TWI545147B - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment treatment agent used in the production of a liquid crystal alignment film and a liquid crystal display element using the liquid crystal alignment treatment agent.

Liquid crystal display elements are currently widely used as a thin, lightweight display device. Generally, in this liquid crystal display element, a liquid crystal alignment film can be used to determine the alignment state of the liquid crystal. Further, in addition to a part of the vertical alignment type liquid crystal display element or the like, almost all of the liquid crystal alignment films are produced by performing some alignment treatment on the surface of the polymer film formed on the electrode substrate.

In the method of treating the alignment of the polymer film, a method generally used in the present invention is a method in which a surface of the film is applied by a cloth having a material such as a thread or the like to perform friction so-called rubbing treatment. A method of using at least one polymer of polyaminic acid or polyimine and a liquid crystal alignment treatment agent containing a specific thermal crosslinking compound has been proposed for a chip of a polymer film which is subjected to such a rubbing treatment. (For example, refer to Patent Document 1), or a method of improving the rubbing resistance by using a curing agent, such as a method of using a liquid crystal alignment treatment agent containing a compound having an epoxy group (see, for example, Patent Document 2).

(previous technical literature) (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 9-185065

Patent Document 2: Japanese Patent Laid-Open No. Hei 9-146100

(disclosure of the invention)

In recent years, the purpose has been to shorten the manufacturing process time of a liquid crystal display element, and the rubbing treatment is performed in a short time and strong friction condition. Therefore, compared with the prior art, the problem of chipping of the polymer film with the rubbing treatment or scratching with the rubbing treatment is often caused. Then, such an abnormality lowers the characteristics of the liquid crystal display element, and further causes one of the causes of a decrease in yield.

Further, with the recent increase in the performance of liquid crystal display elements, liquid crystal display elements can be used for applications such as large-screen and high-definition liquid crystal televisions, or for vehicle applications such as car navigation systems or instrument panels. In such a use, in order to obtain high brightness, a backlight having a large amount of heat is sometimes used. Therefore, the liquid crystal alignment film system has further high reliability from another viewpoint, that is, high stability to light derived from the backlight has been demanded. In particular, when the voltage holding ratio of one of the electrical characteristics of the liquid crystal display element is lowered by the light from the backlight, the sintering failure of one of the display failures of the liquid crystal display element (hereinafter sometimes referred to as line sintering) is likely to occur. A liquid crystal display element with high reliability cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to the initial characteristics, it is desired that the voltage holding ratio is not easily lowered even after exposure to light for a long period of time.

Accordingly, an object of the present invention is to provide a liquid crystal alignment film having the above characteristics. That is, the object of the present invention is to provide a liquid crystal alignment film It is not easy to cause chipping of the polymer film accompanying the rubbing treatment in the manufacturing process of the liquid crystal display element or scratching with the rubbing treatment, and further, in addition to this characteristic, voltage exposure can be suppressed even if exposed to light for a long time. The rate is reduced.

Moreover, an object of the present invention is to provide a liquid crystal alignment element which can provide the liquid crystal alignment treatment agent of the above liquid crystal alignment film and which is obtained by using the liquid crystal alignment treatment agent.

As a result of intensive research, the present inventors have found that a liquid crystal alignment treatment agent containing an amine compound having a specific structure is extremely effective for achieving the above object, and the present invention has been completed.

That is, the present invention has the following gist.

(1) A liquid crystal alignment treatment agent comprising the following component (A) and component (B); component (A) having one primary amino group and a hydroxyl group in the molecule, and the aforementioned primary amine group and a hydroxyl group bond An amine compound bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group; and a component (B): at least one polymer selected from the group consisting of a polyimide intermediate and a polyimide.

(2) The liquid crystal alignment treatment agent according to the above item (1), wherein the amine compound of the component (A) is a compound represented by the following formula [1]; (In the formula [1], X ₁ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and the X ₂ -based single bond, -O-, -NH-, -CO-, -COO-, -OCO- , -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ )CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -, X ₃ is Single bond, benzene ring or cyclohexane ring, X ₄ single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, - N(CH ₃ )CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -, X ₅ is a single bond, an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, n is an integer from 1 to 5).

(3) The liquid crystal alignment treatment agent according to the above item (2), wherein X ₁ of the formula [1] of the amine compound of the component (A) is a linear or branched alkyl group having a carbon number of 1 to 10, and a ring Hexane ring or bicyclohexyl ring.

(4) The liquid crystal alignment treatment agent according to the above (2) or (3), wherein X ₂ of the formula [1] of the amine compound of the component (A) is a single bond, -O-, or -COO-, -OCO -.

(5) The liquid crystal alignment treatment agent according to any one of the items (2) to (4), wherein X ₃ of the formula [1] of the amine compound of the component (A) is a single bond or a benzene ring.

(6) The liquid crystal alignment treatment agent according to any one of the above items (2) to (5), wherein X ₄ of the formula [1] of the amine compound of the component (A) is a single bond, -O-, -NH- Or -CONH-.

(7) (2) to (6) according to any one of the above items liquid crystal alignment treating agent, an amine compound of formula wherein the component (A) of [1] The X ₅ is a single bond, a linear carbon number of 1 to 10 A key or branched alkyl or cyclohexane ring.

(8) Liquid crystal alignment processing according to any one of the above items (1) to (7) And the component (B) is at least 1 selected from the group consisting of polylysine obtained by reacting a diamine component with tetracarboxylic dianhydride and polyimine obtained by dehydration of the polyglycolic acid. Kind of polymer.

(9) The liquid crystal alignment treatment agent according to the above item (8), wherein the diamine component is a diamine compound having a side chain represented by the following formula [2]; (In the formula [2], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₄ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be An alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, or having a steroid skeleton a divalent organic group selected from the organic group having 12 to 25 carbon atoms, and Y ₅ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and the cyclic group Any hydrogen atom may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Substituting, n is an integer of 0 to 4, and Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a carbon number of 1 to 18 Fluoroalkoxy).

(10) The liquid crystal alignment treatment agent according to the above item (8), wherein the diamine component is a diamine compound represented by the following formula [2a]; (In the formula [2a], Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n have the same meanings as defined in the formula [2], and m is an integer of 1 to 4).

(11) The liquid crystal alignment treatment agent according to the above (9) or (10), wherein the diamine compound of the above formula [2a] contains 5 mol% to 80 mol% in the diamine component.

(12) The liquid crystal alignment treatment agent according to any one of the above items (8), wherein the polymer of the component (B) is a polymerization using a tetracarboxylic dianhydride represented by the following formula [3] Object (In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).

(13) The liquid crystal alignment treatment agent according to the above (12), wherein the tetracarboxylic dianhydride has a structure represented by the following formula [3a] to formula [3j]; (In the formula [3a], Z ₂ to Z _{5 may be} a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, and in the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or The methyl groups may be the same or different.

(14) The liquid crystal alignment treatment agent according to any one of the above (1), wherein the polymer of the component (B) is a polyimine obtained by dehydrating a polyamic acid.

The liquid crystal alignment treatment agent according to any one of the above-mentioned items (1), wherein the component (A) is 0.1 parts by mass to 20 parts by mass based on 100 parts by mass of the component (B).

The liquid crystal alignment treatment agent according to any one of the above aspects, wherein the liquid crystal alignment treatment agent contains 5 to 60% by mass of a weak solvent.

(17) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of the above (1) to (16).

(18) A liquid crystal display element comprising the liquid crystal alignment film of the above (17).

(19) The liquid crystal alignment film according to (17) above, wherein a liquid crystal display element produced by the step of: providing a liquid crystal layer between the substrates having one pair of electrodes, and the substrate of the pair of substrates A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the electrodes, and a voltage is applied between the electrodes to polymerize the polymerizable compound.

(20) A liquid crystal display element comprising the liquid crystal alignment film of the above (19).

(21) The liquid crystal alignment film according to the above (17), wherein a liquid crystal display element produced by the step of: providing a liquid crystal layer between the substrates having one pair of electrodes, and the substrate of the pair of substrates A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the electrodes, and a voltage is applied between the electrodes to polymerize the polymerizable group.

(22) A liquid crystal display element comprising the liquid crystal alignment film of the above (21).

By using the liquid crystal alignment treatment agent of the present invention, a liquid crystal alignment film which is less likely to cause chipping of the polymer film accompanying the rubbing treatment or scratching with the rubbing treatment in the manufacturing process of the liquid crystal display element, further, even if long Exposure to light exposure to time also suppresses a decrease in voltage retention. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like.

The present invention relates to a liquid crystal alignment film containing the component (A) and the component (B) described below, a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

Component (A): an amine compound having one amino group and a hydroxyl group in the molecule, and the above-mentioned amine group and a hydroxyl group are bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group (hereinafter, also referred to as Specific amine compound);

Component (B): at least one polymer selected from the group consisting of a polyimide intermediate and a polyimine (hereinafter also referred to as a specific polymer).

It is considered that in the liquid crystal alignment treatment agent of the present invention, the amine group of the specific amine compound forms a salt with a carboxyl group in a specific polymer, or, for a carboxyl group or a carboxyl ester group in a specific polymer, with water or an alcohol The cleavage of the guanamine bond, or the quinone imine group in a particular polymer, undergoes a ring-bonding reaction with a quinone imine group. Further, it is considered that the primary amine group which forms a salt with the carboxyl group in the specific polymer by the firing step in the production of the liquid crystal alignment film forms a guanamine bond by the detachment of water. As a result, it is considered that the liquid crystal of the present invention The treatment agent is not a simple means for mixing in an organic solvent, and a specific amine compound is efficiently bonded to a specific polymer in the liquid crystal alignment film obtained therefrom.

