TWI486380B - 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 same.

Compared with the conventional TN (Twisted Nematic) mode liquid crystal display element, an MVA (Multi-Field Vertical Arrangement) mode in which a wide viewing angle can be obtained is known as a liquid crystal display element having excellent viewing angle characteristics. In the MVA mode, a liquid crystal having a negative dielectric anisotropy, a liquid crystal alignment film that vertically aligns the liquid crystal, and a structure for controlling the alignment of the liquid crystal in the alignment direction are used. Further, when a voltage is applied, the liquid crystal is inclined in the vertical direction along the structure for alignment control. However, in the MVA mode, since the protrusions of the structure for alignment control are formed in the pixels, the aperture ratio is lower than that of the TN mode or the like, and the light transmittance from the backlight is lowered.

For this problem, in order to increase the response speed of the liquid crystal for a high light transmittance, it is proposed to use a polymer to control the alignment direction of the liquid crystal during driving (for example, Patent Document 1). In this method, a liquid crystal material in which a polymerizable compound (also referred to as a monomer) polymerized by heat or ultraviolet irradiation is mixed in a liquid crystal is used. In this method, a monomer is polymerized by heat or ultraviolet irradiation to form a polymer in a state where a voltage is applied between the substrates to tilt the liquid crystal molecules. Thereby, even if the voltage is not applied, a liquid crystal layer having a specified tilt angle (pretilt angle) can be obtained, and a liquid crystal display element having a high light transmittance and a liquid crystal response speed can be obtained.

Prior technical literature

Patent literature

Patent Document 1: JP-A-2003-149647

In the present method, since heat or ultraviolet irradiation is required to control the alignment of the liquid crystal, the liquid crystal alignment film used in the method must have higher reliability than the conventional MVA mode. Therefore, the electrical characteristics of the liquid crystal alignment film, that is, the voltage holding ratio, are required to be excellent not only in the initial characteristics but also in the case of heat or ultraviolet irradiation. When the voltage holding ratio is largely lowered, linear residual images of display failure of the liquid crystal display element are likely to occur, and a highly reliable liquid crystal display element cannot be obtained.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal material in which a polymerizable compound which is polymerized by heat or ultraviolet irradiation is mixed in a liquid crystal, and a polymerizable compound is polymerized while applying a voltage to the liquid crystal layer. In the liquid crystal display device, the liquid crystal display element is obtained by a method of controlling the alignment direction of the liquid crystal during driving, and the liquid crystal alignment treatment agent, the liquid crystal alignment film, and the liquid crystal are excellent in reliability even if the temperature is not lowered by heat or ultraviolet irradiation. Display component.

The inventors conducted intensive studies and found that at least one of a polyimine precursor having a specific side chain structure and a polyimine obtained by dehydrating the polyimine precursor is closed. The liquid crystal alignment treatment agent is extremely effective in achieving the above object, and finally completed the present invention.

That is, the present invention has the following gist.

(1) A liquid crystal alignment agent which is used for a liquid crystal display element and which contains at least one of a polyimine precursor having a side chain represented by the following formula [1] and a polyimine. In the liquid crystal display device, a liquid crystal material obtained by mixing a polymerizable compound which is polymerized by heat or ultraviolet irradiation in a liquid crystal, and a polymer obtained by polymerizing the polymerizable compound while applying a voltage to the liquid crystal layer is used to control the liquid crystal during driving. The method of the direction of alignment,

[Chemical 1]

(In the formula [1], X ₁ is -O-, -CH ₂ O-, -COO-, -(CH ₂ ) _a - (a is an integer of 1 to 10), -NH-, -N(CH) ₃ ) -, -CONH-, -NHCO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or a divalent organic group selected from a single bond, X ₂ is a single bond or _{- (CH 2) b - (} b is an integer of 1 to 10) a divalent organic group selected, X ₃ by a single bond _{lines, - (CH 2) c -} (c is an integer of 1 to 10), - O -, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ ) a divalent organic group selected from CO-, and X ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton. Any hydrogen atom on the cyclic group may be composed of 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, or a carbon number of 1 to 3 a fluoroalkoxy group or a fluorine atom is substituted, and X ₅ represents a divalent cyclic group selected from a cyclohexyl ring, a benzene ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be derived from a carbon number. An alkyl group of 1 to 3, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms The fluorine atom is substituted, and n is an integer of 0 to 4, X 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 carbon. a fluorine-containing alkoxy group having 1 to 18 or a hydrogen atom).

(2) The liquid crystal alignment treatment agent according to the above (1), wherein the polymer is a polymer obtained by using a diamine compound having a side chain of the formula [1] as a part of a raw material.

(3) The liquid crystal alignment treatment agent according to the above (2), wherein the diamine compound having a side chain of the formula [1] is a structure represented by the following formula [1a].

[Chemical 2]

(In the formula [1a], X ₁ is -O-, -CH ₂ O-, -COO-, -(CH ₂ ) _a - (a is an integer of 1 to 10), -NH-, -N(CH) ₃ ) -, -CONH-, -NHCO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or a divalent organic group selected from a single bond, X ₂ is a single bond or _{- (CH 2) b - (} b is an integer of 1 to 10) a divalent organic group selected, X ₃ by a single bond _{lines, - (CH 2) c -} (c is an integer of 1 to 10), - O -, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ ) a divalent organic group selected from CO-, X ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and the ring Any hydrogen atom on the 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, or a fluorine having 1 to 3 carbon atoms. The alkoxy group and the fluorine atom are substituted, and X ₅ represents a divalent cyclic group selected from a cyclohexyl ring, a benzene ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may also be derived from a carbon number of 1. ～3 alkyl group, carbon number 1-3 alkoxy group, carbon number 1-3 fluorine-containing alkyl group, or carbon number 1-3 fluorine-containing alkoxylate , Those substituents selected from a fluorine atom, n-represents an integer of 0 to 4, X ₆ based carbon alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbons, alkoxy having 1 to 18 carbons, A fluorine-containing alkoxy group or a hydrogen atom of 1 to 18, and m is an integer of 1-4.

(4) The liquid crystal alignment treatment agent according to the above (3), wherein the diamine compound having the structure represented by the formula [1a] accounts for 5 to 80 mol% of the diamine component.

(5) The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the polymer is a polymer obtained by using a tetracarboxylic dianhydride represented by the following formula [2].

[Chemical 3]

(In the formula [2], Y 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).

(6) The liquid crystal alignment treatment agent according to the above (5), wherein Y ₁ is a structure represented by the following formula [2a] to formula [2j],

[Chemical 4]

(In the formula [2a], Y ₂ to Y ₅ are groups selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different, and in the formula [2g], Y ₆ and Y ₇ are hydrogen. Atoms or methyl groups, each of which may be the same or different).

