed from a polyimine solution. The liquid crystal alignment treatment agent is applied onto a substrate to form a film. Further, when the liquid crystal is aligned in the direction of the substrate or obliquely aligned, the surface of the substrate is subjected to surface stretching treatment by rubbing treatment. Further, it has been proposed to use a method of anisotropic photochemical reaction such as polarized ultraviolet ray irradiation instead of rubbing treatment, and in recent years, it has been reviewed for industrialization. The liquid crystal alignment film is used for controlling the angle of the liquid crystal to the substrate, that is, the pretilt angle of the liquid crystal. However, the liquid crystal display element is improved in performance, and the use range thereof is expanding year by year, and not only a certain pretilt angle but also a pretilt angle can be obtained. The stability of the dip is also becoming increasingly important. In terms of the stability of the pretilt angle, in the manufacturing process of the liquid crystal alignment film, it is proposed to contain a predetermined pretilt angle regardless of the friction condition, and it is proposed to be contained in the molecule in the polyaniline liquid crystal alignment treatment agent. A compound having two epoxy groups (for example, see Patent Document). Further, in the manufacturing process of the liquid crystal display device, in order to improve the uniformity of the alignment of the liquid crystal, the liquid crystal is sealed after the liquid crystal is sealed, and the liquid crystal is made uniform. However, when the stability of the pretilt angle is low, after the uniformity treatment, the pretilt angle of the target size cannot be obtained, or the problem that the pretilt angle causes an uneven sentence is caused. In particular, in the case of high brightness, a liquid crystal display element using a background light having a large amount of heat, or a liquid crystal display element used in an automobile application, such as a navigator or an instrument panel, may be used for a long time in a high temperature environment or Placement situation. Under such severe conditions, when the pretilt angle is slowly changed, the initial display characteristics or the occurrence of streaks during display cannot be obtained. In recent years, it has been widely used in large-screen, high-definition liquid crystal televisions, which are required to be used in an overly harsh environment when compared with liquid crystal display elements that are mainly used for displaying screen characters or still images. Time to endure the characteristics of use. Therefore, liquid crystal alignment films require higher reliability. In particular, when the voltage holding ratio of one of the electrical characteristics is lowered, there is a case where the display of the liquid crystal display element is likely to be poor, and the liquid crystal display element having high reliability cannot be obtained. Therefore, not only the initial characteristics are required to be good, but also, for example, even after exposure to a high temperature for a long period of time, it is not easy to have a reduced shape. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open No. Hei. No. 7-2, No. 3, No. 4, No. A liquid crystal alignment film having excellent stability of a pretilt angle and suppressing a decrease in voltage holding ratio in a high-temperature environment, a liquid crystal display element having the liquid crystal alignment film, and a liquid crystal alignment treatment agent for forming the liquid crystal alignment film. The inventors of the present invention have further intensively reviewed the results of the review and found that the polyamine containing the specific diamine compound as the diamine component and/or the polyimine-containing liquid crystal obtained by subjecting the polyamic acid to the imine. The alignment treatment agent is extremely effective in achieving the above object, and the present invention has been completed. Further, the above specific diamine compound contains those not described in the literature. In other words, the present invention has the following gist. [1] A liquid crystal alignment treatment agent comprising a polyamic acid selected from the group consisting of a diamine component containing a diamine compound represented by the formula [1] and a tetracarboxylic dianhydride, and the polymerization is carried out. At least one polymer of a group of polyimine obtained by dehydration ring closure of proline.

(In the formula [1], Χι is -0-, -NH-, -N(CH3)-, -CONH-, -NHCO-

X2 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, and a X3 single bond, -0-, -NH-, -N(CH3)-,

-N(CH3)CO- or - 0(CH2)m- (m is an integer of 1 to 5), X4 represents an organic group having 1 to 20 carbon atoms, and n is an integer of 1 to 4) 201137037 (2) The liquid crystal alignment treatment agent according to the above [1], wherein x2 of the formula [丨] is a single bond or an alkylene group having a carbon number of 1 to 5. (3) The liquid crystal alignment treatment agent according to the above [1], wherein X4 of the formula [1] is an alkyl group having 1 to 5 carbon atoms. (4) The liquid crystal alignment treatment agent according to any one of the above-mentioned [1], wherein X in the formula [1] is -0-, -CONH- or -COO-, X3 is a single bond or In the liquid crystal alignment treatment agent according to any one of the above [1] to (4), wherein 5 to 80 mol% of the diamine component is in the formula [1] A diamine compound is shown. (6) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of the above [1] to (5). (7) A liquid crystal display element comprising the liquid crystal alignment film according to (6) above. (8) A diamine compound characterized by the following formula [1]. [Chemical 2]

[1] (in the formula [1], Xi /^-〇-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -ch2o-, -coo-, -oco-, -con (ch3)- or -n(ch3)co-, X2 single bond, aliphatic hydrocarbon group having 1 to 20 carbon atoms, non-aromatic cyclic hydrocarbon group, or aromatic hydrocarbon group, X3 single bond, -〇-, - NH-, -N(CH3)-, -C0NH-, -NHCO-, -COO-, -OCO-, -CON(CH3)-, 201137037 -N(CH3)CO- or - CKCHOn^m system 1~5 (Integer), X4 represents an organic group having 1 to 20 carbon atoms, and an integer of η is 1 to 4) (9) A polyimine which is characterized by containing the formula (8) The polyamine acid obtained by reacting the diamine component of the diamine compound with the tetracarboxylic dianhydride or the polyhydric acid is dehydrated and closed. [Effect of the Invention] The liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in the stability of the pretilt angle even in a high temperature environment for a long period of time, and can suppress a decrease in the voltage holding ratio. Therefore, the liquid crystal display element having the liquid crystal alignment film is excellent in reliability. Moreover, according to the present invention, a useful novel diamine compound which is a raw material of a liquid crystal alignment treatment agent or the like can be improved. [In order to carry out the invention] The liquid crystal alignment agent of the present invention is a diamine compound having an oxetanyl group (hereinafter also referred to as a specific diamine compound) represented by the following formula [1]. [Chemical 3]

[1] (In the formula [1], 乂1 series-0-, -]^1€-, -:^((:113)-, -(:0]^11-, -]^11(:0 -, -CH20-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, 201137037 x2 is a single bond, an aliphatic hydrocarbon group having a carbon number of 1 to 2 0, a non-aromatic ring a hydrocarbon group or an aromatic hydrocarbon group, a Χ3 series single bond, -0-, -ΝΗ-, -N(CH3)-, -CONH-, -NHCO-, -COO-, -0C0-, -CON(CH3)- -N(CH3)CO- or -0(CH2)m- (m is an integer of 1 to 5), X4 represents an organic group having 1 to 20 carbon atoms, and an integer of η is 1 to 4). In the present invention a polylysine obtained by reacting a diamine component containing a specific diamine compound with a tetracarboxylic dianhydride, and a polyimine obtained by subjecting the polyamic acid to dehydration ring closure, also collectively referred to as a polymer The polymer obtained by using the specific diamine compound of the present invention has a side chain of the following formula (1a). [Chemical 4] - XfX2_X3

[la] (in the formula (la), Xi, X2, X3 and X4 have the same meanings as defined in the above formula [1]) oxetanyl group present at the end of the side chain of the formula (la), It reacts with a carboxyl group and/or a hydroxyl group under heating. Further, the two oxetanyl groups may be added to each other to form a polymerization. By this reaction, a plurality of polymer crosslinked structures are formed. Since the oxetane group has higher nuclearity than the epoxy group, the reaction efficiency is high. Therefore, a plurality of polymers having a side chain of the formula (la) are more easily crosslinked, and it is easier to form a liquid crystal alignment film having a high crosslinking density. In addition, since the oxetanyl group is a 4-carbon ring structure, when reacting with a thiol group and/or a thiol group, 'when compared with an epoxy group having a 3-carbon ring structure, 'containing more than 1 at a bonding site. Methylene group. Further, 'the oxetane group which is present at the end of the side chain of the formula (la)-10-201137037, it is easy to obtain a structure having a high crosslinking density and a liquid crystal alignment having high tensile properties or toughness. membrane. From this, it is presumed that it becomes difficult to prevent the elongation of the polymer during rubbing, and it is less likely to cause scratches or cuts. Further, the oxetane group which is present at the end of the side chain of the formula (la) can effectively carry out the crosslinking reaction, whereby the crosslinking property is not caused to cause deterioration of the characteristics of the liquid crystal display element. The case where the unreacted crosslinkable compound remains for the same reason. According to the above, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can improve the pretilt angle to heat stability when compared with a liquid crystal alignment film having no crosslinkable compound or a liquid crystal alignment film to which a crosslinkable compound is added. Sexuality and suppression of a decrease in voltage holding ratio in a high temperature environment. Therefore, since the wire firing of one of the poor display is less likely to occur, 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 5]