Further, the hydroxy group in the specific amine compound is an ester which reacts with a carboxyl group or a carboxyl ester group in a specific polymer, a water or alcohol detachment, or an ester which is accompanied by water detachment between hydroxyl groups in a specific amine compound. The reaction has been known. Therefore, as described above, the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention is a specific amine compound bonded to a specific polymer, a firing step in producing a liquid crystal alignment film, or a liquid crystal display element. The hardening step of the sealant, that is, the calcination step, causes crosslinking reaction between the polymers, improves physical stability, and further improves resistance to heat or light.

Further, in the present invention, the specific amine compound which causes the crosslinking reaction is bonded to the specific polymer, so that the characteristics of the liquid crystal display element caused by the residual of the unreacted component caused by the addition of the crosslinkable compound are not caused. problem.

Therefore, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is less likely to cause chipping of the polymer film accompanying the rubbing treatment in the manufacturing process of the liquid crystal display element or the liquid crystal alignment film not containing the specific amine compound. Further, even if it is exposed to light for a long period of time, it is possible to suppress a decrease in the voltage holding ratio.

Since the specific amine compound is one in the first-order amine group contained in the molecule, it is possible to cause a problem of precipitation or gelation of the polymer when the liquid crystal alignment agent is prepared or during storage of the liquid crystal alignment agent. Can also be avoided.

<Specific amine compound>

The specific amine compound of the present invention is an amine compound having one amine group and a hydroxyl group in the molecule and which is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group in the above-mentioned amine group.

More specifically, it is an amine compound represented by the following formula [1].

In the formula [1], X ₁ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, since the first-stage amine group contained in the specific amine compound is a salt which is easily formed into a salt or a bonding reaction with a specific polymer.

Specific examples of the aliphatic hydrocarbon group include a linear alkyl group, a branched alkyl group, or a hydrocarbon group having an unsaturated bond. Among them, a linear or branched alkyl group having a carbon number of 1 to 20 is preferred. More preferably, it is a linear or branched alkyl group having a carbon number of 1 to 15, preferably a linear or branched alkyl group having a carbon number of 1 to 10.

Specific examples of the non-aromatic cyclic hydrocarbon group may, for example, be a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclodecane ring or a cyclodecane. Ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring , cyclooctadecane ring, cyclopentadecane ring, cycloecosane ring, tricyclohexadecane ring, tricyclotetracosane ring, bicyclohexyl ring, bicycloheptane ring, decalin Ring, nortzene ring, adamantane ring, and the like. Among them, it is preferably a ring composed of 3 to 20 carbon atoms. More preferably, it is a ring composed of carbon numbers 3 to 15, and the best is a non-aromatic ring of a ring composed of carbon numbers 6 to 12. Hydrocarbyl group. Specifically, it is a cyclohexane ring or a bicyclohexyl ring, and particularly preferably a cyclohexane ring.

In the formula [1], X ₂ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ ) CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -. Among them, a single bond, -O-, -NH-, -COO-, -OCO-, -CONH- or -NHCO- is preferred. More preferably, it is a single bond, -O-, -NH-, -OCO- or -NHCO-, and is most preferably a single bond, -O-, -OCO-.

In the formula [1], X ₃ is a single bond, a benzene ring or a cyclohexane ring, more preferably a single bond or a benzene ring.

In the formula [1], X ₄ is a single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ ) CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -. Wherein it is preferably a single bond, -O-, -NH-, -COO-, -OCO-, -CONH- or -NHCO-, more preferably a single bond, -O-, -NH-, -OCO-, or - CONH-, most preferably a single bond, -O-, -NH- or CONH-.

In the formula [1], X ₅ is a single bond, an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Specific examples of the aliphatic hydrocarbon group and the non-aromatic cyclic hydrocarbon group include the above. Among them, a single bond, a linear or branched alkyl group having 1 to 20 carbon atoms, or a non-aromatic cyclic hydrocarbon group composed of 3 to 20 carbon atoms is preferable. More preferably, it is a single bond, a linear or branched alkyl group having 1 to 15 carbon atoms, or a non-aromatic cyclic hydrocarbon group composed of 3 to 15 carbon atoms. The best single bond, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexane ring or a bicyclohexyl ring, particularly preferably a single bond, a linear or branched carbon number of 1 to 10. Alkyl or cyclohexane ring.

In the formula [1], n is an integer of 1 to 5. Among them, it should be an integer of 1~4. More preferably an integer of 1 to 3.

Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ and n in the formula [1] are as shown in Tables 1 to 14.

<Specific polymer>

The specific polymer of the present invention is a polymer selected from the group consisting of a polyimide precursor and a polyimine, and the polyimine precursor system has a structure represented by the following formula [A]. .

(In the formula [A], R ₁ is a tetravalent organic group, R ₂ is a divalent organic group, and A ₁ and A ₂ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different. , n represents a positive integer).

The specific polymer of the present invention is preferably obtained by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as a raw material, which can be relatively easily obtained. Repeated by the formula [D] below The polyamine acid formed by the structural formula of the unit or the polyimine which imidizes the polyphosphonium amide.

(In the formula [B] and the formula [C], R ₁ and R ₂ are the same as those defined by the formula [A]).

(In the formula [D], R ₁ , R ₂ and n are the same as those defined by the formula [A]).

In the formula [A] and the formula [D], each of R ₁ and R ₂ may be one type, or may be a repeating unit having mutually different R ₁ and R ₂ , and a plurality of different types may be combined.

As the diamine component, a diamine compound having a side chain represented by the following formula [2] (hereinafter, sometimes referred to as a specific side chain structure) is preferably used.

(In the formula [2], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. The bond, -(CH ₂ ) _a - (a is an integer from 1 to 15), -O-, -CH ₂ O- or -COO-, is preferred because of the easy synthesis of a side chain structure. More preferably, a single bond, - (CH ₂ ) _a - (a is an integer from 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula [2], Y ₂ is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, it is preferably a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10).

In the formula [2], Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO-. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- is preferred because of ease of synthesis. More preferably, it is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO-.

In the formula [2], Y ₄ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be a carbon number of 1 to 3. An alkyl group, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Further, Y ₄ is a divalent organic group selected from an organic group having a carbon number of 12 to 25 of a steroid skeleton. Among them, an organic group having a carbon number of 12 to 25 which is a benzene ring, a cyclohexane ring or a steroid skeleton is preferable.

In the formula [2], Y ₅ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be a carbon number of 1 to 3. The alkyl group, the alkoxy group having 1 to 3 carbon atoms, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted.

In the formula [2], n is an integer of 0 to 4, and is preferably an integer of 0 to 2.

In the formula [2], Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. . Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Most preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

Preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [2] are as shown in Tables 15 to 56.

In the method of introducing a specific side chain structure into the polymer of the present invention, it is preferred to use a diamine compound (hereinafter also referred to as a specific diamine compound) represented by the following formula [2a] in one part of the raw material.

Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [2a] have the same meanings as defined in [2], and m is an integer of 1 to 4. )

Further, in the above formula [2a], a preferable combination of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n is the same as in the formula [2], as shown in Table 15 to Table 56. in.

In the formula [2a], m is an integer of 1 to 4. It should be an integer of 1.

More specifically, it is a structure shown by the following formula [2-1] - [2-32].

(In the formula [2-1] and the formula [2-2], R ₁ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, and R ₂ is a carbon number 1 or more and 22 or less alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups).

(In the formula [2-3]~form [2-5], R ₃ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, or -CH ₂ -, R ₄ 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).

(In the formula [2-6] and the formula [2-7], R ₅ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ -, or -O-, R ₆ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group).

(In the formula [2-8] and the formula [2-9], R ₇ is an alkyl group having 3 or more and 12 or less carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is trans Isomer).

(In the formula [2-10] and the formula [2-11], R ₈ is an alkyl group having 3 or more and 12 or less carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is trans Isomer).

(In the formula [2-12], A ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₃ is 1,4-cyclohexylene or 1,4-phenylene, and A ₂ is oxygen. atom or -COO - * (but, with "*" as the bonding hand bonded to A _3), A ₁ is an oxygen atom or -COO - * (but, with "*" as the bonding hand and (CH ₂ )a ₂ ) Bonding). Further, 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.

In the present invention, as the diamine component, a diamine compound other than a specific diamine compound (hereinafter sometimes referred to as a diamine compound) may be used as long as the effects of the present invention are not impaired. Specific examples thereof can be exemplified as follows.