The liquid crystal alignment treatment agent according to any one of the above aspects, wherein the liquid crystal alignment treatment agent has a group selected from the group consisting of an epoxy group, an oxetane group, and an isocyanate group. a crosslinkable compound of at least one substituent in a group formed by a cyclic carbonate group; having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, an alkoxy group, and a lower alkoxyalkyl group a crosslinkable compound; or a crosslinkable compound having a polymerizable unsaturated bond.

(8) The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the polymer in the liquid crystal alignment treatment agent is obtained by dehydrating and blocking polyacrylamide.

The liquid crystal alignment treatment agent according to any one of the above-mentioned (1), wherein the liquid crystal alignment treatment agent contains 5 to 60% by mass of a weak solvent.

(10) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to any one of the above (1) to (9).

(11) A liquid crystal display element comprising the liquid crystal alignment film according to (10) above.

By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having a voltage holding ratio which is not lowered even by heat or ultraviolet irradiation can be obtained, and the liquid crystal display element having the liquid crystal alignment film is excellent in reliability.

[Formation of the Invention]

The invention is described in detail below.

The present invention relates to a liquid crystal alignment agent for a liquid crystal display element which uses a liquid crystal material in which a polymerizable compound polymerized by heat or ultraviolet irradiation is mixed in a liquid crystal to apply a voltage to the liquid crystal layer. a polymer obtained by polymerizing the polymerizable compound, a method for controlling an alignment direction of a liquid crystal during driving; a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent; and a liquid crystal display having the liquid crystal alignment film element.

The liquid crystal alignment treatment agent of the present invention contains a polyimine precursor obtained by a reaction between a diamine component and a carboxylic acid dianhydride, and a polyimide obtained by dehydrating and ring-closing the polyimine precursor. At least one selected (also collectively referred to as a polymer).

The polymer of the present invention, which is selected from the group consisting of a polyimine precursor obtained by a reaction of a diamine component and a tetracarboxylic dianhydride, and a polyimine obtained by dehydrating and ring-closing the polyimine precursor At least one of them has a side chain (also referred to as a specific side chain structure) represented by the following formula [1].

[Chemical 5]

(In the formula [1], X ₁ is -O-, -CH ₂ O-, -COO-, -(CH ₂ ) _a - (a is an integer of 1 to 10), -NH-, -N(CH) ₃ ) -, -CONH-, -NHCO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or a divalent organic group selected from a single bond, X ₂ is a single bond or _{- (CH 2) b - (} b is an integer of 1 to 10) a divalent organic group selected, X ₃ by a single bond _{lines, - (CH 2) c -} (c is an integer of 1 to 10), - O -, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ ) a divalent organic group selected from CO-, X ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and the ring Any hydrogen atom on the 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, or a fluorine having 1 to 3 carbon atoms. The alkoxy group and the fluorine atom are substituted, and X ₅ represents a divalent cyclic group selected from a cyclohexyl ring, a benzene ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may also be derived from a carbon number of 1. ～3 alkyl group, carbon number 1-3 alkoxy group, carbon number 1-3 fluorinated alkyl group, or carbon number 1-3 fluoroalkoxy group The fluorine atom is substituted, and n is an integer of 0 to 4, X 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 carbon. a fluorine-containing alkoxy group having 1 to 18 or a hydrogen atom).

The specific side chain structure of the present invention has a cyclic group or a steroid skeleton selected from a benzene ring, a cyclohexyl ring, a hetero ring in a side chain moiety. Thereby, the stability of the side chain portion irradiated by heat or ultraviolet rays is improved. Therefore, it is possible to suppress a decrease in the voltage holding ratio accompanying the decomposition of the side chain component. Then, by using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having a voltage holding ratio which is not lowered even by heat or ultraviolet irradiation can be obtained, and the liquid crystal display element having the liquid crystal alignment film is excellent in reliability.

<specific side chain structure>

The specific side chain structure of the present invention is a structure represented by the following formula [1].

[Chemical 6]

In the formula [1], X ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -NH-, -N(CH ₃ )-, -CONH-, a divalent organic group selected from -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of from 1 to 10), -O-, -CONH-, -CH ₂ O- or -COO- is preferable because a side chain structure is easily synthesized. Particularly preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CONH -, - CH 2 O- or -COO-. More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

In the formula [1], X ₂ is a divalent organic group selected from a single bond or -(CH ₂ ) _b - (b is an integer of from 1 to 10). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of from 1 to 10) is preferred.

In the formula [1], X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -NH-, -N(CH ₃ )-, -CONH-, a divalent organic group selected from -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of from 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO- is preferred because of ease of synthesis. More preferably a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), - O -, - CH 2 O -, - COO- or -OCO-.

In the formula [1], X ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and such a 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, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. The fluorine atom is replaced by a selected one. Among them, a benzene ring or a cyclohexyl ring, that is, an organic group having a carbon number of 12 to 25 having a phenyl group, a cyclohexyl group or a steroid skeleton is preferable.

In the formula [1], X ₅ represents a divalent cyclic group selected from a cyclohexyl ring, a benzene ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms. 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, and the fluorine atom are optionally substituted. Among them, a benzene ring or a cyclohexyl ring is preferred.

In the formula [1], X ₆ is a hydrogen atom, 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. 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. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

In the formula [1], n is an integer of 0 to 4, preferably an integer of 0 to 2.

Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1] are 1-1 to 1-629 shown in the following Tables 1 to 42.

<Specific diamine compound>

As the polymer of the present invention, that is, a polyimine precursor obtained by a reaction of a diamine component and a tetracarboxylic dianhydride, and a polyimine which is obtained by dehydrating and ring-closing the polyimine precursor Among the at least one selected from the above, a method of introducing a specific side chain structure is preferably a part of a raw material using a diamine compound (also referred to as a specific diamine compound) represented by the following formula [1a].

[Chemistry 7]

In the formula [1a], X ₁ is a single bond, -(CH ₂ ) ₈ - (a is an integer of 1 to 10), -O-, -NH-, -N(CH ₃ )-, -CONH-, a divalent organic group selected from -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -(CH ₂ ) _a - (a is an integer of from 1 to 10), -O-, -CONH-, -CH ₂ O- or -COO- is preferable because a side chain structure is easily synthesized. Particularly preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CONH -, - CH 2 O- or -COO-. More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

In the formula [1a], X ₂ is a divalent organic group selected from a single bond or -(CH ₂ ) _b - (b is an integer of from 1 to 10). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of from 1 to 10) is preferred.

In the formula [1a], X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -NH-, -N(CH ₃ )-, -CONH-, a divalent organic group selected from -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -(CH ₂ ) _c - (c is an integer of from 1 to 10), -O-, -CH ₂ O-, -COO- or -OCO- is preferred because of ease of synthesis. More preferably a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), - O -, - CH 2 O -, - COO- or -OCO-.