' X in the formula [1] is selected from -0-, -NH-, -N(CH3)-, -CONH-

-11 - 201137037 -N(CH3)CO- 2 valent organic base. Among them, '-O-'-NH-'-CONH-, -NHCO-, -CON(CH3)-, -CH20., -COO- or -OCO- is preferred because it is easy to synthesize a diamine compound. More preferred are - Ο-, -CON Η-, -CON(CH3)-'-CH20- or -COO-. Particularly preferred is -〇-, -CONH- or -COO- 〇 is preferably -COO - in the formula [1], x2 is a single bond, an aliphatic hydrocarbon group having a carbon number of 1 to 20, and 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. In addition, it may have an unsaturated bond. Specific examples of the non-aromatic hydrocarbon group, such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring, a cyclodecane ring, and a ring Monoalkane, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring 'cyclohexadecane ring, cyclooctadecane ring, cyclopentadecane Ring, cycloecosane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicycloheptane ring, dehydronaphthalene ring, norbornene ring, gold steel ring, and the like. Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a molybdenum ring, an anthracene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, a phenalene ring and the like. Desirable X2 is a single bond, an alkylene group having 1 to 1 carbon atom, an unsaturated alkyl 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, a gold alkyl alkane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an anthracene ring or an anthracene ring, and more preferably a single bond 'carbon number 1 to 1 () Unsaturated polycarbonate with a carbon number of 1 to 10, ring of cyclohexyl ring, thin ring of ortho-azide, alkane ring of gold, benzene ring, naphthalene ring, anthracene ring or anthracene ring, especially preferred is single-12-201137037 bond, carbon A number 1 to 5 alkyl or benzene ring. The most preferred ones are single bonds or alkylene groups having a carbon number of 1 to 5. In the formula [1], X3 is selected from the group consisting of a single bond, -0-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH3)- -N(CH3)CO- or -0(CH2)m- (m is an integer from 1 to 5). Preferably, it is selected from the group consisting of a single bond, -Ο-, -NH-, -CONH-, -NHCO-, -COO-, -OCO-, or -0(CH2)m- (m is an integer of 1 to 5) More preferably, it is a single bond, -〇-, -NH-, -CONH-, -NHCO-, -COO-, -OCO- or -0(CH2)m- (m is an integer of 1 to 5), especially The best one is a single bond, -〇-, -CONH- or -COO-, and the best one is a single bond or -0-. In the formula [1], X4 represents an organic group having 1 to 20 carbon atoms, and may also contain a hetero atom (N, 0, S, Si) in the organic group. Preferred is an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. In the formula [1], η is an integer of 1 to 4. In terms of reactivity with tetracarboxylic dianhydride, it is preferably from 1 to 3, more preferably from 1. The bonding position of the two amine groups (-ΝΗ2) of the formula [1] is not particularly limited. Specifically, the bonding group of the side chain (X 〇, the position of 2, 3 on the benzene ring, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3, 4) In the position of 3, 5, in terms of the reactivity in the synthesis of polylysine, the position of 2, 4, 2, 5 or 3, 5 is preferred. In terms of easiness of time, it is better to position 2 or 4 or 3 or 5. The 乂1 of the formula [1] is -〇-, -C0NH- or -COO-, Χ3 is a single bond or - 〇- ' η is 1 is better. -13- 201137037 and X of the formula [1] is -0-, -CONH- or -COO-, X2 is a single bond or an alkylene group having a carbon number of 1 to 5, and X3 is A single bond or -0-, X4 is an alkyl group having a carbon number of 1 to 5, and !1 is preferably 1. A preferred combination of X1, X2, X3, X4 and η of the formula [1] is shown in Table 1 below. . [Table 1]

Xi X, x3 X* η A- 1 -0- single bond single bond carbon number 1~5 of the yard base 1 Α- 2 carbon number b 5 alkyl group single bond carbon number 1~5 alkyl 1 Α- 3 -0- Carbon number 5 alkyl group * 〇 - alkyl group having 1 to 5 carbon atoms - 1 A - 4 -C0NH- single bond single bond carbon number 5 alkyl group 1 A - 5 -C0NH- carbon Number of 1 to 5 alkyl groups having a single bond carbon number of 1 to 5 1 A- 6 -C0NH- carbon number 5 alkyl group having 1 to 5 alkyl groups 1 A- 7 -COO- single bond Single bond carbon number 1~5 of yard base 1 A- 8 - COO- carbon number 1~5 alkyl group single bond carbon number 1~5 alkyl 1 A- 9 -coo- carbon number 1~5 Alkyl group 1 having a thiol group number of 1 to 5 <Synthesis method of a specific diamine compound> A method for producing a specific diamine compound represented by the formula [1] of the present invention is not particularly limited, and a preferred method For example, the method described below. The specific diamine compound of the present invention can be obtained by synthesizing a dinitro group represented by the following formula (2), reducing the nitro group, and converting it into an amine group. [Chemical 6]

(Χ2, Χ3, χ4, and η of the formula (2) are the same as the definitions of X, Χ2, Χ3, Χ4, and η of the formula [1]) The method for reducing the dinitro group is not particularly limited, and is usually used - 14 - 201137037 Palladium-carbon, platinum oxide, nickel-plated nickel, platinum black, lanthanum-alumina, sulphide-platinum carbon, etc. as a catalyst, in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent A method carried out by hydrogen, hydrazine, hydrogen chloride or the like. The dinitrobenzene of the formula (2) can be produced by a method of bonding -x2-x3 via X!, for dinitrobenzene.

Xi is selected from the group consisting of -〇-(ether bond), -NH-(amine bond), -N(CH3)-(methylated amine bond)'-CONH-(melamine bond), -NHCO-(reverse 醯Amine bond), -CH20- (methylene ether bond), -COO- (ester bond), -OCO- (reverse ester bond), -CON(CH3)-(N-methylated guanamine bond) and - A bonding group of N(CH3)CO-(N-methylated reverse guanamine bond), which can be formed by a general organic synthesis method. For example, when X! is an ether or a methylenediether bond, a corresponding dinitro-containing halogen derivative and a hydroxy derivative containing x2, x3 and x4 are reacted in the presence of a base, or a dinitro group is contained. A method in which a hydroxy derivative and a halogen-substituted derivative having an oxetanyl group having X2, X3 and X4 are reacted in the presence of a base. In the case of an amine bond, for example, a method in which a corresponding dinitro group-containing halogen derivative and a halogen-substituted derivative containing an oxetanyl group having X2, X3 and X4 are reacted in the presence of a base. In the case of a guanamine bond, for example, a method in which a corresponding nitro acid chloride is contained and an amino group-substituted derivative having an oxetanyl group having x2, x3 and x4 is reacted in the presence of a base. In the case of a reverse amide bond, for example, the corresponding nitro group-containing amine substituent and -15-201137037 containing an acid chloride having x2, x3 and χ4 oxetanyl groups are reacted in the presence of a base. method. In the case of an ester bond, for example, a method in which a corresponding nitro acid chloride is contained and a hydroxy-substituted derivative containing an oxetanyl group having X2, x3 and X4 is reacted in the presence of a base. In the case of a reverse ester bond, for example, a method in which a corresponding nitro group-containing hydroxy derivative and an acid chloride having an oxetanyl group having x2, x3 and x4 are reacted in the presence of a base. Specific examples of dinitro-containing halogen derivatives and dinitro-containing derivatives, such as 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene , 3,5-dinitrobenzoic acid chloride, 3,5·dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4·dinitrobenzoic acid, 3,5-di Nitrobenzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,4-dinitroaniline 3,5·dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4-di Nitrophenylacetic acid and the like. One or a plurality of species may be selected in consideration of the availability and reaction of the raw materials. <Other diamine compound> In the present invention, other diamine compounds other than the specific diamine compound may be used as the diamine component without impairing the effects of the present invention. The specifics thereof are as follows. P-phenylenediamine, 2,3,5,6-tetramethyl-P-phenylenediamine, 2,5-dimethyl-P-phenylenediamine, m-phenylenediamine, 2,4-dimethicone Base-m-phenylenediamine, 2,5-diaminomethyl-16-201137037 Benzene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3 ,5-Diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl , 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy- 4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3' -Trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl , 2,3'-diaminobiphenyl, 4,4'-diaminophenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-Diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-di Diphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, two Methyl-bis(4-aminophenyl)decane, dimethylbis(3-aminophenyl)decane, 4,4'-sulfurized diphenylamine, 3,3'-sulfurized diphenylamine, 4,4' -diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine' 2,3'-diaminodiphenylamine , N-methyl (4,4, diaminodiphenyl)amine, N-methyl (3,3'-diaminodiphenyl)amine, N-methyl (3,4'-diamine Diphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'- Diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diamine Benzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8- Diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diamino-7-201137037 naphthalene, 1,2- (4-Aminophenyl)ethane, i,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-double (3· Aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4) -aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-amino group Phenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene' 1,3-bis(4-aminophenoxy) Benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3, 4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[ 1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene bis[( 4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)-methyl Ketone], 1,3-phenylene bis[(3-aminophenyl)methanone] 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-amine Benzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl) Terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, anthracene, Ν'-(1,4- Phenylene) bis(4-aminobenzoguanamine), hydrazine, Ν'-(1,3-phenylene) bis(4-aminobenzophthalamide), hydrazine, Ν'-(1, 4-phenylene) bis(3-aminobenzophthalamide), hydrazine, Ν'-(1,3-phenylene) bis(3-aminobenzophthalamide), hydrazine, Ν'-double (4-Aminophenyl) p-decylamine, hydrazine, Ν'-bis(3-aminophenyl)-p-guanamine, hydrazine, Ν'-bis(4-aminophenyl)isodecylamine ,Ν,Ν'-bis(3-aminophenyl)isodecylamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy) Diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl] -18 - 201137037 Propane, 2,2'-bis[4-(4-aminophenoxy) Phenyl]hexafluoro Propane, 2,2'-bis(4-aminophenyl)hexafluoropropane 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4) _Methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2,-bis(3-aminophenyl)propane, 2,2,_bis (3 _Amino 4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminophenoxy)propyl, l,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane 1,5-bis(4-aminophenoxy)pentane, i,5-bis(3-aminophenoxy)pentane, 16-bis(4-aminophenoxy)hexane, i,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)gum, 1,7-(3-aminophenoxy)glyoxime, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane , i,9-bis(3·aminophenoxy)decane, M〇-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 111 -(1 aminobenzene Oxy) undecane, 1,11-(3-aminophenoxy) eleventh, 1,12-(4-aminophenoxy)dodecane, 1;12-(3-amino group An alicyclic diamine such as an aromatic diamine such as phenoxy)dodecane, bis(4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl)methane; 3-diaminopropyl propyl 1,4-diaminobutane, i,5-diaminopentane, 1,6-diaminohexyl, 1,7-diaminoheptane, 1, 8-Diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. Aliphatic diamine. Further, for example, a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring or a macrocyclic substituent formed thereon in a side chain of a diamine is specifically, for example, the following The amine of the formula [DA1]~[DA32] is the -19-201137037 amine. [Chemistry 7]