P-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylene Diamine, 2,5-diaminomethyl Benzene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-Diaminobenzyl alcohol, 4,6-diaminoxyxylenol, 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'-di Aminobiphenyl, 4,4'-diaminodiphenylmethane, 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'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3 '-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl) ) decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine , 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenyl Amine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3'-diaminodiphenyl) Amine, N-methyl(3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3 '-Diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-Diaminobenzophenone, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6 -diaminonaphthalene, 1,7-diamino group Naphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2 - bis(4-aminophenyl)ethane, 1,2-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-amine 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-phenylphenylbis(methylene)]diphenylamine, 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene bis[ (4-aminophenyl))ethanone], 1,4-phenylphenylbis[(3-aminophenyl)ethanone], 1,3-phenylene bis[(4-aminophenyl) Ethyl ketone], 1,3-phenylene bis[(3-aminophenyl)ethanone], 1,4-phenylene bis(4- Benzoate), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-stretch Phenyl bis(3-aminobenzoate), bis(4-aminophenyl)p-phthalate, bis(3-aminophenyl)p-phthalate, bis(4-aminophenyl) Isodecanoate, bis(3-aminophenyl)isodecanoate, N,N'-(1,4-phenylene)bis(4-aminophenylguanamine), N,N'- (1,3-phenylene) bis(4-aminophenylguanamine), N,N'-(1,4-phenylene)bis(3-aminophenylguanamine), N,N'- (1,3-phenylene) bis(3-aminophenylguanamine), N,N'-bis(4-aminophenyl)-p-amine, N,N'-bis(3-amino group Phenyl) Indoleamine, N,N'-bis(4-aminophenyl)isodecylamine, N,N'-bis(3-aminophenyl)isodecylamine, 9,10-bis(4-amine Phenyl) onion, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2, 2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 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, 1,3'-bis(4-aminophenoxy) Propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butyl Alkane, 1,5-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)butane, 1,5-bis(3-aminophenoxy) Pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy) Heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxyl) Octyl, 1,9-bis(4-aminophenoxy)decane 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-Aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane 1,12-(3-Aminophenoxy)dodecane, 4-(aminomethyl)aniline, 3-(aminomethyl)aniline, 4-(2-aminoethyl)aniline or An aromatic diamine group such as 3-(2-aminoethylaniline); an alicyclic group such as bis(4-aminocyclohexyl)methane or bis(4-amine-3-methylcyclohexyl)methane Amino; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-di Aminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-di An aliphatic diamine such as an aminoundecane or a 1,12-diaminododecane.

Further, as long as the effects of the present invention are not impaired, a diamine compound having an alkyl group or a fluoroalkyl group in the side chain of the diamine can be used.

Specifically, a diamine represented by the following formula [DA1] to formula [DA12] can be exemplified.

(In the formula [DA1] to the formula [DA5], A ₁ is an alkyl group having 1 or more and 22 or less carbon atoms or a fluorine-containing alkyl group).

(In the formula [DA6]~[DA11], A ₂ is -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ₃ It is an alkyl group or a fluorine-containing alkyl group having 1 or more and 22 or less carbon atoms.

(In the formula [DA12], p is an integer from 1 to 10).

Further, the diamine compound represented by the following formula [DA13] to [DA20] may be used as long as the effects of the present invention are not impaired.

(In the formula [DA17], m is an integer of 0 to 3, and in the formula [DA20], n is an integer of 1 to 5).

Further, the diamine compound having a carboxyl group in the molecule represented by the following formula [DA21] to formula [DA24] can be used as long as the effects of the present invention are not impaired.

(In the formula [DA21], m ₁ is an integer of 1 to 4, and in the formula [DA22], A ₄ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, - CF ₂ -, -C(CF ₃ )-, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-, m ₂ and m ₃ are each an integer from 0 to 4, and m ₂ + m ₃ is 1 to 4 In the formula [DA 23], m ₄ and m ₅ are each an integer of 1 to 5, and in the formula [DA 24], A ₅ is a linear or branched alkyl group having 1 to 5 carbon atoms, and m ₆ is 1 An integer of ~5, in the formula [DA25], A ₆ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ )- , -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON (CH ₃ )- or -N(CH ₃ )CO-, m ₇ is an integer from 1 to 4).

The specific diamine compound and the other diamine compound may be used in combination of one type or two types or more depending on the characteristics of the liquid crystal alignment property, the voltage holding ratio, and the accumulated charge when the liquid crystal alignment film is formed.

In order to obtain a specific polymer of the present invention, a tetracarboxylic dianhydride (hereinafter also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [3] is used as a part of the raw material.

In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms, and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.

Specifically, the structure is represented by the following formula [3a] to formula [3j].

In the formula [3a], Z ₂ to Z ₆ are groups selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, and in the formula [3g], Z ₆ and Z ₇ It is a hydrogen atom or a methyl group, which may be the same or different.

In the formula [3], the structure of Z _{1 is} preferably from the reactivity of the polymerization or the ease of synthesis, and is a formula [3a], a formula [3c], a formula [3d], a formula [3e], a formula [3f] or a formula. [3g].

In the present invention, tetracarboxylic dianhydride (hereinafter also referred to as other tetracarboxylic dianhydride) other than tetracarboxylic dianhydride may be used as long as the effects of the present invention are not impaired. Other tetracarboxylic dianhydride systems can be exemplified by the following four Carboxylic dianhydride.

Trimellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6, 7-Onion tetracarboxylic acid, 1,2,5,6-onion tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetra Carboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)anthracene, bis(3) , 4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-dual (3, 4-Dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4,5-pyridine Tetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid Acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The specific tetracarboxylic dianhydride and the other tetracarboxylic dianhydride described above may be used in combination of one type or two types or more depending on the characteristics of the liquid crystal alignment property, the voltage holding ratio, and the accumulated electric charge when the liquid crystal alignment film is formed.

The specific polymer of the present invention is a polymer selected from the group consisting of a polyimide intermediate and a polyimine, and the polyimine precursor system has a structure represented by the formula [A].

In the present invention, the method of synthesizing a specific polymer is not particularly limited. Generally, a diamine component and a tetracarboxylic acid component can be obtained by reaction. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and a derivative thereof, and a diamine component composed of one or a plurality of diamine components are reacted to obtain a polyamine. acid. Specifically, a method in which a tetracarboxylic dianhydride and a diamine component are polycondensed to obtain a poly-proline acid; and a tetracarboxylic acid and a diamine component are removed A method in which a polyglycine is obtained by a water polycondensation reaction or a method in which a tetracarboxylic acid dihalide is condensed with a diamine component to obtain a polyamic acid.

In order to obtain a polyamic acid alkyl ester system, a method of polycondensing a carboxylic acid group by dialkyl esterification of a tetracarboxylic acid with a diamine component; a dicarboxylic acid esterification of a carboxylic acid group by dialkylation A method of polycondensing a halide with a diamine component or a method of converting a carboxyl group of a polyamic acid to an ester.

Further, in order to obtain a polyimine type, a method of forming a polyimine by subjecting the above polyamic acid or polyalkyl amide to ruthenium iodide can be used.

The liquid crystal alignment film obtained by using the specific polymer of the present invention has a higher content ratio of the specific diamine compound in the above diamine component, and the liquid crystal pretilt angle can be increased. The purpose of improving this property is preferably 5 mol% or more and 80 mol% or less of the diamine component as a specific diamine compound. In particular, from the viewpoint of the coatability of the liquid crystal alignment agent or the electrical properties of the liquid crystal alignment film, it is preferably 5 mol% or more and 60 mol% or less of the diamine component as a specific diamine compound.

Further, in order to obtain a specific polymer of the present invention, it is preferred to use a specific tetracarboxylic dianhydride for the tetracarboxylic acid component. In this case, 1 mol% or more of the tetracarboxylic acid component is preferably a specific tetracarboxylic dianhydride, more preferably 5 mol% or more, and most preferably 10 mol% or more. Further, 100 mol% of the tetracarboxylic acid component may be a specific tetracarboxylic dianhydride.

The reaction of the diamine component with the tetracarboxylic acid component is generally carried out in an organic solvent. The organic solvent to be used at this time is not particularly limited as long as it is dissolved in the produced polyimide precursor. Specific examples thereof can be exemplified as follows.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2- Pyrrolidone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropanol, methoxymethyl Pentanol, dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, 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-tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoethyl Acid ester, diethylene glycol dimethyl ether, dipropylene glycol monoacetate 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-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol , diisopropyl ether, ethyl isobutyl ether, Diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, 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, acetone Methyl ester, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3 - methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used alone or in combination. Further, it may be a range in which the solvent for dissolving the polyimide precursor is not precipitated in the produced polyimide precursor. It can be used by mixing with the above solvent. Further, the water in the organic solvent inhibits the polymerization reaction, and further causes the produced polyimine precursor to be hydrolyzed. Therefore, it is preferred to use a dehydrated organic solvent.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a method in which a diamine component is dispersed or dissolved in an organic solvent, and the tetracarboxylic acid component is directly or dispersed or dissolved in an organic solvent, is added; On the other hand, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent; a method of alternately adding a tetracarboxylic acid component and a diamine component, or the like can be used. In addition, when a plurality of kinds of the diamine component or the tetracarboxylic acid component are reacted by using a plurality of kinds, the reaction can be carried out in a state of being mixed in advance, and the reaction can be carried out in an individual order, and the low-molecular weight of the individual reaction can be mixed and reacted. polymer. The polymerization temperature at this time may be any temperature from -20 ° C to 150 ° C, but preferably in the range of -5 ° C to 100 ° C. Further, the reaction system can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a specific polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and it is difficult to uniformly stir. Therefore, it is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter, an organic solvent can be added.

In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. In general, the polycondensation reaction is similar. The closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimine precursor.