In the formula [1a], X ₄ is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and such a cyclic group. Any of the above hydrogen atoms 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, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. The fluorine atom is preferably substituted with a benzene ring, a cyclohexyl ring or an organic group having 12 to 25 carbon atoms having a steroid skeleton.

In the formula [1a], X ₅ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms. 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, and the fluorine atom are optionally substituted. Among them, a benzene ring or a cyclohexyl ring is preferred.

In the formula [1a], the X ₆ -based hydrogen atom or 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 is contained. Fluoroalkoxy. 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. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

In the formula [1a], n is an integer of 0 to 4, preferably an integer of 0 to 2.

Preferred combinations of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , X ₆ and n in the formula [1a] are as shown in Tables 1 to 42 in the same manner as in the formula [1].

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

Specifically, for example, the structure shown by the following formula [1a-1] - formula [1a-32].

[化8]

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

[Chemistry 9]

(In the formula [1a-3]~Form [1a-5], R ₃ represents -COO-, -OCO-, -CONH-, -NHCO-, -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).

[化10]

(In the formula [1a-6] and the formula [1a-7], R ₅ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O- or -NH-, R ₆ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, a methyl group, a Alkoxy or hydroxy).

[11]

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

[化12]

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

[Chemistry 13]

(In the formula [1a-12], A ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group, and the A ₂ system Oxygen atom or -COO-* (except for "*" combined with A ₃ bond), A ₁ oxygen atom or -COO-* (only with "*" combined hand and (CH ₂ a ₂ bond). 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.

[Chemistry 14]

[化15]

[Chemistry 16]

[化17]

[化18]

<Other diamine compounds>

In the present invention, as long as the effects of the present invention are not impaired, other diamine compounds other than the specific diamine compound may be used in combination as the diamine component. The following is a detailed example.

P-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylene Diamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3, 5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamino resorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl- 4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl , 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4' -diaminobiphenyl, 3,4'-diaminobiphenyl, 3.3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4 , 4'-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 , 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl-double (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'-diaminodiphenylamine, 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'-diaminodiyl) Phenyl)amine, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 1,4-diamine Naphthalene, 2,2'-diaminodiphenyl ketone, 2,3'-diaminodiphenyl ketone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7 -diaminonaphthalene, 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-double (4-Aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-amino group Phenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amine Phenoxy)benzene, 1,4-bis(4-aminophenyl)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 -phenylphenylbis(methylene)]diphenylamine, 3,4'-[1,4-phenylenebis(methylene)]diphenylamine, 3,4'-[1,3-phenylene Bis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine, 3,3'-[1,3-phenylene bis (nara Diphenylamine, 1,4-phenylphenylbis[(4-aminophenyl)methanone], 1,4-phenylphenylbis[(3-aminophenyl)methanone], 1, 3-phenylphenylbis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone], 1,4-phenylene bis(4) -aminobenzoic acid ester), 1,4-phenylene bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3 - phenyl bis(3-aminobenzoate), bis(4-aminophenyl)-paraben Acid ester, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate , N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide) Amine, N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzene Methionine), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N '-Bis(4-Aminophenyl)m-phenylenediamine, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl) Bismuth, 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-aminobenzene) Hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'- Bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzene Formic acid, 1,3-bis(4-amino group Oxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy) Butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminobenzene Oxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminobenzene Oxy) heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-amine Phenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminobenzene Oxy) decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminobenzene Aromatic diamines such as oxy)dodecane and 1,12-(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3- An alicyclic diamine such as methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamino Hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diamine Undecane, 1,12 An aliphatic diamine such as diaminododecane.

In addition, a diamine having an alkyl group or a fluorine-containing alkyl group in the side chain of the diamine may be mentioned, and specifically, a diamine represented by the following formula [DA1] to formula [DA12] can be exemplified.

[Chemistry 19]

(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).

[Chemistry 20]

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

[Chem. 21]

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

The other diamine compound may be used in combination of one type or two types or more in accordance with characteristics such as liquid crystal alignment property, voltage holding ratio, and charge accumulation when the liquid crystal alignment film is used.

<tetracarboxylic dianhydride>

In order to obtain the polymer of the present invention, a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [2] is preferably used as a part of the raw material.

[化22]

In the formula [2], Y 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.

Specifically, Y _{1 is} , for example, a tetravalent group represented by the following formula [2a] to formula [2j].

[化23]

In the formula [2a], Y ₂ to Y ₅ are each a group selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different, and the Y ₆ and Y ₇ hydrogen atoms in the formula [2g]. Or methyl groups, each of which may be the same or different.

In the formula [2], the particularly preferable structure of Y ₁ is a formula [2a], a formula [2c], a formula [2d], a formula [2e], and a formula [2f] from the viewpoints of polymerization reactivity or ease of synthesis. Or formula [2g].

<Other tetracarboxylic dianhydride>

In the present invention, other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride may be used in combination as long as the effects of the present invention are not impaired. Specific examples thereof are dianhydrides of the following compounds.

Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6, 7-decanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetra Carboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-diphenyl ketone tetracarboxylic 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-nonanedicarboxylic acid , 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The other tetracarboxylic dianhydride may be used in combination of one type or two types or more in accordance with characteristics such as liquid crystal alignment property, voltage holding ratio, and charge accumulation when the liquid crystal alignment film is used.

<polymer>

The polymer used in the present invention is a polyimine precursor having a specific side chain structure represented by the above formula [1], or a polyazide obtained by dehydrating and ring-closing the polyimine precursor, as described above. amine.

The method for synthesizing the polymer of the present invention is not particularly limited, and a diamine component and a tetracarboxylic acid can be used in the same manner as a general method for synthesizing a polyimide intermediate (for example, polyglycolic acid) or polyimine. A method of reacting an acid dianhydride. In this case, a tetracarboxylic acid derivative such as a tetracarboxylic acid or a tetracarboxylic quinone dihalide can also be used.

When the polymer of the present invention is obtained, the specific diamine compound represented by the above formula [1a] is preferably used as the diamine component.

In the liquid crystal alignment film obtained by using the polymer of the present invention, the more the content ratio of the specific diamine compound in the diamine component is, the more the liquid crystal alignment film can be obtained without any decrease in voltage holding ratio even after heat or ultraviolet irradiation. The liquid crystal display element having such a liquid crystal alignment film is excellent in reliability.

For the purpose of improving the above characteristics, 1 mol% or more of the diamine component is preferably a specific diamine compound. Further, 5 mol% or more of the diamine component is preferably a specific diamine compound, more preferably 10 mol% or more. Further, 100 mol% of the diamine component may be a specific diamine compound, but the specific diamine compound is preferably a diamine component from the viewpoint of uniform coatability when the liquid crystal alignment treatment agent is applied. The ear is below the ear%, more preferably 40% by mole or less.