[DA1] CDA2]

[DA5] (In the formula [DA1] to the formula [DA5], R is an alkyl group having a carbon number of 1 or more and 22 or less or a fluorine-containing alkyl group] [Chemical Formula 8]

(In the formula [DA6]~form [DA11], R2 is -COO-'-OCO-'-CONH-, -NHCO-, -CH2-, -Ο-, -CO- or -NH-, and R3 is a carbon number 1 or more, 22 or less alkyl or fluorine-containing alkyl groups) [Chemical 9]

(In the formula [DA12] and the formula [DA13], R4 is -0., -OCH2-, -CH20-, -COOCH2 or -CH2OCO-, and R5 is an alkyl group having 1 or more and 22 or less, an alkoxy group or Fluorinated alkyl or fluorine-containing alkoxy) -20- 201137037 [10]

[DAI 4] [DA 15] [DA16] (In the formula [DA14]~[DA16], R6 is -COO-'-OCO-'-CONH-, -NHCO-, -COOCH2-, -CH2OCO- ' - CH20-, -OCH" or -CH2-, R7 is an alkyl group having 1 or more and 22 or less carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group)

H2N nh2 [DA1 8]

Rg

(In the formula [DAI 7] and the formula [DAI 8], R 8 is -C Ο Ο -, - OC Ο -, - C Ο N Η-' -NHCO- > -COOCH2- ' -CH2OCO- > - CH2O- ' -OCH2- ' -CH2-, -O- or -NH-, R9 is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, an ethyl group Oxy or hydroxy) [Chemical 12]

(In the formula [DA19] and the formula [DA20], R10 is a carbon number of 3 or more and 12 or less - 21 - 201137037 alkyl group, and the cis-trans isotropic of 1,4-cyclohexene is trans isomerism. () 13]

HzN

[DA21] [DA22] (In the formula [DA21] and the formula [DA22], ' Rii is an alkyl group having a carbon number of 3 or more and 12 or less, and the cis-trans isotropic of 1,4-cyclohexene is each a trans Isomer) [Chem. 14]

-22- 201137037 [Chem. 15]

HCHN/CH3\CH3 H2N-丨_{CH2h_NH2 [DA33] \ CH3/PCH3 (p is an integer of i to 10 in the formula [DA33]) Further, for example, a diamine of the following formula [DA34]. [ΠΠ] nh2H2N~ci^ .{C H2)ai—Ai—(C H2) Qiao-A〗-A3.

PA34| (In the formula [DA34], A4 is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom] A3 is I,4-cyclohexenyl or 1,4-phenylene, and A2 is an oxygen atom or -23- 201137037 -COO-* (where 'the key with "*" is linked with A3), A, is the oxygen atom or -COO-* (where 'the key with '*' and the key of (CH2)a2) Further, al is an integer of 0 or 1, 32 is an integer of 2 to 10, and a3 is an integer of 0 or 1.) The other diamine compound is regarded as a liquid crystal alignment property and voltage when used as a liquid crystal alignment film. It is possible to mix one type or two or more types depending on the characteristics of the characteristics and the charge storage. <tetracarboxylic dianhydride> The tetracarboxylic dianhydride used in the present invention is not particularly limited, and specific examples thereof are as follows. Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6, 7-蒽tetracarboxylic acid ' 1,2,5,6-nonanetetracarboxylic 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) maple, double (3,4 -dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4- Dicarboxyphenyl)propane 'bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic acid Acid, 2,6-bis(3,4-dicarboxyphenyl)pyridinium, 3,3,4,4,-diphenylstilbenetetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid Acid, 1,3_diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, dimercaptotetracarboxylic acid, I,2,3,4-cyclobutanetetracarboxylic acid, 1,2 , 3,4-cyclopentane tetracarboxylic acid, 1,2,3,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-l,2,3,4-ring Butane tetracarboxylic acid ' 1,2-dimethyl-i,2,3,4-cyclobutane tetracarboxylic acid, iota, 3-dimethyl-1,2,3,4-cyclo-24 - 201137037 Dingyuan tetracarboxylic acid, 〗 〖, 2,3,4-cyclobutane tetracarboxylic acid, 2,3,4,5-tetrahydrofuran tetraresidic acid '3,4-one residue cyclohexyl succinic acid, 2,3, 5-_Tricarboxycyclopentyl acetic acid, 3,4-carboxyl^-tetrahydro-indole-naphthylsuccinic acid~Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylate Acid, bicyclo[4,3,0]nonane-2,4,7,9_ tetraresidic acid, bicyclo[4,4,pyridin-2,4,7,9-tetracarboxylic acid, two Cyclo [4,4,〇]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6,3,0,0 < 2,6 >]undecane-3,5,9 , 11-tetramic acid, butane tetracarboxylic acid, 4_(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, two Ring [2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuranyl)_3 methyl-3-cyclohexane-1, 2-Dicarboxylic acid, tetracyclo[^丨,丨,^?]dodecane·4,5,9,10-tetraresidic acid, 3,5,6-tricarboxy-norbornane_2:3,5 : 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and the like. The tetracarboxylic dianhydride may be used in the form of a liquid crystal alignment film, a voltage-holding property, and a charge-accumulating property, and may be used alone or in combination of two or more. <Polymer> The polymer of the present invention is a polyamic acid having a specific diamine compound as a raw material as described above, or a polyimine obtained by dehydrating and ring-closing the polyamic acid. In the liquid crystal alignment film obtained from the polymer of the present invention, the more the content ratio of the specific diamine compound in the above diamine component, the higher the stability of the pretilt angle with respect to heat. In order to improve the above characteristics, it is preferred to use a diamine component of 1 mol or more -25 to 201137037 as a specific diamine compound. Further, it is preferable to use a specific amine compound of 5 mol% or more of the diamine component, more preferably 1 mol% or more. Further, 100 mol% of the amine component may be a specific diamine compound in terms of uniform coating properties when the liquid crystal alignment agent is applied. 'The specific diamine compound is 80 mol% or less of the diamine component. It is better to use 4% or less. When the polyamine component of the present invention is obtained by reacting a diamine component with a tetracarboxylic dianhydride, a conventional synthesis method can be used. In general, a method of reacting a tetracarboxylic acid dianhydride with a diamine in an organic solvent. The reaction of the tetracarboxylic dianhydride with the diamine is relatively easy to carry out in an organic solvent, and is extremely advantageous without the occurrence of by-products. The organic solvent used in the reaction of the tetracarboxylic dianhydride with the diamine is as long as It is possible to dissolve the produced polylysine, and there is no particular limitation. This is specifically described below. >1,1<1-dimethylformamide '1^,;^dimethylacetamide, :methyl-2-pyrrolidone, N-methylhexylamine, dimethyl azine, Tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl pentanone, methyl hydrazine Ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Propylene glycol·3rd butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, • 26-201137037 Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetic acid Ester, tripropylene glycol methyl ether, 3-methyl-3-methoxy Butanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, dibutyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxins Alkane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate , propylene glycol monoethyl ether acetate, methyl trimethylacetate, ethyl trimethylacetate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropionic acid Ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diterpene, 4-hydroxy-4-methyl- 2-pentanone and the like. These can be used alone or in combination. Further, it may be used in the above solvent in a range in which the polylysine is not dissolved and the produced polyamine is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and causes the produced polyamic acid to be hydrolyzed, it is preferred to use an organic solvent to be dehydrated. When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, for example, a solution in which a diamine is dispersed or dissolved in an organic solvent is stirred, and tetracarboxylic dianhydride is directly added or dispersed or dissolved in an organic solvent. A method of adding the mixture, and a method of adding a diamine to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of adding a tetracarboxylic dianhydride and a diamine to each other, etc. A method. Further, when it is composed of a plurality of compounds of a tetracarboxylic dianhydride or a diamine component, the reaction may be carried out in a state of -27-201137037 which is previously mixed, or the reaction may be carried out in an individual order, or the low molecular weight body of the individual reaction may be further advanced. The local molecular weight body of the mixed reaction is smashed. The temperature at which the tetracarboxylic dianhydride and the diamine component are allowed to react may be selected from any temperature of -200 ° C to 150 ° C, preferably in the range of - 5 ° C to 10 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid becomes high, and it becomes difficult to uniformly stir. It is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and an organic solvent is added. In the polymer of polyamic acid, the ratio of the total number of moles of the tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polylysine becomes. The polyimine of the present invention is a polyimine obtained by dehydrating and ring-closing the polyamic acid described above, and is extremely useful as a polymer when a liquid crystal alignment film is obtained. In the polyimine of the present invention, the dehydration ring closure ratio of the proline group (the imidization ratio) does not necessarily have to be 1%, depending on the purpose or purpose, for example, it can be adjusted to 4 5~ 8 5 % range, etc. A method of imidating polylysine with ruthenium is, for example, a hydrazine imidization in which a solution of polylysine is directly heated, and a catalyst which is added to a solution of polyphthalic acid to imidize. The temperature at which the polyaminic acid is thermally imidized in the solution is from 100 t to 400 ° C, preferably from 120 T: to 250 ° C, to remove water formed by the hydrazine imidization reaction. Out of the line and the performer is better. -28- 201137037 The phthalocyanine of poly-proline is imidized by adding a basic catalyst and an acid anhydride to the solution of poly-proline, at -20~250 ° C (preferably 〇~ 1 The stirring is carried out under 8 (TC). The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the proline group, and the amount of the anhydride is 1 of the proline group. ~50 moles, preferably 3 to 30 moles. Basic catalysts such as pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc., wherein pyridine is suitable for carrying out the reaction Preferably, the acidity is, for example, acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc., wherein when acetic anhydride is used, it is preferred to carry out the purification after completion of the reaction. The imine imine is imidized by the catalyst. The rate can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. When recovering the polylysine or polyimine from the reaction solution of poly-proline or polyimine, the reaction solution can be obtained. It is poured into a poor solvent and precipitated. The poor solvent used in the precipitation, such as methanol, acetone, hexane, butyl cellosolve, Alkane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. The polymer precipitated in a poor solvent can be filtered and recovered, under normal pressure or reduced pressure, at normal temperature or under heating. Drying is also carried out. Further, when the polymer recovered by precipitation is redissolved in an organic solvent and the operation of reprecipitation is repeated 2 to 10 times, impurities in the polymer can be reduced. At this time, the poor solvent such as alcohols and ketones In the case of a hydrocarbon or the like, when three or more kinds of poor solvents selected from the above are used, the efficiency of the purification can be further improved. Therefore, the polyamine and the polyimine contained in the liquid crystal alignment treatment agent of the present invention are preferred. The molecular weight is considered to be the GPC (Gel Permeation -29-201137037) considering the strength of the coating film obtained and the workability at the time of forming the coating film, and the uniformity of the coating film.