The polyimine of the present invention is a polyimine obtained by dehydration ring closure of the aforementioned polyimide precursor, which can be used as a liquid crystal alignment film. polymer.

In the polyimine of the present invention, the dehydration ring closure ratio (the imidization ratio) of the proline group is not necessarily 100%, and can be arbitrarily adjusted depending on the purpose or purpose.

The method for imidating the polyimine precursor ruthenium may, for example, be a hydrazine imidization in which a solution of the polyimide precursor is directly heated or a catalyst contact in a solution of the polyimide precursor Media imidization.

The temperature at which the polyimide precursor is thermally imidated in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and should be removed to the outside of the system by the water formed by the imidization reaction. The method of doing it.

The catalyst oxime imidization of the polyimide precursor is added to the solution of the polyimide precursor to add a base catalyst and an acid anhydride, and is stirred at -20 ° C to 250 ° C, preferably at 0 ° C to 180 ° C. . The amount of the alkaline catalyst is 0.5 moles to 30 moles of the proline group, preferably 2 moles to 20 moles, and the amount of the anhydride is 1 mole of the prolyl group. Mohr times, preferably 3 moles ~ 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate basicity in carrying out the reaction. The acid anhydride may, for example, be acetic anhydride, trimellitic anhydride or pyromellitic anhydride. Among them, when acetic anhydride is used, the purification after the completion of the reaction becomes easy, which is preferable. The ruthenium imidization rate produced by the imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be precipitated by putting the reaction solution into a solvent. The solvent used for precipitation may, for example, be methanol. Acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated by the solvent is recovered by filtration, and then dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, if the precipitated and recovered polymer is redissolved in an organic solvent, the operation of reprecipitation and recovery is repeated twice to 10 times to reduce impurities in the polymer. The solvent at this time may, for example, be an alcohol, a ketone or a hydrocarbon. When three or more types of solvents selected from these are used, the efficiency of purification is further improved, which is preferable.

The molecular weight of the specific polymer of the present invention is preferably a weight average measured by a GPC (Gel Permeation Chromatography) method, in consideration of the strength of the obtained polymer film, the workability when the polymer film is formed, and the uniformity of the polymer film. The molecular weight is 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Liquid 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 coating liquid containing a specific amine compound, a polymer component containing a specific polymer, and an organic solvent.

The content of the specific amine compound in the liquid crystal alignment agent of the present invention is preferably from 0.1 part by mass to 150 parts by mass based on 100 parts by mass of the specific polymer, and a crosslinking reaction is carried out to exhibit a desired film hardenability, and Since the alignment of the liquid crystal is lowered, it is more preferably 0.1 part by mass to 100 parts by mass. The optimum is 0.1 parts by mass to 50 parts by mass, and particularly preferably 0.1 parts by mass to 20 parts by mass.

The polymer component in the liquid crystal alignment treatment agent of the present invention may all be a specific polymer used in the present invention, and other polymers other than the polymer of the present invention may be mixed. In this case, the content of the polymer other than the polymer component is from 0.5% by mass to 15% by mass, preferably from 1% by mass to 10% by mass. Other polymers other than this may, for example, be a polyimine precursor or a polyimine obtained from a diamine component not containing a specific diamine compound and a tetracarboxylic acid component not containing a specific tetracarboxylic dianhydride. Further, specific examples of the polyimine precursor and the polymer other than the polyimine may, for example, be an acrylic polymer, a methacrylic polymer, polystyrene or polyamine.

The organic solvent in the liquid crystal alignment treatment agent of the present invention is preferably from 70% by mass to 99% by mass based on the viewpoint of forming a uniform polymer film by coating. This content can be appropriately changed depending on the film thickness of the intended liquid crystal alignment film. The organic solvent in this case is not particularly limited as long as it is an organic solvent in which the specific polymer is dissolved. More specifically, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone , N-ethyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 1,3- Dimethyl-imidazoline copper, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, carbonic acid Propylene ester, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used alone or in combination.

The liquid crystal alignment treatment agent of the present invention is as long as the effect of the present invention is not impaired Further, a crosslinkable compound having an epoxy group, an isocyanate group or an oxetanyl group, and a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group may be introduced. A crosslinkable compound having a polymerizable unsaturated bond.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl trimer isocyanate, and tetraglycidyl. Aminodiphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl etherethane, three Phenyl glycidyl ether ethane, bisphenol hexafluoroacetamido diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl- 2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl M-xylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropane) Oxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-() 1-(4-(2,3-Enooxypropoxyphenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

The crosslinkable compound having an oxetane group has at least two crosslinkable compounds of an oxetanyl group represented by the following formula [4].

Specifically, it is a cross-linking compound represented by the following formula [4a] to formula [4k]. Things.

The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group may, for example, be an amine-based resin having a hydroxyl group and/or an alkoxy group, for example, a melamine resin, a urea resin, or a hydrazine. Amine resin, glycol urea-formaldehyde resin, succinimide-formaldehyde resin, ethylene urea-formaldehyde resin, and the like. Specifically, a melamine derivative, a benzoguanamine derivative, a glycolureido group or the like in which a hydrogen atom of an amine group is substituted with a methylol group, an alkoxymethyl group or both can be used. The melamine derivative or the benzoguanamine derivative may be present in a form of 2 or 3 parts. It is preferable that these one triazine ring has an average of 3 or more and 6 or less of a methylol group or an alkoxymethyl group.

Examples of such a melamine derivative or a benzoguanamine derivative include, for example, MX-750 in which each methoxymethyl group of one triazine ring of a commercially available product is substituted, and one triazine ring per one. The methoxymethyl group was substituted with an average of 5.8 MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methylated melamine, Cymel 235, 236, 238, 212, 253, 254, etc. methoxymethylated butoxymethylated melamine, Cymel 506, 508, etc., butoxymethylated melamine, Cymel 1141 a methoxymethylated isobutoxymethylated melamine containing a carboxyl group, a methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123, a methoxymethyl group such as Cymel 1123-10 Butoxymethylated benzoguanamine, a butoxymethylated benzoguanamine such as Cymel 1128, a carboxyl group-containing methoxymethylated ethoxymethylated benzene such as Cymel 1125-80 Indoleamine (above, manufactured by Mitsui Cyanamide Co., Ltd.). Further, examples of the glycolic urea group include, for example, a butoxymethylated glycolyl group of Cymel 1170, such as Hydroxymethylated glycolylurea of Cymel 1172, such as methoxymethylolated glycolylurea of Powderlink 1174, and the like.

Examples of the benzene or phenolic compound having a hydroxyl group and/or an alkoxy group include 1,3,5-glycol (methoxymethyl)benzene, 1,2,4-para(isopropylmethyl)benzene, and 1 , 4-bis(second butoxymethyl)benzene, 2,6-dihydroxymethyl-t-butylphenol, and the like.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tris(A). a cross-linking compound having three polymerizable unsaturated groups in the molecule, such as oxyethoxy trimethylolpropane, glycerol polyglycidyl ether poly(meth) acrylate, etc. (Meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate Ester, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate , propylene oxide bisphenol A type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(meth) acrylate, B Glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, bismuth citrate a cross-linking compound having two polymerizable unsaturated groups in the molecule, such as a diester (meth) acrylate or a neopentyl glycol bis(meth) acrylate, a 2-hydroxyethyl group Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxime-2-hydroxypropyl phthalate, 3 -Chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2-(methyl) propylene oxiranyl ethyl phosphate, N- hydroxymethyl (meth) acrylamide It is equivalent to a crosslinkable compound having one polymerizable unsaturated group in the molecule.

Further, a compound represented by the following formula [5] can also be used.

(In the formula [5], E ₁ is a group selected from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an onion ring, and a phenanthrene ring. E ₂ is a group selected from the following formula [5a] and formula [5b], and n is an integer of 1 to 4).

The compound is an example of a crosslinkable compound, and is not limited thereto. In addition, the crosslinkable compound contained in the liquid crystal alignment treatment agent of the present invention may be one type or two or more types.

The content of the crosslinkable compound in the liquid crystal alignment agent of the present invention is preferably from 0.1 part by mass to 150 parts by mass based on 100 parts by mass of the polymer component, and the crosslinking reaction proceeds to exhibit the intended effect without lowering the liquid crystal. Orientation, so it is more preferably 0.1 parts by mass to 100 parts by mass, particularly preferably 1 part by mass. ~50 parts by mass.

A compound which promotes charge transfer in a liquid crystal alignment film and promotes charge removal using a liquid crystal cell of the liquid crystal alignment film, and a nitrogen-containing impurity represented by the following formula [M1] to [M156] is preferably added to the liquid crystal alignment treatment agent. Cyclic amine compound. It is also possible that the amine compound is directly added to a solution of a specific polymer. It is preferred to form a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass, with a suitable solvent. The solvent is not particularly limited as long as it is an organic solvent in which the specific polymer is dissolved.

In the liquid crystal alignment treatment agent of the present invention, an organic solvent which improves the film thickness uniformity or surface smoothness of the polymer coating film when the liquid crystal alignment treatment agent is applied can be used as long as the effect of the present invention is not impaired (hereinafter, also referred to as Weak solvent) or compound. Further, a compound which enhances the adhesion between the liquid crystal alignment film and the substrate can also be used.