Moreover, in order to obtain the polymer of the present invention, it is preferred to use the specific tetracarboxylic dianhydride represented by the above formula [2] as the tetracarboxylic dianhydride. In this case, 1 mol% or more of the tetracarboxylic dianhydride is preferably a specific tetracarboxylic dianhydride. Further, 5 mol% or more of the tetracarboxylic dianhydride is preferably a specific tetracarboxylic dianhydride, more preferably 10 mol% or more. Further, 100 mol% of the tetracarboxylic dianhydride may be a specific tetracarboxylic dianhydride.

When the polyimine precursor of the present invention is obtained by the reaction of a diamine component with a tetracarboxylic dianhydride, a well-known synthetic method can be used. A method of reacting a diamine component with a tetracarboxylic dianhydride in an organic solvent is generally employed. The reaction of the diamine component with the tetracarboxylic dianhydride is relatively easy to carry out in an organic solvent, and is advantageous in that no by-products are produced.

The organic solvent used in the reaction between the diamine component and the tetracarboxylic dianhydride is not particularly limited as long as it can dissolve the produced polyimide precursor. Specific examples thereof will be given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylhexamidine, dimethyl hydrazine, tetramethyl Urea, pyridine, dimethyl hydrazine, tridecyl hexamethyl phosphate, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl fluorenyl Ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate Ester, 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 tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate Monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol 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, amyl acetate, butyl butyrate, dibutyl ether, diisobutyl ketone, methylcyclohexene , propyl ether, dihexyl ether, two Alkane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, methyl propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid Butyl ester, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3-methoxypropionic acid Ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4 -Methyl-2-hexanone and the like. These may be used alone or in combination. Further, even a solvent which does not dissolve the polyimide precursor can be used by mixing the solvent in a range in which the produced polyimide precursor is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably used by dehydration.

When the diamine component and the tetracarboxylic dianhydride are reacted in an organic solvent, a solution in which an organic solvent in which a diamine component is dispersed or dissolved in an organic solvent is stirred, and tetracarboxylic dianhydride is directly added or dispersed or a method of dissolving in an organic solvent and adding a diamine component in a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent; and a tetracarboxylic dianhydride and a diamine component are alternately added. Method, etc.; any of these methods can be used. Further, when the diamine component or the tetracarboxylic dianhydride is composed of a plurality of compounds, the reaction may be carried out in a state of being mixed in advance, or may be individually reacted in order, and a low molecular weight body which can be individually reacted may be used. The mixed reaction is carried out to obtain a high molecular weight body.

The polymerization temperature at that time may be any temperature from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. Further, the reaction system can be carried out at any concentration. If the concentration is too low, it is difficult to obtain a copolymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid becomes too high, and uniform stirring becomes difficult. Therefore, it is preferably 1 ～50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the polymerization of the polyimine precursor, the molar ratio of the molar number of the synthetic amine of the diamine component to the total amount of the tetracarboxylic dianhydride is preferably 0.8 to 1.2. As in the usual polycondensation reaction, 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 can be used as a polymer for obtaining a liquid crystal alignment film by using a polyimine which is obtained by dehydration of a polyamic acid of the polyimine precursor.

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

The method for carrying out the ruthenium imidization of the polyimine precursor may be a thermal hydrazine imidization in which the solution of the polyimide precursor is directly heated, and a catalyst is added to the solution of the polyimide precursor. Catalytic ruthenium.

The temperature at which the polyimide precursor is subjected to thermal imidization in a solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, preferably by shifting the water formed by the hydrazine imidization reaction. In addition to the department, the way to do it.

The catalytic ruthenium imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride in a solution of the polyimide precursor, at -20 to 250 ° C, preferably 0 to 180 ° C. Stirring is carried out. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine has a moderate basicity for allowing the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. When acetic anhydride is used, the purification after completion of the reaction becomes easy. The rate of ruthenium imidization of the ruthenium imidization 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 put into a weak solvent to precipitate. Examples of the weak solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated by being added to a weak solvent can be collected by filtration and then dried at room temperature or under reduced pressure under normal pressure or reduced pressure. Further, if the polymer recovered by the precipitation is re-dissolved in an organic solvent 2 to 10 times, and the operation of reprecipitation and recovery is repeated, impurities in the polymer can be reduced. Examples of the weak solvent in this case include alcohols, ketones, and hydrocarbons. When three or more kinds of weak solvents selected from the above are used, the efficiency of further purification is preferably improved.

When the molecular weight of the polyimide film obtained by the liquid crystal alignment agent of the present invention or the polyimine is considered, the strength of the coating film obtained therefrom, the workability at the time of coating film formation, and the uniformity of the coating film are considered. The weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 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 used for forming a coating liquid for a liquid crystal alignment film, and is a solution for forming a resin component of a resin film dissolved in an organic solvent. Here, the resin component contains the polymer of the present invention described above, that is, at least one polymer selected from the group consisting of a polyimine precursor having a specific side chain structure represented by the above formula [1] and a polyimine. Resin composition. In this case, the content of the resin component is preferably from 1% by mass to 20% by mass, more preferably from 3% by mass to 15% by mass, even more preferably from 3% by mass to 10% by mass.

In the present invention, the resin component may be entirely the polymer of the present invention, and other polymers other than the polymer may be mixed in the polymer of the present invention. In this case, the content of the resin component other than the polymer of the present invention is from 0.5% by mass to 15% by mass, preferably from 1% by mass to 10% by mass.

Examples of the other polymer include a polyimide intermediate having no specific side chain structure, a polyimine, and the like.

In the liquid crystal alignment treatment agent of the present invention, for the purpose of obtaining a liquid crystal alignment film which does not lower the voltage holding ratio even when irradiated with heat or ultraviolet rays, it is preferred to introduce a crosslinkable compound of a compound which crosslinks the polymer, specifically Is a crosslinkable compound having at least one substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, and a cyclic carbonate group; having a group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and an alkoxy group. a crosslinkable compound of at least one substituent selected from the group consisting of a lower alkoxyalkyl group; or a crosslinkable compound having a polymerizable unsaturated bond. Further, these substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone epoxy propyl ether, phenol novolac epoxy resin, methyl novolac epoxy resin, and trisepoxypropyl isocyanuric acid. Acid ester, tetraglycidyl propyl diphenyl, tetraglycidyl-m-xylene diamine, tetra-epoxypropyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl Epoxypropyl ether ethyl ether, triphenyl epoxypropyl ether ethane, bisphenol hexafluoroacetic acid diepoxypropyl ether, 1,3-bis(1-(2,3-epoxyoxypropoxy) 1, 3-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triepoxypropyl -p-Aminophenol, tetraepoxypropylm-xylylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-double) (4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane, 1,3-bis(4-(1-(4-(2,3-epoxyoxypropoxy)) Phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy) 2-propanol and the like.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetanyl groups represented by the following formula [3].