The weight average molecular weight determined by the Chfomatography method is preferably 5,000 to 1,000,000, more preferably 〇, 〇〇〇 1515 〇, 〇〇〇. <Liquid Crystal Alignment Treatment Agent> The liquid crystal alignment treatment agent of the present invention is a coating liquid when a liquid crystal alignment film is formed, and a solution in which a resin component is dissolved in an organic solvent when a resin coating film is formed. Here, the above resin component is a resin component containing at least one polymer selected from the above polymers of the present invention. In this case, the content of the resin component is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, and most preferably from 3 to 10% by mass. In the present invention, the above-mentioned resin component may be all of the polymers used in the present invention, and other polymers other than the above may be mixed in the polymer of the present invention. In this case, the content of the other polymer in the resin component is from 0.5% by mass to 15% by mass, preferably from 1% by mass to 10% by mass. The other polymer is, for example, a polyamine or a polyimine obtained by using a diamine other than a specific diamine compound as a diamine component which reacts with a tetracarboxylic dianhydride. The organic solvent to be used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the above resin component. The liquid crystal alignment treatment agent of the present invention may contain components other than the above. For example, a solvent or a compound which improves film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied, a compound which improves adhesion between a liquid crystal alignment film and a substrate, and the like can be used. -30- 201137037 A specific example of a solvent for improving film thickness uniformity or surface smoothness is as follows. For example, isopropanol, methoxymethylpentanol, methyl cellosolve 'ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Acetate, propylene glycol monomethyl ether, propylene glycol - 3-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetic acid Ester monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Butyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, dibutyl ether , diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether 'methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, vinegar N-butyl ester, n-butyl acetate, propylene glycol monoethyl ether, methyl trimethylacetate, ethyl trimethylacetate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol monoacetic acid Ester, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate Ethyl lactate, n-propyl lactate, n-butyl lactate, a solvent having a low surface tension such as -31 - 201137037 isoamyl lactate. The solvent species for improving the uniformity of the film thickness or the surface smoothness may be used in combination of plural kinds. When the solvent is used, the amount of the solvent contained in the liquid crystal alignment agent is preferably from 5% to 60% by mass. A compound which improves film thickness uniformity or surface smoothness, a surfactant, a polyoxyalkylene surfactant, a nonionic system, and the like. More specifically, for example, F-top EF301 EF352 (manufactured by Tokemu Products Co., Ltd.), Megafac FI R-30 (manufactured by Dainippon Ink Co., Ltd.), Flolite FC43 1 (manufactured by Sumitomo 3 M Co., Ltd.), A s ah i G u ar d 3 82 , SC 1 01 , SC 102 , SC103 , SC 104 SC106 (manufactured by Asahi Glass Co., Ltd.). The ratio of the interface activity is preferably 0.01 to 2 parts by mass, more preferably 0.01%, based on the amount of the resin contained in the liquid crystal alignment agent. A compound which improves the adhesion between the liquid crystal alignment film and the substrate is a functional decane-containing compound or a ring-containing material shown below. For example, 3-aminopropyltrimethoxydecane, 3-aminopropane, 2-aminopropyltrimethoxydecane, 2-aminopropylalkane, Ν(2-aminoethyl)-3 -Aminopropyltrimethoxysulfonylethyl)-3-aminopropylmethyldimethoxydecane, 3-urea' can be used as a solvent of 5 to 80 masses such as fluorine-based interfacial activity Agent, EF303, 71, F173, FC430, AG7 1 0, S-, SC105, the use of the agent is divided into 100 parts, 1 part by mass, more specific examples, the compound of the oxy group, triethoxytriethoxy ruthenium N-(2-Aminopropyltrimethyl-32-201137037 oxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N -ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxymethylidenepropyltriethyltriamine, N-trimethoxycarbamidopropyltriethylenetriamine, 10 -trimethoxycarbamido-1,4,7-triazadecane, 10-triethoxycarbamimidyl-1,4,7-triazadecane, 9-trimethoxyformamidinyl _3,6-diazepine acetate, 9-triethoxycarbamido-3,6-diazepine acetic acid , N-Benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxy Decane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide)-3-aminopropyltrimethoxydecane, N-bis(ethylene oxide)-3-aminopropyl Triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, new Pentanol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibrominated neopentyl diglycidyl ether, 1,3, 5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N'·tetraepoxypropyl-m-xylenediamine, 1,3-double (N,N -diglycidylaminomethyl)cyclohexane, >^ small, 1^', :^'-tetraepoxypropyl-4,4'-diaminodiphenylmethane, etc. When the compound is in contact with the substrate, the amount of the compound used is 0.1 to 3 parts by mass based on 1 part by mass of the resin component contained in the liquid crystal alignment agent. Preferably, it is 1 to 20 parts by mass. When it is less than 1 part by mass, the effect of improving the adhesion cannot be expected. When the amount is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated. In the alignment treatment agent, a dielectric or a conductive liquid for the purpose of changing electrical properties such as liquid crystal ratio or conductivity may be added in addition to the above, in addition to the above-mentioned effects. Membrane/Liquid Crystal Display Device The liquid crystal alignment treatment agent of the present invention can be applied to the substrate by rubbing treatment or light irradiation, and the alignment treatment is not applied to the use or the like. The substrate having high transparency can be limited, and a glass substrate, an acrylic substrate, a polycarbon plastic substrate, or the like can be used. Further, it is preferable to use a substrate for performing liquid crystal driving electrodes or the like in terms of simplification of the process. When the crystal display element is only on one side of the substrate, the sputum may be used. In this case, the electrode may be coated with a light-reflecting liquid crystal alignment treatment agent such as aluminum, and in particular, there is a sieve in the industry. A method of web printing, lithography, and flexibility. Other coating methods include an immersion slit coater, a rotator, etc., depending on the purpose, a heating means such as baking after applying a liquid crystal alignment agent on a substrate, at 50 to 300 ° C (more) The film is evaporated to form a coating film. The thickness of the coating film after baking is too thick to indicate that the power consumption of the device is unfavorable, and when it is too thin, the reliability is lowered, so that it is preferably 5 to 300 nm. J 1 OOnm. When the liquid crystal is horizontally aligned or tilted, the coating film is treated with a dielectric material of the alignment film by rubbing or polarized ultraviolet irradiation, etc. The board is fired or vertically aligned with the alignment film. A special acid ester substrate or the like is formed of ITO, a material that is impermeable to a reflective liquid crystal, or the like, and is generally limited to a general printing, an inkjet, a roll coater, or the like. When the solution is dissolved under °c), the liquid crystal display element E is preferably 1 〇~, and after the firing, the liquid crystal display element of the present invention, the liquid crystal alignment treatment agent is prepared to have a liquid attached thereto. Making a liquid crystal cell and making it as a liquid crystal cell For example, if a plate is used, the liquid crystal alignment film surface of one substrate is inside, the method of bonding the other surface, or the spacer is dispersed; and the method of sealing the bonded substrate is preferably 1~ 30 μm, more preferably, as described above, the crystal display element of the present invention is used to form a liquid crystal television having excellent reliability and high definition. [Embodiment] The following examples are more limited by the examples. According to the above method, after the crystal of the present invention is aligned to the substrate of the film, the liquid crystal is not known. 1 A pair of spacers are formed on the substrate on which the liquid crystal alignment film is formed, and a liquid crystal alignment plate is used, and liquid crystal is injected under reduced pressure to seal the liquid crystal on the L liquid crystal alignment film surface. At this time, the thickness of the separator is 2 to 10 μm. The liquid crystal prepared by the liquid crystal alignment agent can be suitably used as a large screen to explain the present invention in detail, but is not subject to the synthesis of the [Examples] [Specific diamine compound of the present invention <Example 1> Diamine compound (4) Synthesis -35- 201137037 [Chem. 18]