Specific examples of the weak solvent for improving the film thickness uniformity or the surface smoothness are as follows.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Kikabi alcohol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol , propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether Dipropylene glycol monoacetate single Methyl 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-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl Acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-heptane, n-octane, diethyl ether, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxy Butyl propionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol Monoacetate, propylene glycol diacetate, 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, isoamyl lactate, etc. with low surface tension Organic solvent.

These weak solvents can be used in one type or in a plurality of types. When the weak solvent is used, it is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, based on the total of the organic solvent contained in the liquid crystal alignment treatment agent.

Examples of the compound which improves film thickness uniformity or surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant.

More specifically, for example, Eftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

Specific examples of the compound which enhances the adhesion between the liquid crystal alignment film and the substrate include a functional decane-containing compound or an epoxy group-containing compound shown below.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N -(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureido Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymethyl decyl propyl triethylene triamine, N-trimethoxymethyl decyl propyl triethylene triamine, 10-trimethoxymethyl decyl-1 4,7-Trisazocane, 10-triethoxycarbamido-1,4,7-trisazocane, 9-trimethoxycarbamido-3,6-diazoindolyl Acetate, 9-triethoxycarbamido-3,6-diazoindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl- 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-benzene 3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltriethoxylate Base decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-four Glycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamino) Base) cyclohexane, N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When the compound is used to improve the adhesion to the substrate, it is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. . If it is less than 0.1 part by mass, the effect of improving the adhesion is not expected, and if it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

In the liquid crystal alignment treatment agent of the present invention, in addition to the compound which enhances the above-mentioned crosslinkable compound, weak solvent, uniformity of film thickness or surface smoothness, and a compound which improves adhesion to a substrate, A dielectric or a conductive material for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the liquid crystal alignment film may be added to the range of the effects of the invention.

<Liquid crystal alignment film, liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention is applied onto a substrate, and after firing, it is subjected to alignment treatment by rubbing treatment or light irradiation, and can be used as a liquid crystal. Orientation film. Further, in the case of vertical alignment use or the like, it can be used as a liquid crystal alignment film even without alignment treatment. The substrate to be used in this case is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate may be used in addition to the glass substrate. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like for driving a liquid crystal is formed. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer may be used as the substrate on only one side, and in the case of the electrode system, a material that reflects light such as aluminum may be used.

The coating method of the liquid crystal alignment agent is not particularly limited, and industrially, it is generally a method of screen printing, lithography, flexographic printing, ink jet method, or the like. Other coating methods include a dipping method, a roll coating method, a die coating method, a spin coating method, a spray coating method, and the like, and these may be used according to the purpose.

After the liquid crystal alignment agent is applied onto the substrate, the polymer film is formed by evaporating the solvent at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate. If the thickness of the polymer film after firing is too thick, it is disadvantageous in the power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 nm to 300 nm, more preferably 10nm~100nm. When the liquid crystal is aligned horizontally or obliquely, the polymer film after firing is treated by rubbing or polarized ultraviolet rays or the like.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention, and a liquid crystal cell is produced by a known method to form a liquid crystal display element.

The method for fabricating a liquid crystal cell is to prepare a pair of substrates on which a liquid crystal alignment film is formed, and to spread a spacer on a liquid crystal alignment film of a single substrate to make a liquid crystal The method in which the alignment film surface is on the inner side, the other substrate is bonded, the liquid crystal is injected under reduced pressure, and the liquid crystal is dropped on the liquid crystal alignment film surface of the spacer, and the substrate is bonded and sealed.

Further, in the liquid crystal alignment treatment agent of the present invention, it is preferable to use a liquid crystal display element produced by the following steps: a liquid crystal layer is provided between the substrates having one pair of electrodes, and the active energy is disposed between the pair of substrates A liquid crystal composition of a polymerizable compound in which at least one of a wire and a heat is polymerized, and a step of applying a voltage between the electrodes and polymerizing the polymerizable compound by at least one of irradiation with an active energy ray and heat. Here, the active energy ray is suitably ultraviolet light.

The above liquid crystal display element controls the pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, and a liquid crystal cell is assembled, and a photopolymerizable compound is irradiated with ultraviolet rays or the like by applying a specific voltage to the liquid crystal layer. The resulting polymer controls the pretilt angle of the liquid crystal molecules. Since the alignment state of the liquid crystal molecules at the time of polymer formation is also stored after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer or the like. In the PSA method, since the rubbing treatment is not required, it is suitable for the formation of the vertical alignment type liquid crystal layer which is difficult to control the pretilt angle by the rubbing treatment.

In other words, the liquid crystal display device of the present invention obtains a liquid crystal cell from a substrate having a liquid crystal alignment film from the liquid crystal alignment agent of the present invention, and polymerizes the polymerizable compound by at least one of irradiation and heating of ultraviolet rays. To control the alignment of liquid crystal molecules.

For example, in an example of liquid crystal cell formation, a pair of substrates of a liquid crystal alignment film are prepared, and a spacer is spread on a liquid crystal alignment film of one of the substrates so that the liquid crystal alignment film surface becomes inside, and then the other substrate is bonded. A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dispensed onto a liquid crystal alignment film surface of a spacer, and a substrate is bonded and sealed.

A polymerizable compound which is polymerized by liquid crystal mixing by heat or ultraviolet irradiation. The polymerizable compound is, for example, a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. The polymerizable compound is preferably from 0.01 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 5 parts by mass, per 100 parts by mass of the liquid crystal molecule. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound is not polymerized, and the alignment of the liquid crystal cannot be controlled. When the amount is more than 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the sintering characteristics of the liquid crystal display element are lowered.

After the liquid crystal cell is produced, a voltage of alternating current or direct current is applied to the liquid crystal cell, and the polymerizable compound is polymerized by irradiating heat or ultraviolet light. Thereby, the alignment of the liquid crystal molecules can be controlled.

Further, in the liquid crystal alignment treatment agent of the present invention, it is preferable to use a liquid crystal display element which is produced by the step of providing a liquid crystal layer between the substrates having one pair of electrodes, and arranging the activity between the pair of substrates A liquid crystal alignment film of a polymerizable group in which at least one of energy rays and heat is polymerized, and a step of applying a voltage between the electrodes. Here, the active energy ray is suitably ultraviolet light.

A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is added, for example, to a liquid crystal alignment treatment agent. A method of using a compound having such a polymerizable group, or a method of using a polymer component containing a polymerizable group. Since the liquid crystal alignment treatment agent of the present invention contains a specific amine compound having a double bond site by heat or ultraviolet irradiation, at least one of irradiation and heating of the ultraviolet rays can control the alignment of the liquid crystal molecules. Further, the double bond portion may, for example, be an acrylic group, a methacryl group, a vinyl group or a myristyl group.

For example, in an example of liquid crystal cell formation, a pair of substrates of a liquid crystal alignment film are prepared, and a spacer is spread on a liquid crystal alignment film of one of the substrates so that the liquid crystal alignment film surface becomes inside, and then the other substrate is bonded. A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dispensed onto a liquid crystal alignment film surface of a spacer, and a substrate is bonded and sealed.

After the liquid crystal cell is produced, the voltage of the alternating or direct current is applied to the liquid crystal cell, and the alignment of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays.

As described above, the liquid crystal display device produced by using the liquid crystal alignment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but not limited thereto.

[Synthesis of Polyimine Precursor and Polyimine] (tetracarboxylic dianhydride)

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

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

TCA: tetracarboxylic dianhydride represented by the following formula

TDA: tetracarboxylic dianhydride represented by the following formula

(specific diamine compound)

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-PBCH5DABz: 1,3-diamino-5-{4-[4-(trans-4-n-pentylcyclohexyl)phenyl]phenoxymethyl}benzene

CoIDAB-1: a specific diamine compound represented by the following formula

CoIDAB-2: a specific diamine compound represented by the following formula

(other diamine compounds)

p-PDA: p-phenylenediamine

m-PDA: m-phenylenediamine

DBA: 3,5-diamino benzoic acid

AP18: 1,3-diamino-4-octadecyloxybenzene

(specific amine compound)

A-1: Aminoethanol

A-2: 3-amino-1-propanol

(Organic solvents)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Measurement of molecular weight of polyimine precursor and polyimine)

The number average molecular weight and the weight average molecular weight of the polyimine in the synthesis example are a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., Ltd.), and a column (KD-83, KD- 845) (manufactured by Shodex Co., Ltd.) was measured as follows.

Column temperature: 50 ° C

Solvent: N,N'-dimethylformamide (in terms of additives, lithium bromide-water and water (LiBr.H ₂ O) is 30 mmol / liter (liter), phosphoric acid, anhydrous crystals (o-phosphoric acid) is 30 mmol /L, tetrahydrofuran (THF) is 10ml / liter)

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000, 1,000) (Polymer laboratory system).

(Measurement of sulfhydrylation rate)

The oxime imidization ratio of the polyimine in the synthesis example was measured as usual. 20 mg of polyimine powder was placed in a NMR sample tube (NMR sampling tube standard) 5 (manufactured by Kusano Scientific Co., Ltd.), 0.53 ml of a mixture of dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane)) was added, and ultrasonic waves were applied thereto to completely dissolve. This solution was measured for proton NMR at 500 MHz by an NMR measuring machine (JNW-ECA 500) (manufactured by JEOL Ltd.). The ruthenium imidization rate determines the proton derived from the unaltered structure before and after the imidization as the reference proton, and the peak value of the proton is used and the NH group derived from the vicinity of 9.5 to 10.0 ppm and derived from proline The proton peak integrated value is obtained by the following formula.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is derived from the proton peak integrated value of the NH group of the proline, the peak integrated value of the y-based reference proton, and the α-poly-proline (the imidization ratio is 0%). The ratio of the number of reference protons to the NH proton of proline.