[Chem. 24]

Specifically, it is a crosslinkable compound represented by the following formula [3a] - formula [3k].

[化25]

[Chem. 26]

[化27]

The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group may, for example, be a hydroxyl group, an alkoxy group or a lower alkoxyalkyl group. The amine-based resin, for example, melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinimide-formaldehyde resin, ethylglycol-formaldehyde resin, and the like. Further, the lower alkoxyalkyl group is, for example, an alkoxyalkyl group having 1 to 4 carbon atoms.

The crosslinkable compound can be, for example, a melamine derivative, a benzoguanamine derivative or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both. The melamine derivative and the benzoguanamine derivative may also exist as a dimer or a trimer. These are preferably for every three The ring has an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups.

Examples of such a melamine derivative or a benzoguanamine derivative include one per commercially available product. The ring is replaced by methoxymethyl group with an average of 3.7 MX-750, one per three The methoxy group in which the ring is substituted by methoxymethyl group by an average of 5.8 (the above is manufactured by Sanwa Chemical), or the methoxy of Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methylated melamine, methoxymethylated butoxymethylated melamine of Cymel 235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine of Cymel 506, 508, etc. a methoxymethylated isobutoxymethylated melamine containing a carboxyl group such as Cymel 1141, such as methoxymethylated ethoxymethylated benzoguanamine of Cymel 1123, such as Cymel 1123-10 a methoxymethylated butoxymethylated benzoguanamine such as a butoxymethylated benzoguanamine of Cymel 1128, such as a carboxymethylated ethoxylated carboxyl group of Cymel 1125-80 Methylated benzoguanamine (above is Mitsui CYANAMID). Further, examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, hydroxymethylated glycoluril such as Cymel 1172, and the like, such as Powdering 1174 methoxymethylolated glycoluril, and the like. .

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxy group include 1,3,5-tris(methoxymethyl)benzene and 1,2,4-tris(isopropoxymethyl)benzene. 1,4-bis(second butoxymethyl)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

More specifically, it is a crosslinkable compound represented by the following formula [6-1] - formula [6-48].

[化28]

[化29]

[化30]

[化31]

[化32]

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tri (( Methyl) propylene methoxy ethoxy trimethylolpropane, glycerol polyepoxy propyl ether poly(meth) acrylate, etc., having three crosslinkable compounds having a polymerizable unsaturated group in the molecule, And ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol II (Meth) acrylate, polypropylene glycol di(meth) acrylate, butane diol di(meth) acrylate, neopentyl glycol di(meth) acrylate, ethylene oxide bisphenol A type II ( Methyl) acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(methyl) Acrylate, ethylene glycol diepoxypropyl ether di(meth)acrylate, diethylene glycol diepoxypropyl ether di(meth)acrylate, phthalic acid diepoxy a crosslinkable compound having two polymerizable unsaturated groups in a molecule, such as propyl ester di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, and (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(A) Acryloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth)acrylate, mono (meth) acrylate, 2-(methyl) propylene hydride A crosslinkable compound having one polymerizable unsaturated group in the molecule, such as oxyethyl phosphate or N-methylol (meth) acrylamide.

Further, a compound represented by the following formula [4] can also be used.

[化33]

(In the formula [4], Z ₁ is an n-valent group selected from a cyclohexyl ring, a bicyclohexyl ring, a benzene ring, a biphenyl ring, a biphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring. Z ₂ is a group selected from the following formula [4a] or formula [4b], and n is an integer of 1 to 4).

[化34]

An example of the above-mentioned compound-based crosslinkable compound 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 a combination of two or more types.

The content of the crosslinkable compound in the liquid crystal alignment agent of the present invention is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the polymer of the present invention obtained from a polyimide or a polyimide. 150 parts by mass, more preferably from 0.1 to 100 parts by mass, particularly from 1 to 50 parts by mass, in order not to lower the alignment property of the liquid crystal for the purpose of the crosslinking reaction.

The organic solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the above resin component. For example, N-methyl-2-pyrrolidone or butyl cellosolve can be mentioned.

Further, in the liquid crystal alignment treatment agent of the present invention, it is preferred to contain a weak solvent. The weak solvent refers to a solvent which improves film thickness uniformity or surface smoothness when a liquid crystal alignment agent is applied. Specific examples of the weak solvent include the following.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate Ester, butyl carbitol, 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 II Methyl 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 single Acetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, B Isobutyl butyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, positive Octane, diethyl ether, Methyl ester, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3- Methyl ethyl ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxy Butyl propyl 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- A solvent having a low surface tension such as ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate.

These solvents may be used in one type or in a mixed plural type. When the weak solvent as described above is used, it is preferably from 5 to 80% by mass, and more preferably from 20 to 60% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent.

The liquid crystal alignment agent of the present invention may contain components other than the above. In the case of coating a liquid crystal alignment treatment agent, a compound which improves film thickness uniformity or surface smoothness, and a compound which improves adhesion between a liquid crystal alignment film and a substrate, and the like are used.

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 TOHKEM PRODUCTS), Megafac F171, F173, R-30 (made by Dainippon Ink), Florad FC430, FC431 (manufactured by Sumitomo 3M), Asahiguard AG710, Surflon S -382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent.

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

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane may be mentioned. , N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3- Ureapropyl propyl trimethoxy decane, 3-ureidopropyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyl trimethoxy decane, N-ethoxycarbonyl-3-amino group Propyltriethoxydecane, N-triethoxydecylpropyltriamine, N-trimethoxydecylpropyltriamine, 10-trimethoxydecyl-1,4 , 7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate , 9-triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyl Triethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide)-3-amine Propyltrimethoxydecane, N-bis(ethylene oxide) 3-aminopropyltriethoxydecane, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, propylene glycol diepoxypropyl ether, tripropylene glycol diepoxypropyl ether , polypropylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, glycerol diepoxypropyl ether, 2,2-dibromo new Pentyl glycol diepoxypropyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N',N',-tetraepoxypropyl-inter Xylene diamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N,N',N',-tetraepoxypropyl-4,4' -Diaminodiphenylmethane and the like.

When the compound is in contact with the substrate, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent. When the amount is less than 0.1 part by mass, the effect of improving the adhesion property cannot be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal is deteriorated.

In addition to the above, the liquid crystal alignment treatment agent of the present invention may be added with a dielectric or an electric property for changing the dielectric constant or conductivity of the liquid crystal alignment film insofar as the effects of the present invention are not impaired. Conductive material.