3-methyl-3-oxetanine ethanol (2) (14.95 g, 146.4 mmol) and triethylamine (16.29 g, I60.1 mmol) were added to a nitrogen-substituted 4-neck flask at room temperature. After the reaction with tetrahydrofuran (150 nll), it was kept below 15 ° C, and a solution of 3,5-dinitrobenzyl benzhydryl [l] (33.70 g, 146.2 mmol) in tetrahydrofuran (40 ml) was added dropwise. After completion of the reaction, the reaction solution was poured into 1 L of pure water, and the resulting crystals were filtered and washed with pure water. The crystals were stirred in ethanol (200 ml), filtered, and washed with ethanol to give compound (3) (white crystals, 36.3 g, yield: 84%). 'H-NMR (400MHz, CDCl3, 5ppm): 9.2 6 (1 Η, t, J = 2.0 Η z) , 9.16 (lH, dd, J = 1.2 Hz), 4.63 - 4.50 (4H, m), 4.59 ( 2H, s), 1.47 (3H, s) A mixture of compound (3) (30.00 g, 10 mmol) and 5% Pd-C (3 g) in tetrahydrofuran (300 ml) was stirred in the presence of hydrogen at room temperature. . After completion of the reaction, filtration was carried out to concentrate the chlorine solution under reduced pressure. To the obtained crude product, hexane (200 ml) was added and stirred. After stirring, the crystals were filtered and washed with hexane. Then, the obtained crystals were added to ethanol (100 ml), stirred, and the crystals were filtered, and washed with ethanol to obtain a diamine compound (4) (white crystal, 21.45 g, yield 90%) = -36- 201137037 • 4Hz) 'H-NMR (400MHz, CDCl3, 6ppm)·. 6.7 8 (2 H, d , J = 2 ' 6.18(lH,t,J = 2.4Hz), 4.63(2H,d, J = 6.0 Hz), 4.44 (2H, d, J = 6.0 Hz), 4.32 (2H, s) ' 3 · 745 (4H, brord) 1.40 (3H, s) [Polyuric acid and polyimine Synthesis] Amidin polyamine The following amines and the following Examples 2 to 9 and Comparative Examples 1 to 4 are examples of synthesis of poly or polyimine, and the meanings of the abbreviations and acids used in the respective descriptions. And the measurement of the molecular weight of the polyimine and the measurement of the imidization ratio, and the contents of the polyfluorene polyimides synthesized in Examples 2 to 9 and Comparative Examples 1 to 4 are shown in Table 2 and Table 3, respectively. (tetracarboxylic dianhydride) CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride BODA: bicyclo[3,3,0]octane-2,4,6,8- Tetracarboxylic dianhydride [Chemical 19]

(specific diamine compound) diamine (4): diamine compound synthesized as in Example 1 -37-201137037

(Other diamine compounds) p-PDA: p-phenylenediamine PCH7DAB: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene PBCH5DAB: 1,3-Diamino-4-{4-(trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl)phenoxy}benzene m-PBCH5DAB: 3,5-diamine Base - {4-[trans-4-(trans- 4-n-pentylcyclohexyl)cyclohexyl]phenyl}benzoate [Chem. 21]

(Crosslinking compound) KK 1 : [Chem. 22]

KK2: -38- 201137037 [化23] h3c

KK2 (organic solvent) Ν Μ P : N _methyl-2-pyrrolidone BCS: butyl cellosolve (measurement of molecular weight of poly phthalic acid, polyimine) molecular weight of poly phthalic acid and polyimine A room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Showa Denko Co., Ltd., and a column (KD-803, KD-8 05) manufactured by Shodex Co., Ltd. were used, and the measurement was carried out as follows.