<Synthesis Example 1>

CBDA (3.10 g, 15.8 mmol), PCH7DAB (3.01 g, 7.90 mmol), and p-PDA (0.85 g, 7.90 mmol) were mixed in NMP (20.9 g), and reacted at 40 ° C for 6 hours to obtain a resin solid fraction. Polylysine solution (1) having a concentration of 25.0% by mass. The polyammonic acid solution had a number average molecular weight of 26,100 and a weight average molecular weight of 74,200.

<Synthesis Example 2>

BODA (5.31 g, 21.2 mmol), PCH7DAB (3.03 g, 7.96 mmol), and DBA (2.82 g, 18.6 mmol) were mixed in NMP (20.1 g), and reacted at 80 ° C for 5 hours, then CBDA (1.04 g) was added. , 5.30 mmol) and NMP (16.5 g), reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass. (2). The polyamine solution had a number average molecular weight of 25,300 and a weight average molecular weight of 65,100.

<Synthesis Example 3>

After adding NMP to the polyamic acid solution (2) (20.0 g) having a solid content concentration of 25.0% by mass of the resin obtained in Synthesis Example 2, and diluting it to 6 mass%, acetic anhydride as a ruthenium catalyst was added. (2.50 g) and pyridine (1.90 g) were reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (320 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (3). The polyamidimide had a ruthenium iodide ratio of 58%, a number average molecular weight of 21,500, and a weight average molecular weight of 5,1900.

<Synthesis Example 4>

BODA (5.36 g, 21.4 mmol), PBCH5DAB (4.05 g, 9.36 mmol), and DBA (2.65 g, 17.4 mmol) were mixed in NMP (21.6 g), and reacted at 80 ° C for 5 hours, then CBDA (1.05 g) was added. 5.35 mmol) and NMP (17.7 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) as a ruthenium amide catalyst were added at 90 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (400 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyimine had a hydrazine imidization ratio of 80%, a number average molecular weight of 19,600, and a weight average molecular weight of 49,100.

<Synthesis Example 5>

BODA (3.27 g, 13.1 mmol), m-PBCH5DABz (2.51 g, 5.61 mmol), and p-PDA (1.42 g, 13.1 mmol) were mixed in NMP (13.7 g), and reacted at 80 ° C for 5 hours, and then added. CBDA (1.10 g, 5.61 mmol) and NMP (11.2 g) were reacted at 40 ° C for 6.5 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamidic acid solution (20.1 g) and diluting it to 6 mass%, acetic anhydride (4.52 g) and pyridine (3.35 g) as a ruthenium amide catalyst were added at 90 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (430 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyamidimide had an imidization ratio of 81%, a number average molecular weight of 20,200, and a weight average molecular weight of 50,300.

<Synthesis Example 6>

BODA (5.26 g, 21.0 mmol), CoIDAB-1 (2.06 g, 3.94 mmol), and DAB (3.40 g, 22.3 mmol) were mixed in NMP (19.4 g), and reacted at 80 ° C for 5 hours, and then CBDA was added ( 1.03g, 5.25mmol) and NMP (15.9g), reacted at 40 ° C for 7 small At this time, a polyaminic acid solution having a resin solid content concentration of 25.0% by mass was obtained.

After adding NMP to the obtained polyamic acid solution (20.2 g) and diluting it to 6 mass%, acetic anhydride (2.55 g) and pyridine (1.92 g) as a ruthenium amide catalyst were added at 80 ° C. Reaction for 4 hours. This reaction solution was poured into methanol (310 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 17,200, and a weight average molecular weight of 45,900.

<Synthesis Example 7>

BODA (3.36 g, 13.4 mmol), CoIDAB-2 (1.42 g, 2.88 mmol), and p-PDA (1.77 g, 16.3 mmol) were mixed in NMP (12.7 g), and reacted at 80 ° C for 5 hours, and then added. CBDA (1.13 g, 5.76 mmol) and NMP (10.4 g) were reacted at 40 ° C for 7 hours to obtain a polyamic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2.48g) and pyridine (1.90g) which are a ruthenium-imidation catalyst were added, and it was 90 degreeC. Reaction for 3 hours. The reaction solution was poured into methanol (330 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyamidimide had a ruthenium iodide ratio of 53%, a number average molecular weight of 15,600, and a weight average molecular weight of 44,200.

<Synthesis Example 8>

TCA (3.12 g, 13.9 mmol), PCH7DAB (1.59 g, 4.18 mmol), and m-PDA (1.05 g, 9.71 mmol) were mixed in NMP (17.3 g), and reacted at 40 ° C for 6 hours to obtain a resin solid fraction. Polyammonic acid solution (8) having a concentration of 25.0% by mass. The polyamine has a number average molecular weight of 26,700 and a weight average molecular weight of 74,200.

<Synthesis Example 9>

TCA (3.10 g, 13.8 mmol), PBCH5DAB (1.79 g, 4.14 mmol), and DBA (1.47 g, 9.66 mmol) were mixed in NMP (19.1 g), and reacted at 40 ° C for 6 hours to obtain a resin solid content concentration of 25.0% by mass of a polyaminic acid solution.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6% by mass, acetic anhydride (2.46 g) as a ruthenium amide catalyst and pyridine (1.96 g) were added at 80 ° C. Reaction for 4 hours. The reaction solution was poured into methanol (320 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyimine had a hydrazine imidation ratio of 54%, a number average molecular weight of 23,200, and a weight average molecular weight of 59,600.

<Synthesis Example 10>

TCA (3.08 g, 13.7 mmol), CoIDAB (1.35 g, 2.74 mmol), and m-PDA (1.19 g, 11.0 mmol) were made in NMP ( 16.9 g) was mixed and reacted at 40 ° C for 8 hours to obtain a polyamic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (2.46 g) and pyridine (1.95 g) as a ruthenium amide catalyst were added at 80 ° C. Reaction for 4 hours. The reaction solution was poured into methanol (320 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyamidimide had a ruthenium iodide ratio of 53%, a number average molecular weight of 21,100, and a weight average molecular weight of 53900.

<Synthesis Example 11>

TDA (1.98 g, 6.59 mmol), PBCH5DAB (2.85 g, 6.59 mmol), and p-PDA (1.66 g, 15.4 mmol) were mixed in NMP (15.7 g), and reacted at 80 ° C for 5 hours, and then CBDA was added ( 3.01 g, 15.3 mmol) and NMP (12.8 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) as a ruthenium amide catalyst were added at 90 ° C. Reaction for 3 hours. This reaction solution was poured into methanol (450 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyimine had a hydrazine imidation ratio of 79%, a number average molecular weight of 19,100, and a weight average molecular weight of 48,500.

<Synthesis Example 12>

TDA (1.99 g, 6.64 mmol), m-PBCH5DABz (2.97 g, 6.65 mmol), and DBA (2.36 g, 15.5 mmol) were mixed in NMP (17.1 g), and reacted at 80 ° C for 5 hours, and then CBDA was added ( 3.04 g, 15.5 mmol) and NMP (14.0 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (20.5 g) and diluting it to 6 mass%, acetic anhydride (4.46 g) and pyridine (3.32 g) as a ruthenium amide catalyst were added at 90 ° C. . Reaction for 3 hours. This reaction solution was poured into methanol (450 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (12). The polyimine had a hydrazine imidation ratio of 80%, a number average molecular weight of 19,900, and a weight average molecular weight of 50,100.

<Synthesis Example 13>

BODA (5.61 g, 22.4 mmol), AP18 (3.17 g, 8.42 mmol), and DBA (2.99 g, 19.7 mmol) were mixed in NMP (21.2 g), and reacted at 80 ° C for 5 hours, then CBDA (1.10 g) was added. 5.61 mmol) and NMP (17.4 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

Adding NMP to the obtained poly-proline solution (20.0 g) After being released to 6 mass%, acetic anhydride (2.54 g) as a ruthenium amide catalyst and pyridine (1.95 g) were added, and the mixture was reacted at 80 ° C for 4.5 hours. The reaction solution was poured into methanol (330 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (13). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 18,200, and a weight average molecular weight of 46,200.

The poly-proline and polyimine of the present invention are shown in Table 57.

"Manufacture of Liquid Crystal Alignment Treatment Agent of the Present Invention"

In the following Examples 1 to 14 and Comparative Examples 1 to 4, the production examples of the liquid crystal alignment treatment agent are described, but each liquid crystal alignment treatment agent is used for evaluation. Further, the liquid crystal alignment treatment agents of the present invention are shown in Tables 58 and 59.

"Production of Liquid Crystal Alignment Film", "Evaluation of Rubbing Resistance", "Production of Liquid Crystal Cell (General Cell)", "Production of Liquid Crystal Cell (PSA Cell)" and "Evaluation of Electrical Characteristics" are as follows Like. Further, the characteristics of the respective liquid crystal alignment treatment agents obtained in Examples 1 to 14 and Comparative Examples 1 to 4 are shown in Tables 60 to 64. Tables 60 and 61 show the evaluation of the rubbing resistance, Table 62 and Table 63 show the evaluation of the electrical characteristics of the general cell, and Table 64 shows the evaluation results of the electrical characteristics of the PSA cell.