<Liquid alignment film ‧ Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention is applicable to a liquid crystal alignment film used in a liquid crystal display element, which is a liquid crystal material in which a polymerizable compound polymerized by heat or ultraviolet irradiation is mixed in a liquid crystal. In the liquid crystal layer, a polymer obtained by polymerizing the polymerizable compound is applied to a liquid crystal layer, and a method of controlling the alignment direction of the liquid crystal during driving is obtained. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency. For the limitation, a plastic substrate such as a glass substrate, an acrylic substrate, or a polycarbonate substrate can be used. Further, a substrate on which an electrode such as ITO or aluminum for liquid crystal driving is formed 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, offset printing, inkjet, or the like. As another coating method, there are dipping, roll coating, slit coating, spin coating, etc., and these can be used according to the purpose.

The baking after the liquid crystal alignment agent is applied onto the substrate is carried out by heating the solvent at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate to form a coating film. When the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element is lowered, so it is preferably 5 to 300 nm, more preferably It is 10 to 100 nm.

In the liquid crystal display device of the present invention, after the substrate having the liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention, a liquid crystal cell is produced, and the polymerizable compound is polymerized by irradiation with heat or ultraviolet rays to become a controlled liquid crystal. Aligned liquid crystal display elements.

In an example of the production of the liquid crystal cell, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and a spacer is spread on the liquid crystal alignment film of one of the substrates, and the liquid crystal alignment film surface is formed inside, and the other is bonded to the other. The substrate is filled with a liquid crystal under reduced pressure, and is sealed, or a liquid crystal alignment film surface on which a spacer is dispersed, a liquid crystal is dropped, a substrate is bonded, and a method of sealing is performed. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

The liquid crystal used at this time is mixed with a polymerizable compound which is polymerized by heat or ultraviolet irradiation. The polymerizable compound is a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. 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 unreacted polymerizable compound increases, and the printing property of the liquid crystal display element is lowered. .

After the liquid crystal cell is produced, by applying an alternating current or a direct current voltage to the liquid crystal cell, the polymer or the ultraviolet ray is irradiated to polymerize the polymerizable compound, whereby the alignment of the liquid crystal can be controlled.

As described above, the liquid crystal display element produced by using 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.

Example

The invention is illustrated in more detail below by way of examples without limitation.

"Synthesis of Polyimine Precursor and Polyimine of the Invention"

(tetracarboxylic dianhydride)

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

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

TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4:2,3-dianhydride

TDA: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride

[化35]

(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)cyclohexyl]phenoxymethyl}benzene

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

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

[化36]

(other diamine compounds)

p-PDA: p-phenylenediamine

m-PDA: m-phenylenediamine

DBA: 3,5-diaminobenzoic acid

AP18: 1,3-diamino-4-octadecyloxybenzene

[化37]

(crosslinkable compound)

Crosslinkable compound (1): YH-434L (manufactured by Tohto Kasei Co., Ltd.) (epoxy group-crosslinkable compound)

Crosslinkable compound (2): OXT-221 (manufactured by Toagosei Co., Ltd.) (oxetane-based cross-linking compound)

Crosslinkable compound (3): Cymel 303 (manufactured by Mitsui Chemicals, Inc.) (methoxymethylated melamine-based cross-linking compound)

Crosslinkable compound (4): a crosslinkable compound represented by the following formula (hydroxylated phenol-based crosslinkable compound)

Crosslinkable compound (5): KAYARADDPHA-40H (manufactured by Nippon Kasei Co., Ltd.) (unsaturated bonding group cross-linking compound)

[化38]

(Organic solvents)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

(Measurement of molecular weight of polyimine precursors and polyimine)

The molecular weight of the polyimine in the synthesis example is a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko), a column (KD-803, KD-805) (manufactured by Shodex). It was measured as follows.

Column temperature: 50 ° C

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr‧H ₂ O) is 30 mmol/L, phosphoric acid ‧ anhydrous crystals (orthophosphoric acid) is 30 mmol/L, Tetrahydrofuran (THF) is 10ml/L)

Flow rate: 1.0ml/min

Standard sample for calibration curve preparation: 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) (manufactured by Polymer Laboratory) .

(Measurement of yttrium imidation rate)

The ruthenium imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (NMR sampling tube standard Φ5 (manufactured by Kusano Scientific)), and a hydrogenated dimethyl hydrazine (DMSO-d6, 0.05% TMS (tetramethyl decane) mixture) was added. 0.53 ml, ultrasonic waves were applied to completely dissolve. For this solution, a NMR measuring machine (JNW-ECA500) (manufactured by JEOL DATUM) was used, and a proton NMR of 500 MHz was measured. The ruthenium imidization rate is a proton determined from a structure that has not changed before and after imidization, and the peak value of the proton is used and the proton of the NH group derived from proline is present near 9.5 to 10.0 ppm. The peak cumulative value is obtained by the following formula.

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

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

<Synthesis Example 1>

CBDA (4.90 g, 25.0 mmol), PCH7DAB (4.76 g, 12.5 mmol), p-PDA (1.35 g, 12.5 mmol) were mixed with NMP (32.1 g), and the reaction was carried out at 40 ° C for 6 hours to obtain a resin solid component. Polylysine solution (1) having a concentration of 25.5% by mass. The polyamine has a number average molecular weight of 27,900 and a weight average molecular weight of 76,900.

<Synthesis Example 2>

BODA (4.38 g, 17.5 mmol), PCH7DAB (4.76 g, 12.5 mmol), p-PDA (1.35 g, 12.5 mmol) were mixed in NMP (19.5 g). After reacting at 80 ° C for 5 hours, CBDA (1.47) was added. g, 7.50 mmol) and NMP (16.0 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25.2% by mass. The polyamine had a number average molecular weight of 25,400 and a weight average molecular weight of 61,800.

<Synthesis Example 3>

BODA (5.25 g, 21.0 mmol), PCH7DAB (5.71 g, 15.0 mmol), DBA (2.28 g, 15.0 mmol) were mixed with NMP (24.6 g). After reacting at 80 ° C for 4 hours, CBDA (1.76 g, 8.97 mmol) and NMP (20.2 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 25.1% by mass. The polyamic acid had a number average molecular weight of 22,400 and a weight average molecular weight of 59,200.

<Synthesis Example 4>

In the polyaminic acid solution (3) (20.0 g) having a resin solid content concentration of 25.1% by mass obtained in Synthesis Example 3, NMP was added to dilute it to 6 mass%, and then acetic anhydride as a ruthenium catalyst was added. (2.49 g) and pyridine (1.91 g) were reacted at 80 ° C for 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). This polyimine had a ruthenium iodide ratio of 58%, a number average molecular weight of 21,100, and a weight average molecular weight of 50,100.