Column temperature: 50 °C Dissolution: N, N'-dimethylformamide (additive is lithium bromide monohydrate (LiBr. H2O) 30 mmol / L, phosphoric acid. Anhydrous crystal (〇-phosphoric acid) 30 mmol / L, Tetrahydrofuran (THF) 10 ml/L) Flow rate: 1.0 ml/min Test line for standard preparation: TSK standard polyethylene oxide manufactured by Torsol Co., Ltd. (molecular weight: about 900,000, 150,000, 100, 〇〇〇, 3 〇, 〇〇〇) Polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) manufactured by Polymer Laboratory Co., Ltd. (measurement of ruthenium imidation rate) 2 〇mg of polyimine powder was added to NMR sample tube (NMR produced by Kusano Scientific Co., Ltd.) In Sampling Tube Standard Φ 5), add 0.5-201137037 hydrogenated dimethyl hydrazine (DMSO-d6, 0.05% TMS (tetramethyl decane) mixture) 0.5 3 ml, apply ultrasonic waves to completely dissolve. This solution was measured for proton NMR at 500 MHz by an NMR measuring instrument (JWN-ECA500) manufactured by E.L. Datum. The ruthenium imidization ratio is determined by using a proton having a structure which has not changed before and after the imidization as a reference proton, and the peak of the proton is used to form an average of 値 and the NH group derived from lysine which is present in the vicinity of 9.5 to 10. Oppm. The proton peaks are cumulatively obtained by the following formula. Ruthenium amination rate (%) = (1 - a . x / y) x 1 00 In the above formula, x is the proton peak accumulation 醯 from the NH group of proline, and the peak accumulation of the y-based reference proton, The ratio of the alpha matrix to the ruthenium matrix of lysine relative to one polylysine (the oxime iodization rate is 0%) is the ratio of the number of reference protons. &lt;Example 2 &gt; BODA (3.51 g, 1 4.0 mmol), PC Η 7 DAB (0.8 9 g, 2.34 mmol), p-PDA (1.77 g, 16.4 mmol), diamine (4) (1.10 g) , 4.66 mmol), mixed in NMP (14.4 g), and reacted at 80 ° C for 5 hours, then force D into CBDA (1.84 g ' 9.38 mmol) and NMP (12.3 g), and react at 40 ° C A solution of polyamic acid (A) (concentration: 25.4% by mass) was obtained for 6 hours. The polyamic acid had a number average molecular weight of 23,900 and a weight average molecular weight of 59,500. &lt;Example 3 &gt; In the same manner as in Example 2, NMP was added to the obtained solution of polyamic acid (A)-40-201137037 (20.0 g), diluted to a concentration of 6 mass%, and then added as a yam. Acetylation catalyst acetic anhydride (2.48 g) and pyridine (1.90 g) were reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 ° C to obtain a powder of polyimine (B). The polyimine had a ruthenium iodide ratio of 53%, a number average molecular weight of 21,300, and a weight average molecular weight of 51,200. &lt;Example 4&gt; BODA (3.48 g, 13.9 mmol), PCH7DAB (0.44 g, 1.16 mmol), p-PDA (1.63 g, 15.1 mmol), and diamine (4) were mixed in NMP (14.6 g). 1 _64 g, 6.94 mmol), after reacting at 80 ° C for 5 hours, CBDA (1.82 g, 9.27 mmol) and NMP (12.7 g) were added, and the reaction was carried out at 4 ° C for 6 hours. A solution of polylysine (C) (concentration 24.8% by mass). The polyamic acid had a number average molecular weight of 24,100 and a weight average molecular weight of 594,200. &lt;Example 5&gt; In the same manner as in Example 4, NMP was added to the obtained solution of polylysine (C) (20.2 g), diluted to a concentration of 6 mass%, and then added as a ruthenium-based catalyst. Acetic anhydride (2.50 g) and pyridine (1.95 g) were reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (300 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a powder of polyimine (D). The polyimine of -41 - 201137037 has a ruthenium amination rate of 55% 'the number average molecular weight is 22,4 〇〇, and the weight average molecular weight is 52,500 β &lt;Example 6&gt; Mixing B in NMP (17.5 g) 〇DA (3.50g, 14.0mm〇l), PCH7D AB (4.44g, 1 1 · 7 m mo 1), p _ pd A (1.01 g, 9 · 3 4 mm 〇1) 'diamine ( 4) (0.55 g, 2.33 mmol), after reacting at 80 ° C for 5 hours, CBDA (1.83 g, 9.33 mmol) and NMP (15.9 g) were added, and the reaction was carried out at 40 ° C for 6 hours. Polylysine solution (concentration 25.3% by mass). NMP was added to the obtained polyaminic acid solution (20.0 g), and diluted to a concentration of 6 mass%, and acetic anhydride (4.53 g) and pyridine (3.31 g) as a ruthenium amide catalyst were added at 90 ° C. The reaction was carried out for 3 hours. The reaction solution was poured into methanol (3 10 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 1 Torr to obtain a powder of polyimine (E). The polyimine had an oxime imidization ratio of 80%, a number average molecular weight of 16,300, and a weight average molecular weight of 45,400. &lt;Example 7&gt; BODA (3.50 g, 14.0 mmol), PCH5D AB (0.50 g, 1.16 mm ο 1), p-PDA (1.89 g, 1 7) were mixed in NMP (14.9 g). · 5 mm ο 1), diamine (4) (1.10 g, 4.66 mmol) ' After reacting at 80 ° C for 5 hours, CBDA (1.83 g, 9.33 mmol) and NMP (12.3 g) were added at 4 The reaction was carried out at 0 ° C for 6 hours to obtain a polyaminic acid solution (concentration 2 4.5 mass - 42 - 201137037 %). NMP was added to the obtained polyamic acid solution (20. g), diluted to a concentration of 6 mass%, and then acetic anhydride (2.45 g) and pyridine (1.93 g) as a ruthenium catalyst were added. The reaction was carried out for 4 hours at 8 Torr. The reaction solution was poured into methanol (280 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol at 1 Torr. (: The powder of polyimine (F) was obtained by drying under reduced pressure. The polyamidimide had a ruthenium imidation ratio of 55%, a number average molecular weight of 22,600, and a weight average molecular weight of 53,100. Example 8&gt; BODA (3.55 g, 14.2 mmol), PCH5DAB (3.07 g, 7.10 mmol), p-PDA (1.28 g, 11.8 mmol), diamine (4) (1.12 g, 4.74) were mixed in NMP (16_5g). Mm〇l), after reacting at 80 ° C for 5 hours, CBDA (1 - 86 g, 9.48 mmol) and NMP (15.9 g) were added, and the reaction was carried out at 4 ° C for 6 hours to obtain a polyamidonic acid solution. (concentration: 25.2 mass 〇 / 〇). After adding NMP 'diluted to a concentration of 6 mass% in the obtained polyamidic acid solution (20.5 g), 'added acetic anhydride (4.50 g) as a ruthenium amide catalyst, pyridine (3.30 g) 'The reaction was carried out at 90 ° C for 3 hours. The reaction solution was poured into methanol (330 ml) to 'filter the separately formed precipitate. The precipitate was washed with methanol' at .10 ° C The powder of the polyimine (G) was obtained by drying under reduced pressure. The polyamidimide had a ruthenium iodide ratio of 81% and a number average molecular weight of 16,100 and a weight average molecular weight of 44,800. 43 - 201137037 &lt;Example 9&gt; 8008 (3.50 §, 14.〇111111〇1), 111-PCH5DAB (3.12 g, 7 · 0 0 mm ο 1), p was mixed in NMP (16.4 g) - PDA (1 · 2 6 g, 1 1 · 7 mm ο 1), diamine (4) (1.10 g, 4.66 mmol), and reacted at 80 ° C for 5 hours, then added CBDA (1.83 g, 9.33 mmol) and NMP (1 5.3 g) were reacted at 4 ° C for 6 hours to obtain a polyaminic acid solution (concentration: 25.4% by mass). The obtained polyglycine solution (20.0 g) was added. NMP was diluted to a concentration of 6 mass%, and acetic anhydride (2.48 g) and pyridine (1.95 g) as a ruthenium-imiding catalyst were added, and the reaction was carried out for 4 hours at 80 ° C. The reaction solution was poured into methanol ( The precipitate formed separately was filtered in 300 ml. The precipitate was washed with methanol, and dried under reduced pressure at 10 ° C to obtain a powder of polyimine (H). The imidization ratio was 55%, the number average molecular weight was 1,800, and the weight average molecular weight was 48,500. <Comparative Example 1 &gt; BODA (3.53 g, M.lmmol) and PCH7DAB were mixed in NMP (13.1 g) ( 0.89g, 2.3 4m m ο 1), p - PDA (2.2 9 g, 2 1 . 2 mm ο 1), after reacting at 80 ° C for 5 hours, CBDA (1.85 g, 9.43 mmol) and NMP (12.4 g) were added, and the reaction was carried out at 40 ° C for 6 hours. A solution of polyamine (I) (concentration: 25.0% by mass) was obtained. The polyimine has a number average molecular weight of 25,400 and an average dead weight of 63,300. &lt;Comparative Example 2 &gt; -44-201137037 In the same manner as in Synthesis Example 1, NMP was added to a solution (20.0 g) of the obtained polyaminic acid (I), and the mixture was diluted to a concentration of 6 mass%, and then added as a hydrazine. The imidization catalyst acetic anhydride (2.48 g) and pyridine (1.92 g) were reacted at 8 (TC for 4 hours). The reaction solution was poured into methanol (2 90 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a powder of polyimine (J). The polyamidimide had a hydrazine imidization ratio of 55% and a number average molecular weight of 22,300. The weight average molecular weight was 56,300. &lt;Comparative Example 3&gt; BODA (3.51 g, 14.0 mmol), PCH7D AB (4.45 g, 1 1 _ 7 mm ο 1), p-PDA (1.2) were mixed in NMP (1 7.3 g). 6 g '1 1 . 7 mm ο 1), after reacting at 80 ° C for 5 hours, adding CBDA (1.83 g, 9.3 3 mmol) and NMP (15.3 g), at 4 (TC) The reaction was carried out for 6 hours to obtain a polyaminic acid solution (concentration: 25.3% by mass). Ν Μ P was added to the obtained polyaminic acid solution (200 g), diluted to a concentration of 6 mass%, and then added as a hydrazine. Imine exposure The acetic acid of the medium: (4.5 〇g), pyridine (3.30 g)' was reacted at 90 ° C for 3 hours. The reaction solution was poured into methanol (32 ml), and the resulting precipitate was filtered. The precipitate was washed with methanol and dried under reduced pressure at 1 ° C to obtain a powder of polyimine (K). The polyamidimide had an oxime imidization ratio of 80% and a number average molecular weight of 16,100, weight average molecular weight was 44,2 〇〇. &lt;Comparative Example 4&gt; -45- 201137037 BODA (3.50 g, 14.0 mmol), PCH5DAB (3.03 g, 7.00 mmol), p- were mixed in NMP (16.2 g). PDA (1.77 g, 16.4 mmol) was reacted at 80 ° C for 5 hours, and then CBDA (1.83 g, 9.33 mmol) and NMP (15.0 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyfluorene. Amino acid solution (concentration: 24.5% by mass). NMP was added to the obtained polyaminic acid solution (20.0 g), diluted to a concentration of 6 mass%, and acetic anhydride (4.4 8 g) as a ruthenium catalyst was added. Pyridine (3.2 8 g) was reacted for 3 hours at 90 ° C. The reaction solution was poured into methanol (320 ml) to filter the precipitates formed separately. The precipitate was washed with methanol to dry under reduced pressure at 10 ° C to obtain a powder of polyimine (L). The polyamidimide had a ruthenium iodide ratio of 81%', a number average molecular weight of 19,500, and a weight average molecular weight of 49,400. -46 - 201137037 [Table 2] Polymer tetracarboxylic dianhydride [g/rnnol] Diamine component [g/mmol] oxime imidization ratio (%) Example 2 Polyglycine (A) C6DA [1.84/ 9. 38] B0DA [3. 51/14.0] Diamine (4) D. 10/4. 66] PCH7DAB [0. 89/2. 34] p-PDA [l. 77/16. 4] Example 3 Polyimine (B) CBDA [1.84/9. 38] B0DA [3. 51/14.0] Diamine (4) [1. 10/4. 66] PCH7DAB [0. 89/2. 34] p-PDA [l. 77/16. 4] 5 3 Example 4 Polylactoic acid (C) CBDA [1. 82/9.27] B0DA [3.48/13.9] Diamine (4) [1.64/6. 94] PCH7DAB[0 44/1.16] p-PDA [l. 63/15.1] Example 5 Polyimine (D) CBDA [1.82/9. 27] B0DA [3. 48/13.9] Diamine (4) [1· 64 /6. 96] PCH7DAB [0. 44/1. 16] p-PDA [l. 63/15.1] 5 5 Example 6 Polyimine (E) CBDAtl.83/9. 33] B0DA [3. 50 /14. 0] Diamine (4) [0. 55/2. 33] PCH7DAB [4.44/11. 7] p-PDA [l.01/9.34] 8 0 Example 7 Polyimine (F) CBDA [1. 83 /9.33] BODA [3. 50/14.0] Diamine (4) [1. 10/4. 66] PBCH5DAB [0. 50/1. 16] p-PDA [1.89/17. 5] 5 5 Example 8 Polyimine (G) CBDA [1. 86/9.48] B0DA [3. 55/14. 2] Diamine (4) [1. 12/4. 74] PBCH5DAB [3. 07/7 . 10] p-PDA[1.28/11 .8] 8 1 Example 9 Polyimine (H) CBDA [1.83/9. 33] BODA [3. 50/14.0] Diamine (4) [1. 10/4. 66] m-PBCH5DAB [3.12 /7.00] p-PDA [1.26/ll. 7] 5 5 [Table 3] Polymer tetracarboxylic dianhydride [g/mmol] Diamine component [g/mmol] Brewing imidization ratio (%) Comparative Example 1 Poly (proline) α) CBDA [1. 85/9.43] B0DA [3. 53/14. l] PCH7DAB [0. 89/2. 34] p-PDA [2. 29/21. 2] Comparative Example 2醯imine (7) CBDA [1.85/9. 43] B0DA [3. 53/14.1] PCH7DAB [0. 89/2. 34] p-PDA [2. 29/21. 2] 5 5 Comparative Example 3 Polysaccharide Amine (Κ) CBDA [1. 83/9. 33] B0DA [3. 51/14.0] PCH7DAB [4 45/11.7] p-PDA [1. 26/11. 7] 8 0 Comparative Example 4 Polyimine (L) CBDA [1. 83/9. 33] B0DA[3_ 50/14.0] PBCH5DAB[3. 03/7. 00] p-PDA[l. 77/16. 4] 8 1 [Liquid alignment treatment agent [Production] In the following Examples 1 to 7 and Comparative Examples 5 to 1 1, a production example of a liquid crystal alignment treatment agent was used, and [liquid crystal cell production] and [liquid crystal] used for evaluation of each liquid crystal alignment treatment agent were used. Evaluation of Orientation and Pretilt Angle] and [Evaluation of Sex-47-201137037], as described below. Further, the contents and characteristics of each of the liquid crystal alignment treatment agents obtained in Examples 1 to 17 and Comparative Examples 5 to 1 are shown in Tables 4 and 5. [Production of liquid crystal cell] Rotating and coating a liquid crystal alignment agent on a 3x4 cm surface with a ruthenium electrode 'heat treatment on a hot plate at 80 ° C for 5 minutes, in a heat cycle type clean oven, 210 ° Heat treatment was carried out for 30 minutes at C to obtain a polyimide film having a film thickness of 100 nm. The coating film surface was rubbed with a roll diameter of 120 mm, a friction device of a Thunder cloth, a number of revolutions of 7 rpm, a moving speed of 40 mm/sec, and a pushing amount of 0 · 3 mm to obtain a substrate with a liquid crystal alignment film. . Two substrates with the liquid crystal alignment film were used, and the liquid crystal alignment film surface was placed inside, sandwiched at intervals of 6 μm, and combined in a direction opposite to the rubbing direction, and the periphery was adhered with a sealant to prepare an empty cell. Liquid crystal (manufactured by Merck. Japan, ZLI-2293) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain an antiparallel alignment nematic liquid crystal cell (hereinafter also referred to as liquid crystal crystal). Cell). In the case of Example 14 4, Example 16 and Example 17, and Comparative Example 3 to Comparative Example 7, MLC-6608 (manufactured by Merck. Japan Co., Ltd.) was used as the liquid crystal. [Evaluation of liquid crystal alignment and pretilt angle]