"Production of Liquid Crystal Alignment Film"

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of a substrate of 30 mm × 40 mm with an ITO electrode, heat-treated at 80 ° C for 5 minutes on a hot plate, and heat-treated at 220 ° C for 30 minutes in a heat cycle type dust-free oven to obtain a film. A substrate of a 100 nm thick agglomerated quinone liquid crystal alignment film.

"Evaluation of friction resistance"

In the coating film surface of the substrate with the liquid crystal alignment film obtained in the above-mentioned "production of liquid crystal alignment film", a screw fabric having a roll diameter of 120 mm was used, and the number of rotations of the roller was 300 rpm, the speed of the roller was 20 mm/sec, and Betting The friction treatment was carried out under the condition of an input of 0.4 mm. The surface of the liquid crystal alignment film in the vicinity of the center of the substrate after the rubbing treatment was observed at a random position by a laser microscope set at a magnification of 100 times, and the friction scratch and the friction shaving confirmed from the range of about 6.5 mm of the observation field of view. The average value of the amount of (attachment) was evaluated for the rubbing resistance. Moreover, the evaluation criteria are determined as follows.

(assessment basis)

A: 20 or less friction scraping or friction shavings

B: 20 to 40 friction scraping or friction shavings

C: 40 to 60 friction scraping or friction shavings

D: more than 60 friction scraping or friction shavings

"The production of liquid crystal cells (general unit cell)"

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of a substrate of 30 mm × 40 mm with an ITO electrode, heat-treated at 80 ° C for 5 minutes on a hot plate, and heat-treated at 220 ° C for 30 minutes in a heat cycle type dust-free oven to obtain a film. An ITO substrate of a 100 nm thick agglomerated quinone liquid crystal alignment film. The coating film surface of the ITO substrate was rubbed with a screw device having a roll diameter of 120 mm, and subjected to rubbing treatment under the conditions of a number of roll rotations of 1000 rpm, a roll speed of 50 mm/sec, and a pushing amount of 0.1 mm.

Two sheets of the obtained ITO substrate with the liquid crystal alignment film were prepared, and the liquid crystal alignment film surface was placed inside as a spacer of 6 μm, and the sealing agent was adhered to the periphery to form an empty cell. In this empty cell, MLC-6608 (manufactured by Merck Japan Co., Ltd.) was injected by a reduced pressure injection method, and the injection port was sealed to obtain a liquid. Unit cell (general unit cell).

With respect to the liquid crystal cells obtained in the examples and the comparative examples, the alignment uniformity of the liquid crystal was confirmed by a polarizing microscope. In any of the liquid crystal cells, there is no shaving or misalignment with the rubbing treatment, and the liquid crystal system is uniformly aligned.

"Liquid Cell Production (PSA Cell)"

The liquid crystal alignment treatment agent was spin-coated on a 10 mm × 10 mm substrate with an ITO electrode having a pattern interval of 20 μm, and an ITO surface of a substrate of 10 mm × 40 mm with an ITO electrode was spin-coated on the center, and heated at 80 ° C on a hot plate. After treating for 5 minutes, the film was heat-treated at 220 ° C for 30 minutes in a heat cycle type dust-free oven to obtain a polyimide film having a film thickness of 100 nm. The coating film surface was washed with pure water, and then heat-treated at 100 ° C for 15 minutes in a heat cycle type dust-free oven to obtain a substrate with a liquid crystal alignment film.

Here, the substrate of the liquid crystal alignment film was attached, and the liquid crystal alignment film surface was placed inside as a spacer of 6 μm, and the sealing agent was adhered to the periphery to form an empty cell. In the empty cell, 100% by weight of MLC-6608 (manufactured by Merck Japan Co., Ltd.) was injected into the liquid crystal, and 0.3% by mass of the polymerizable compound (1) represented by the following formula was injected, and then sealed. At the entrance, the liquid crystal cell is obtained.

A voltage of 5 V was applied to the obtained liquid crystal cell, and a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was intercepted, and ultraviolet irradiation of 20 J/cm ^{2 was} performed in a conversion of 365 nm to obtain a liquid crystal cell in which the alignment direction of the liquid crystal was controlled. (PSA unit cell). The temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was 50 °C.

The response speed of the liquid crystal before the ultraviolet irradiation and the liquid crystal after the ultraviolet irradiation was measured. The response speed is determined by a penetration rate of 90% to a penetration rate of 10% of T90→T10. It was confirmed that the PSA cell line obtained in the examples and the comparative examples had a faster response speed of the liquid crystal cell after the ultraviolet irradiation than the liquid crystal cell before the ultraviolet irradiation, so that the alignment direction of the liquid crystal can be controlled.

Further, the liquid crystal cells of either of them were observed by a polarizing microscope to confirm that the liquid crystals were uniformly aligned.

"Evaluation of Electrical Characteristics"

In the liquid crystal cell obtained by the above-mentioned "liquid crystal cell production (general cell)" and "liquid crystal cell production (PSA cell)", a voltage of 1 V was applied at a temperature of 80 ° C for 60 μm, and after 16.67 ms, After 50ms, the calculated voltage can be maintained as the voltage holding ratio (VHR). In addition, the measurement system used a voltage retention rate measuring device (manufactured by Toyo Corporation, VHR-1), and set a voltage (applied voltage): ±1 V, Pulse Width (applied pulse): 60 μs, and Flame Period: 16.67 ms. Or 50ms.

The liquid crystal cells whose measurement of the voltage holding ratio was terminated were irradiated with ultraviolet rays of 50 J/cm ² in terms of 365 nm, and then VHR was measured under the same conditions. Further, for the ultraviolet irradiation, a desktop type UV curing device (HCT 3B28 HEX-1) (manufactured by Sen Light Co., Ltd. (SEN LIGHT CORPORATION) was used.

<Example 1>

The polyamic acid solution (1) (10.0 g), NMP (5.67 g), and A-1 NMP solution (1.50 g) of the resin having a solid content concentration of 25.0% by mass obtained in Synthesis Example 1 were mixed (A-1 was 5 mass% of NMP solution) and BCS (25.8g) were stirred at 25 ° C for 2 hours to obtain a liquid crystal alignment treatment agent (1). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (1), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell and the PSA unit cell were carried out under the above conditions.

<Example 2>

The polyamic acid solution (2) (10.5 g), NMP (8.95 g), and A-1 NMP solution (2.51 g) of the resin having a solid content concentration of 25.0% by mass obtained in Synthesis Example 2 were mixed (A-1 was 5 mass% of NMP solution) and BCS (22.0 g) were stirred at 25 ° C for 2.5 hours to obtain a liquid crystal alignment treatment agent (2). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (2), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions. .

<Example 3>

NMP (13.8 g) was added to the polyimine powder (3) (2.48 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-1 in NMP (1.49 g) (A-1 was 5.0% by mass of NMP solution), NMP (8.13 g) and BCS (19.2 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment. Treatment agent (3). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (3), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell and the PSA unit cell were carried out under the above conditions.

<Example 4>

NMP (13.6 g) was added to the polyimine powder (3) (2.51 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-2 in NMP (2.51 g) (A-2 was 5.0% by mass of NMP solution), NMP (8.00 g) and BCS (19.8 g) were added to the solution, and the mixture was stirred at 50 ° C for 12 hours to obtain a liquid crystal alignment. Treatment agent (4). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (4), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions. .

<Example 5>

NMP (13.3 g) was added to the polyimine powder (4) (2.50 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-1 in NMP (3.50 g) (A-1 was 5.0% by mass of NMP solution), NMP (7.77 g) and BCS (20.1 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment. Treatment agent (5). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (5), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Example 6>

NMP (13.5 g) was added to the polyimine powder (5) (2.55 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-2 in NMP (3.57 g) (A-2 was 5.0% by mass of NMP solution), NMP (7.93 g) and BCS (20.5 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment. Treatment agent (6). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (6), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions. .

<Example 7>

NMP (19.2 g) was added to the polyimine powder (6) (2.51 g) obtained in Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-1 in NMP (1.51 g) (A-1 was 5.0% by mass of NMP solution), NMP (9.46 g) and BCS (12.9 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment. Treatment agent (7). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (7), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Example 8>

NMP (15.3 g) was added to the polyimine powder (7) (2.50 g) obtained in Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-2 in NMP (1.50 g) (A-2 was 5.0% by mass of NMP solution), NMP (8.97 g) and BCS (17.2 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment. Treatment agent (8). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (8), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions. .