<Synthesis Example 5>

BODA (4.00 g, 16.0 mmol), PCH7DAB (2.28 g, 6.00 mmol), DBA (2.13 g, 14.0 mmol) were mixed in NMP (15.1 g), and after reacting at 80 ° C for 5 hours, CBDA (0.78 g, 4.00 mmol) and NMP (12.4 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.

After adding NMP to the obtained polyamic acid solution (20.1 g), and diluting it to 6 mass%, acetic anhydride (4.52g) and pyridine (3.30g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 90 degreeC. 3 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimine had a hydrazide conversion ratio of 80%, a number average molecular weight of 19,800, and a weight average molecular weight of 48,500.

<Synthesis Example 6>

BODA (3.50 g, 14.0 mmol), PBCH5DAB (2.60 g, 6.00 mmol), p-PDA (1.51 g, 14.0 mmol) were mixed in NMP (14.4 g), and the reaction was carried out at 80 ° C for 5 hours, then CBDA (1.18) was added. g, 6.02 mmol) and NMP (11.7 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.2% by mass.

After adding NMP to the obtained polyamic acid solution (20.5 g), and diluting it to 6% by mass, acetic anhydride (2.53 g) and pyridine (1.95 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). This polyimine has a hydrazide conversion ratio of 60%, a number average molecular weight of 18,200, and a weight average molecular weight of 46,300.

<Synthesis Example 7>

BODA (3.00 g, 12.0 mmol), PBCH5DAB (3.46 g, 8.00 mmol), DBA (1.83 g, 12.0 mmol) were mixed in NMP (16.5 g), and after reacting at 80 ° C for 5 hours, CBDA (1.57 g, 8.01 mmol) and NMP (13.5 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 24.7% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g), and diluting it to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 90 ° C. 3 hours. The reaction solution was poured into methanol (330 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). This polyimine has a hydrazide conversion ratio of 80%, a number average molecular weight of 17,300, and a weight average molecular weight of 46,300.

<Synthesis Example 8>

BODA (3.00 g, 12.0 mmol), m-PBCH5DABz (3.57 g, 7.99 mmol), DBA (1.83 g, 12.0 mmol) were mixed in NMP (16.5 g), and after reacting for 5 hours at 80 ° C, CBDA (1.57) was added. g, 8.01 mmol) and NMP (13.5 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 24.9% by mass.

After adding NMP to the obtained polyamic acid solution (20.5 g), and diluting it to 6% by mass, acetic anhydride (4.48 g) and pyridine (3.32 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 90 ° C. 3 hours. The reaction solution was poured into methanol (330 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimine had an oxime imidization ratio of 81%, a number average molecular weight of 18,200, and a weight average molecular weight of 47,900.

<Synthesis Example 9>

BODA (4.38 g, 17.5 mmol), ColDAB-1 (2.61 g, 4.99 mmol), m-PDA (2.16 g, 20.0 mmol) were mixed in NMP (17.5 g), and CBDA was added after reacting at 80 ° C for 6 hours. (1.47 g, 7.50 mmol) and NMP (14.3 g) were reacted at 40 ° C for 8 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 (2.51 g) and pyridine (1.97 g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyimine had a ruthenium iodide ratio of 57%, a number average molecular weight of 22,900, and a weight average molecular weight of 55,100.

<Synthesis Example 10>

BODA (3.50 g, 14.0 mmol), ColDAB-2 (1.97 g, 4.00 mmol), DBA (2.43 g, 16.0 mmol) were mixed in NMP (15.0 g), and after reacting at 80 ° C for 6 hours, CBDA (1.18) was added. g, 6.02 mmol) and NMP (12.3 g) were reacted at 40 ° C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (20.1 g), and diluting it to 6 mass%, acetic anhydride (2.50 g) and pyridine (1.95 g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyamidimide had a ruthenium iodide ratio of 65%, a number average molecular weight of 19,200, and a weight average molecular weight of 48,700.

<Synthesis Example 11>

TCA (4.48 g, 20.0 mmol), PCH7DAB (3.81 g, 10.0 mmol), DBA (1.52 g, 9.99 mmol) were mixed in NMP (29.3 g), and the reaction was carried out at 40 ° C for 6 hours to obtain a solid concentration of the resin. 25.1% by mass of a polyaminic acid solution (11). The polyglycolic acid had a number average molecular weight of 24,700 and a weight average molecular weight of 61,200.

<Synthesis Example 12>

TCA (4.48 g, 20.0 mmol), PCH7DAB (3.04 g, 8.00 mmol), m-PDA (1.30 g, 12.0 mmol) were mixed in NMP (26.5 g), and reacted at 40 ° C for 6 hours to obtain a resin solid component. A polyaminic acid solution having a concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (20.2 g), and diluting it to 6 mass%, acetic anhydride (2.46 g) and pyridine (1.97 g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (12). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 25,900, and a weight average molecular weight of 63,200.

<Synthesis Example 13>

TCA (4.48 g, 20.0 mmol), PBCH5DAB (2.60 g, 6.01 mmol), DBA (2.13 g, 14.0 mmol) were mixed with NMP (27.0 g), and the reaction was allowed to stand at 40 ° C for 8 hours to obtain a solid concentration of the resin. 25.4% by mass of a polyaminic acid solution.

After adding NMP to the obtained polyamic acid solution (20.0 g), and diluting it to 6 mass%, acetic anhydride (2.51 g) and pyridine (1.95 g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (13). The polyimine has a hydrazine imidation ratio of 55%, a number average molecular weight of 23,100, and a weight average molecular weight of 60,100.

<Synthesis Example 14>

TCA (4.48 g, 20.0 mmol), ColDAB-1 (1.57 g, 3.00 mmol), DBA (2.59 g, 17.0 mmol) were mixed in NMP (25.7 g), and the reaction was allowed to stand at 40 ° C for 8 hours to obtain a resin solid component. A polyaminic acid solution having a concentration of 25.2% 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 (1.95g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (14). The polyamidimide had a quinone imidization ratio of 55%, a number average molecular weight of 26,800, and a weight average molecular weight of 66,200.

<Synthesis Example 15>

BODA (4.38 g, 17.5 mmol), PCH7DAB (4.76 g, 12.5 mmol), DBA (1.90 g, 12.5 mmol) were mixed with NMP (20.9 g). After reacting at 80 ° C for 5 hours, TCA (1.68 g, 7.49 mmol) and NMP (17.1 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.1% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g), and diluting it to 6 mass%, acetic anhydride (2.42g) and pyridine (1.92g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (15). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 20,200, and a weight average molecular weight of 49,900.