The liquid crystal cell obtained by the above [manufacture of liquid crystal cell] was subjected to heat treatment at 95 ° C for 5 minutes after the liquid crystal injection (initial) (treatment 1 in Table 4) and at 120 ° C. After heat treatment for 5 hours, heat treatment was performed at 95 ° C -48 - 201137037 for 5 minutes (treatment 2 in Table 4), and the pretilt angle was measured for each. The pretilt angle is measured at the center of the liquid crystal cell and at a distance of 1 cm from the center to the upper and lower sides, and the average enthalpy is used as the pretilt angle. In this case, the measurement was performed at room temperature using a pretilt angle measuring apparatus (Model PAS-301 manufactured by ELS IC Co., Ltd.) ° and 'relevant liquid crystal cell after initial and each heat treatment, and observed by a polarizing microscope' Orientation uniformity. The liquid crystal is evaluated as 〇 for a uniform alignment state, and X is evaluated for a liquid crystal alignment disorder. [Evaluation of Electrical Characteristics] The liquid crystal cell obtained by the above [Production of Liquid Crystal Cell] was applied with a voltage of 4 V at a temperature of 80 ° C for 60 ps, and the voltage after 16.67 ms and after 16 6 ms was measured. The degree to which the voltage can be maintained is taken as the voltage holding ratio (initial voltage holding ratio in Table 5). In addition, the liquid crystal cell after the measurement of the voltage holding ratio was placed in a thermostat bath set at 1 Torr for 21 days, and the voltage holding ratio (the voltage holding ratio after the high temperature standing in Table 5) was performed in the same manner as above. Evaluation of the frictional resistance] The surface of the substrate with the liquid crystal alignment film after the rubbing treatment obtained by the above-mentioned [liquid crystal cell production] was observed by a confocal laser microscope to confirm the presence or absence of frictional scratches. The scar was -49-201137037 <Example> 〇> In the same manner as in Example 2, a solution (10.2 g) of the obtained polyamic acid (A), NMP (9.71 g), and BCS (20.0 g) were obtained. The mixture was mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent [1 ]». The liquid crystal alignment treatment agent was found to be a uniform solution without turbidity or precipitation, etc. &lt;Example 11&gt; 3, the obtained polyimine (B) powder (2.51 g), NMP (24. 5 g) and BCS (ll·6 g) were mixed at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent ( 2) The liquid crystal alignment agent has no abnormality such as turbidity or precipitation, and can be confirmed to be uniform. Solution. <Example 12> In the same manner as in Example 4, the obtained solution of polylysine (c) (1 0.5 g), NMP (1 1.6 g) and BCS (1 8.0 g) were at 25°. C is mixed for 12 hours to obtain a liquid crystal alignment treatment agent (3). The liquid crystal alignment treatment agent has no abnormality such as turbidity or precipitation, and can be confirmed as a uniform solution. <Example 1 3> The same as Example 5 The obtained polyimine (D) powder (2.50 g), NMP (18.7 g) and BCS (17.3 g) were mixed at 5 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (4). The liquid crystal alignment treatment agent was not found to be a turbid or precipitated abnormality, and was confirmed to be a homogeneous solution. -50-201137037 &lt;Example 1 4 &gt; In the same manner as in Example 6, 'the obtained polyimine (£) The powder (2.55 g), NMP (26.9 g), and BCS (9.8 lg) were mixed at 50° C. for 15 hours to obtain a liquid crystal alignment treatment agent (5). The liquid crystal alignment treatment agent had no abnormality such as turbidity or precipitation. It was confirmed that it was a homogeneous solution. <Example 15> In the same manner as in Example 7, the obtained polyimine (F) powder (2.48 g), NMP (16.6 g), and BCS (19) were obtained. .2g) The liquid crystal alignment treatment agent (6) was prepared by mixing at 50 ° C for 15 hours. The liquid crystal alignment treatment agent was free from abnormalities such as turbidity or precipitation, and was confirmed to be a uniform solution. [Example 1 6 &gt In the same manner as in Example 8, the obtained polyimine (G) powder (2.5 〇g), NMP (28.3 g), and BCS (7.69 g) were mixed at 50 ° C for 15 hours to obtain a liquid crystal alignment. Treatment agent (7). The liquid crystal alignment agent was not abnormally mixed, such as elution or precipitation, and was confirmed to be a uniform solution. &lt;Example 17&gt; The obtained polyimine (H) powder (2,5 〇g), NMP (22.6 g), and BCS (13.40 g) were mixed at 50 ° C in the same manner as in Example 9. The liquid crystal alignment treatment agent (8) was produced in 15 hours. The liquid crystal alignment agent was not abnormally mixed, such as elution or precipitation, and was confirmed to be a uniform solution. -51 - 201137037 &lt;Comparative Example 5&gt; In the same manner as in Comparative Example 1, the obtained solution of polylysine (I) (10 g), NMP (9.71 g), and BCS (20.2 g) were used in 2 5 . (: The mixture was mixed for 12 hours to obtain a liquid crystal alignment treatment agent (9). &lt;Comparative Example 6 &gt; In the same manner as in Comparative Example 2, the obtained polyimine powder (2.45 g) and NMP (24.0 g) were obtained. And BCS (1 1.3 g) were mixed at 5 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (10). &lt;Comparative Example 7 &gt; In the same manner as in Comparative Example 3, the obtained polymerization was carried out. The powder of quinone imine (K) (2.50 g), NMP (26.4 g) and BCS (9·62 g) were mixed at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (Π). &lt;Comparative Example 8 &gt In the same manner as in Comparative Example 3, the obtained polyimine (K) powder (2.45 g), NMP (31.1 g), BCS (11.3 g), and crosslinkable compound KK 1 (0.4 9 g) were at 50 °. The liquid crystal alignment treatment agent (12) was obtained by mixing for 15 hours under C. <Comparative Example 9> The powder of the polyimine (L) obtained in Comparative Example 4 (2.50 g) 'NMPinJg^BCSdl.Sg) and The compound KK1 (0.50 g) was mixed at -52 to 201137037 5 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (13). &lt;Comparative Example 1 0 &gt; In the same manner as in Comparative Example 3, the obtained polyimine (K) powder (2.48 g), NMP (32.0 g), BCS (ll.lg), and crosslinkable compound KK2 were obtained. (0.50 g) was mixed at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (14). &lt;Comparative Example 1 1 &gt; In the same manner as in Comparative Example 4, the obtained polyimine (L) powder (2.52 g), NMP (31.8 g), BCS (11.4 g), and crosslinkable compound KK2 ( 0.51 g) was mixed at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (15) ° [Table 4] Liquid crystal alignment [Protective agent pre-mo-oriented friction-resistant polymer cross-linking polymer initial treatment 1 treatment 2 Example 10 Polyproline (A) 7.8 7.8 7.7 〇〇 Example 11 Polyimine (B) 6.8 6.7 6.6 〇 6 Example 12 Polyamide (Q 4. 1 4.1 4.0 〇 6 Example 13 Polyimine (D) 3. 5 3.5 3.4 〇δ Example 14 Polyimine (E) 88.2 88.3 88. 3 〇 6 Example 15 Polyimine (F) 7.5 7.6 7.5 〇〇 Example 16 Polymerization醢imine (6) 84.3 84.5 84, 5 〇〇 Example 17 Polyimine (H) 89.2 89.1 89.2 〇〇Comparative Example 5 Polyproline (I) 7.3 Γ 7.3 6.4 XX Comparative Example 6 Polyimine (J 6.2 6.1 5.3 XX Comparative Example 7 Polyimine (K) 85.3 85,4 85.5 XX Comparative Example 8 Polyimine ΠΟ KK1 87.6 87.6 87.8 〇〇Comparative Example 9 Polyimine (L) KK1 84.8 84,8卜84. 9 〇〇 Comparative Example 10 Polyimine ΠΟ KK2 87.4 87.5 87.6 〇〇Comparative Example 11 Polyimine (D KK2 84.6 84.7 84.8 〇〇-53- 201137037 [Table 5] Liquid crystal alignment agent voltage retention rate (%) * Initial 髙Polymer-crosslinkable compound after warming 16.67 ms 1667 ms 16. 67 ms 1667 ms Example 10 Polyproline (A) 97.3 65. 1 96. 3 64.2 Example 11 Polyimine (B) 98.2 67.5 97.9 67. 1 Example 12 Polyproline (C) 97.4 65.4 96.7 64.9 Example 13 Polyimine (D) 98.4 67.6 98. 2 67.3 Example 14 Polyimine (E) 98.9 .68.8 98.8 68.8 Example 15醯imine (F) 98.3 67,5 97.8 67.0 Example 16 Polyimine (G) 98.8 68,8 98.7 68.6 Example 17 Polyimine (H) 98,5 68.4 98. 2 68.2 Comparative Example 5 Proline (I) 97. 1 65.0 94. 5 63. 1 Comparative Example 6 Polyimine (1) 98. 1 67.5 96.9 65.8 Comparative Example 7 Polyimine (K) 98.4 67.5 97.2 66.6 Comparative Example 8 Polysaccharide Amine (K) KK1 98.4 68.2 97.0 65.2 Comparative Example 9 Polyimine (L) KK1 98.3 68.1 96.9 65.0 Comparative Example 10 Polyimine (K) KK2 98.5 68.4 97. 1 65. 6 Comparative Example 11 Amine (K) KK2 98.6 68.5 97.5 66.0 From the above results, it is understood that the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of Example 1 to has a uniform alignment property and can improve the stability of the pretilt angle to heat. Moreover, even if it is exposed to a high temperature for a long period of time, the situation in which the voltage holding ratio is lowered can be suppressed. Further, in the liquid crystal alignment film obtained by the liquid crystal alignment treatment agents of Comparative Examples 5 to 7, the liquid crystal alignment disorder due to the scratch caused by the rubbing was observed. Further, after heat treatment at 1 2 0 ° C for 5 hours (heat treatment 2), the pretilt angle was greatly lowered. Further, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agents of Comparative Examples 8 to 1 had a large voltage holding ratio after high-temperature placement for the initial voltage holding ratio. Further, in the case of the first embodiment, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the example was compared with the case of the comparative example 5, and the examples 1 1 and 13 3 to 17 were compared with the comparative examples 6 and 7. There is no scratching condition accompanying the rubbing treatment' and the pretilt angle greatly improves the heat stability. Thereby, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present embodiment can be produced without occurrence of display spots even under severe conditions during use or placement in a long-term, high-temperature environment of -54-201137037. Liquid crystal display element. Further, in Examples 1 and 12, compared with Comparative Example 9, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example was obtained even when the examples 1 1 and 1 3 to 17 were compared with the comparative examples 6 and 7. When exposed to high temperatures for a long time, the voltage holding rate can be suppressed from being lowered. Thereby, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present embodiment can be obtained with high reliability even in an extremely severe condition, and can be produced without causing poor display of the liquid crystal display element. Liquid crystal display element. Further, in the liquid crystal alignment film obtained from the liquid crystal alignment treatment agents of Comparative Examples 8 to 11, the initial voltage holding ratio was greatly lowered after the high temperature standing. [Industrial use price 値] The liquid crystal alignment treatment agent of the present invention is useful for TN elements 'S TN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements, and is particularly suitable for use in large-screen and high-definition liquid crystal televisions. . The entire contents of the specification, the scope of the application, and the abstract of the Japanese Patent Application No. 2009-29 5 190, filed on Dec. 25, 2009, are hereby incorporated by reference. -55-