<Example 9>

The polyaminic acid solution (8) (11.0 g), NMP (4.00 g), and A-1 NMP solution (2.50 g) of the resin obtained in Synthesis Example 8 at a solid concentration of 25.0% by mass were mixed (A-1 was 5 mass% of NMP solution) and BCS (26.3 g) were stirred at 25 ° C for 2.5 hours to obtain a liquid crystal alignment treatment agent (9). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (9), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Example 10>

NMP (12.0 g) was added to the polyimine powder (9) (2.53 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-1 in NMP (3.54 g) (A-1 was 5.0% by mass of NMP solution), NMP (7.00 g) and BCS (22.6 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment. Treatment agent (10). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (10), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Example 11>

NMP (15.4 g) was added to the polyimine powder (10) (2.46 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A-2 NMP solution (4.92 g) (A-2 was 5.0% by mass of NMP solution), NMP (9.00 g) and BCS (15.8 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment. Treatment agent (11). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (11), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Example 12>

NMP (13.6 g) was added to the polyimine powder (11) (2.50 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A-2 NMP solution (2.50 g) (A-2 was 5.0% by mass of NMP solution), NMP (7.98 g) and BCS (19.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 12 hours to obtain a liquid crystal alignment. Treatment agent (12). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (12), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Example 13>

NMP (13.6 g) was added to the polyimine powder (12) (2.43 g) obtained in Synthesis Example 12, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-1 in NMP (1.46 g) (A-1 was 5.0% by mass of NMP solution), NMP (7.95 g) and BCS (18.8 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a liquid crystal alignment. Treatment agent (13). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (13), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Example 14>

NMP (13.6 g) was added to the polyimine powder (13) (2.50 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 24 hours to dissolve. A solution of A-1 in NMP (2.50 g) (A-1 was 5.0% by mass of NMP solution), NMP (5.78 g) and BCS (19.7 g) were added to the solution, and the mixture was stirred at 50 ° C for 12 hours to obtain a liquid crystal alignment. Treatment agent (14). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (14), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Comparative Example 1>

The polyaminic acid solution (1) (10.5 g), NMP (7.00 g), and BCS (26.3 g) having a solid content concentration of 25.0% by mass of the resin obtained in Synthesis Example 1 were mixed and stirred at 25 ° C for 2 hours to obtain Liquid crystal alignment treatment agent (15). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (15), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell and the PSA unit cell were carried out under the above conditions.

<Comparative Example 2>

NMP (14.3 g) was added to the polyimine powder (3) (2.48 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to dissolve. NMP solution (8.41 g) and BCS (18.6 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (16). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (16), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell and the PSA unit cell were carried out under the above conditions.

<Comparative Example 3>

In the polyimine powder (4) (2.50 g) obtained in Synthesis Example 4 NMP (14.5 g) was added, and the mixture was stirred at 70 ° C for 24 hours to dissolve. NMP solution (8.50 g) and BCS (18.8 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (17). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (17), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

<Comparative Example 4>

NMP (13.2 g) was added to the polyimine powder (13) (2.51 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 24 hours to dissolve. NMP solution (7.75 g) and BCS (20.9 g) were added to the solution, and the mixture was stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent (18). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that the solution was a uniform solution.

Using the obtained liquid crystal alignment treatment agent (18), the evaluation of the rubbing resistance and the evaluation of the electrical characteristics of the general unit cell were carried out under the above conditions.

From the above results, it is understood that the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has less friction shaving due to the rubbing treatment than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example, and further Even after prolonged exposure to ultraviolet light, the voltage retention rate is reduced.

In Comparative Examples 1 to 4 which did not contain a specific amine compound, friction rubbing caused by friction treatment was large, and further, the voltage holding ratio after long-term exposure to ultraviolet rays was also lowered.

Further, in the comparison of the examples of the same polyamine imine precursor or polyimine, and the specific amine compound, and the comparative example containing no specific amine compound, in the embodiment containing the specific amine compound, even if it is long After the time is exposed to ultraviolet light, the voltage retention rate is also reduced. Specifically, the comparison between Example 1 and Comparative Example 1, the comparison between Example 3 and Example 4 and Comparative Example 2, the comparison between Example 5 and Comparative Example 3, and the comparison between Example 14 and Comparative Example 4.

Industrial use possibility

By using the liquid crystal alignment treatment agent of the present invention, a liquid crystal alignment film which is less likely to cause chipping of the polymer film accompanying the rubbing treatment or scratching with the rubbing treatment in the manufacturing process of the liquid crystal display element, further, even if Long-term exposure to light can also suppress a decrease in voltage retention. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like. It can be used for TN elements, STN elements, TFT liquid crystal elements, especially vertical alignment liquid crystal display elements.

Further, when a liquid crystal display element is produced from the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention, it is useful even for a liquid crystal display element which is required to be irradiated.

That is, it can also be used for a liquid crystal display device manufactured by the steps of: providing a liquid crystal layer between the substrates having one pair of electrodes, and disposing at least one of the active energy rays and the heat between the pair of substrates; a polymerized polymerized liquid crystal alignment film that applies a voltage between the electrodes a step of polymerizing the polymerizable compound; further, the liquid crystal display device produced by the step of providing a liquid crystal layer between the substrates having one pair of electrodes, and disposing the active energy between the pair of substrates A liquid crystal alignment film of a polymerizable group in which at least one of a line and a heat is polymerized, and a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

The specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2010-292723, filed on Dec.

Claims (20)

A liquid crystal alignment treatment agent comprising the following components (A) and (B); component (A): an amine compound represented by the following formula [1]; and component (B): selected from a diamine component a polymer of at least one of a polyammonium acid obtained by reacting a tetracarboxylic dianhydride and a polyimine obtained by dehydration of the polyglycolic acid; In the formula [1], X ₁ is an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and the X ₂ -based single bond, -O-, -NH-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N(CH ₃ )CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -, X ₃ is a single Bond, benzene ring or cyclohexane ring, X ₄ single bond, -O-, -CO-, -COO-, -OCO-, -NH-, -N(CH ₃ )-, -NHCO-, -N (CH ₃ )CO-, -CONH-, -CON(CH ₃ )-, -S- or -SO ₂ -, X ₅ is a single bond, an organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, n It is an integer from 1 to 5. The liquid crystal alignment treatment agent of the first aspect of the invention, wherein the X ₁ of the formula [1] of the amine compound of the component (A) is a linear or branched alkyl group having a carbon number of 1 to 10, and a cyclohexane. Ring or bicyclohexyl ring. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein X ₂ of the formula [1] of the amine compound of the component (A) is a single bond, -O-, or -OCO-. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein X ₃ of the formula [1] of the amine compound of the component (A) is a single bond or a benzene ring. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein X ₄ of the formula [1] of the amine compound of the component (A) is a single bond, -O-, -NH- or -CONH-. The scope of the patent application of the liquid crystal alignment treating agent of paragraph 1 or 2, the amine compound of formula wherein the component (A) of [1] The X ₅ is a single bond, a C 1-4 straight or branched form bonds having 1 to 10 An alkyl or cyclohexane ring. The liquid crystal alignment treatment agent of claim 1, wherein the diamine component is a diamine compound having a side chain represented by the following formula [2]; In the formula [2], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ₂ is Single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ₄ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be carbon a number of 1 to 3 alkyl groups, a carbon number of 1 to 3 alkoxy groups, a carbon number of 1 to 3 fluorine-containing alkyl groups, a carbon number of 1 to 3 fluorine-containing alkoxy groups or a fluorine atom, or a steroid skeleton a divalent organic group selected from an organic group having 12 to 25 carbon atoms, and Y ₅ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any of these cyclic groups The hydrogen atom may be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. n is an integer of 0 to 4, and Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a fluorine having 1 to 18 carbon atoms. Alkoxy. The liquid crystal alignment treatment agent of claim 7, wherein the diamine component is a diamine compound represented by the following formula [2a]; Formula [. 2A] _{In, Y 1, Y 2, Y} 3, Y 4, Y 5, Y 6 and n have the same lines of the definition of the formula [2] of significance, m is an integer of 1 to 4. The liquid crystal alignment treatment agent of claim 8, wherein the diamine compound of the above formula [2a] contains 5 mol% to 80 mol% of the diamine component. The liquid crystal alignment treatment agent of the first aspect of the invention, wherein the polymer of the component (B) is a polymer using a tetracarboxylic dianhydride represented by the following formula [3]; In the formula [3], Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms, and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms. The liquid crystal alignment treatment agent according to claim 10, wherein the tetracarboxylic dianhydride has a structure represented by the following formula [3a] to formula [3j]; In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, which may be the same or different, and in the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or a group. The bases may be the same or different. The liquid crystal alignment treatment agent according to claim 1, wherein the polymer of the component (B) is a polyimine obtained by dehydration of the polyamic acid. The liquid crystal alignment treatment agent of the first aspect of the invention, wherein the component (A) is from 0.1 part by mass to 20 parts by mass per 100 parts by mass of the component (B). The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the liquid crystal alignment treatment agent contains 5 to 60% by mass of a weak solvent. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of claims 1 to 14. A liquid crystal display element having a liquid crystal alignment film according to item 15 of the patent application. A liquid crystal alignment film according to claim 15 which is used in a liquid crystal display device which has a liquid crystal layer between a substrate having one pair of electrodes and is disposed between the pair of substrates A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat, a step of applying a voltage between the electrodes and polymerizing the polymerizable compound. A liquid crystal display element having a liquid crystal alignment film according to item 17 of the patent application. A liquid crystal alignment film according to claim 15 which is used in a liquid crystal display device which has a liquid crystal layer between a substrate having one pair of electrodes and is disposed between the pair of substrates A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, a step of applying a voltage between the electrodes and polymerizing the polymerizable group. A liquid crystal display element having a liquid crystal alignment film according to claim 19 of the patent application.