Claims (1)

201137037 VII. Patent application scope 1. A liquid crystal alignment treatment agent characterized by containing a polyamic acid selected from the group consisting of a diamine component containing a diamine compound represented by formula π] and a tetracarboxylic dianhydride. And at least one polymer of the group of polyimine obtained by subjecting the polyamic acid to dehydration ring closure, (In the formula [1], Χι is -Ο-, -NH-, N(CH3)-, -CONH-, -NHCO-, -CH20-, -COO-, -OCO-, -CON(CH3)- , or -N(CH3)CO-, x2 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, and X3 is a single bond, -〇-, -:^1 ·!-, -N(CH3)-, -CONH·, -NHCO-, -COO-, -OCO-, -CON(CH3)-, -N(CH3)CO- or,-0(CH2)m- (m is an integer of 1 to 5), X4 represents an organic group having 1 to 20 carbon atoms, and η is an integer of 1 to 4). 2. In the liquid crystal alignment treatment agent of claim 1, wherein Χ2 of the formula [1] is a single bond or a carbon number of 1 to 5. 3. The liquid crystal alignment treatment agent according to Item 1 or 2 of the patent application, wherein Χ4 of the formula [1] is an alkyl group having 1 to 5 carbon atoms. The liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein Χι of the formula [1] is -0-, -CONH-, or -COO·, Χ3 is a single bond or -0- , η is 1. The liquid crystal alignment agent according to any one of claims 1 to 4, wherein 5 to 80 mol% of the diamine component is a diamine compound represented by the formula []. A liquid crystal alignment film which is obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 5. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 6 of the patent application. 8. A diamine compound' characterized by the following formula [1] [Chemical 2] [1] (In the formula [1], 1 is -0-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH20-, -COO-, -OCO-, -CON (CH3)-, or -N(CH3)CO-, X2 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, and X3 is a single bond, -Ο-, -NH_, -N(CH3)-, -CONH-...NHCO-, -COO-, -OCO-, -CON(CH3)-, -N(CH3)CO-, or -CKCHOn^m is 1~5 Integer), X4 represents an organic group having 1 to 20 carbon atoms, and η is an integer of 1 to 4). 9. A polyimine, which is characterized by containing the formula [1] as in the scope of claim 8 The diamine component of the diamine compound shown, the polylysine obtained by reacting with a tetracarboxylic dianhydride, or the polyglycolic acid is subjected to dehydration ring closure. -57- 201137037 IV. Designation of representatives: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. :式(1) (化1) [1]