<Synthesis Example 16>

BODA (3.75 g, 15.0 mmol), PBCH5DAB (3.24 g, 7.49 mmol), DBA (2.66 g, 17.5 mmol) were mixed in NMP (19.4 g), and after reacting at 80 ° C for 5 hours, TCA (2.24 g, 9.99 mmol) and NMP (15.9 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.2% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g), and diluting it to 6 mass%, acetic anhydride (4.50g) and pyridine (3.33g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 90 degreeC. 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (16). The polyamidimide had an oxime imidization ratio of 80%, a number average molecular weight of 18,800, and a weight average molecular weight of 48,100.

<Synthesis Example 17>

BODA (4.38 g, 17.5 mmol), PBCH5DAB (3.24 g, 7.49 mmol), p-PDA (1.89 g, 17.5 mmol) were mixed in NMP (18.2 g), and the reaction was allowed to stand at 80 ° C for 5 hours, then TCA (1.68) was added. g, 7.49 mmol) and NMP (14.9 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.3% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g) and diluting it to 6 mass%, acetic anhydride (4.51 g) and pyridine (3.31 g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 90 ° C. 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (17). This polyimine has a quinone imidization ratio of 80%, a number average molecular weight of 19,200, and a weight average molecular weight of 50,900.

<Synthesis Example 18>

TDA (1.80 g, 5.99 mmol), PCH7DAB (2.28 g, 5.99 mmol), DBA (2.13 g, 14.0 mmol) were mixed with NMP (14.8 g), and after reacting at 80 ° C for 6 hours, CBDA (2.75 g, 14.0 mmol) and NMP (12.1 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 (2.54 g) and pyridine (1.99 g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (18). This polyimine has a hydrazide conversion ratio of 60%, a number average molecular weight of 21,100, and a weight average molecular weight of 50,200.

<Synthesis Example 19>

TDA (1.80 g, 5.99 mmol), PBCH5DAB (2.60 g, 6.01 mmol), p-PDA (1.51 g, 14.0 mmol) were mixed in NMP (14.3 g). After reacting at 80 ° C for 6 hours, CBDA (2.75) was added. g, 14.0 mmol) and NMP (11.7 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% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 90 ° C. 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to give a polyimine powder (19). The polyimine has a hydrazide conversion ratio of 79%, a number average molecular weight of 18,100, and a weight average molecular weight of 48,300.

<Synthesis Example 20>

TDA (1.80 g, 5.99 mmol), m-PBCH5DABz (2.68 g, 6.00 mmol), DBA (2.13 g, 14.0 mmol) were mixed in NMP (15.6 g), and after reacting at 80 ° C for 6 hours, CBDA (2.75) was added. g, 14.0 mmol) and NMP (12.8 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 24.8% 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 (3.31 g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 90 ° C. 3 hours. This reaction solution was poured into methanol (350 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (20). The polyamidimide had an oxime imidization ratio of 80%, a number average molecular weight of 18,800, and a weight average molecular weight of 49,700.

<Synthesis Example 21>

TDA (1.80 g, 5.99 mmol), ColDAB-1 (1.57 g, 3.00 mmol), DBA (2.59 g, 17.0 mmol) were mixed in NMP (14.3 g). After reacting at 80 ° C for 6 hours, CBDA (2.75) was added. g, 14.0 mmol) and NMP (11.7 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.1% by mass.

After adding NMP to the obtained polyamic acid solution (20.0 g), and diluting it to 6% by mass, acetic anhydride (2.55 g) and pyridine (1.95 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (21). The polyimine had a hydrazide conversion ratio of 59%, a number average molecular weight of 23,800, and a weight average molecular weight of 56,100.

<Synthesis Example 22>

CBDA (4.90 g, 25.0 mmol), AP18 (4.71 g, 12.5 mmol), p-PDA (1.35 g, 12.5 mmol) were mixed with NMP (32.9 g), and the reaction was carried out at 40 ° C for 6 hours to obtain a resin solid component. Polyuric acid solution (22) having a concentration of 25.0% by mass. The polyamine has a number average molecular weight of 28,100 and a weight average molecular weight of 78,100.

<Synthesis Example 23>

BODA (4.38 g, 17.5 mmol), AP18 (4.71 g, 12.5 mmol), DBA (1.90 g, 12.5 mmol) were mixed with NMP (20.5 g). After reacting at 80 ° C for 5 hours, CBDA (1.47 g, 7.50 mmol) and NMP (16.7 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (23) having a resin solid content concentration of 25.1% by mass. The polyamic acid had a number average molecular weight of 24,200 and a weight average molecular weight of 61,100.

<Synthesis Example 24>

BODA (4.38 g, 17.5 mmol), AP18 (4.71 g, 12.5 mmol), DBA (1.90 g, 12.5 mmol) were mixed with NMP (20.5 g). After reacting at 80 ° C for 5 hours, CBDA (1.47 g, 7.50 mmol) and NMP (16.7 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.1% by mass.

NMP was added to the obtained polyamic acid solution (20.0 g), and after diluting it to 6 mass %, acetic anhydride (2.54g) and pyridine (1.95g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 degreeC. 4 hours. This reaction solution was poured into methanol (310 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (24). This polyimine has a hydrazide conversion ratio of 60%, a number average molecular weight of 18,800, and a weight average molecular weight of 46,500.

<Synthesis Example 25>

BODA (4.38 g, 17.5 mmol), AP18 (3.77 g, 10.0 mmol), DBA (2.28 g, 15.0 mmol) were mixed with NMP (19.5 g), and after reacting at 80 ° C for 5 hours, CBDA (1.47 g, 7.50 mmol) and NMP (15.9 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.2% by mass.

After adding NMP to the obtained polyamic acid solution (20.3 g), and diluting it to 6 mass%, acetic anhydride (4.55g) and pyridine (3.35g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 90 degreeC. 3 hours. This reaction solution was poured into methanol (390 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (25). The polyimine had a hydrazide conversion rate of 80%, a number average molecular weight of 16,200, and a weight average molecular weight of 44,200.

<Synthesis Example 26>

TCA (5.60 g, 25.0 mmol), AP18 (4.71 g, 12.5 mmol), DBA (1.90 g, 12.5 mmol) were mixed in NMP (36.2 g), and the reaction was allowed to stand at 40 ° C for 8 hours to obtain a solid concentration of the resin. 25.2% by mass of a polyaminic acid solution.

After adding NMP to the obtained polyamic acid solution (20.0 g), and diluting it to 6 mass%, acetic anhydride (2.50 g) and pyridine (1.90 g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (26). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 19,300, and a weight average molecular weight of 53,400.

<Synthesis Example 27>

BODA (4.38 g, 17.5 mmol), AP18 (4.71 g, 12.5 mmol), DBA (1.90 g, 12.5 mmol) were mixed with NMP (20.9 g). After reacting at 80 ° C for 5 hours, TCA (1.68 g, 7.49 mmol) and NMP (17.1 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 (2.42g) and pyridine (1.92g) which are a ruthenium-imidation catalyst were added, and the reaction was carried out at 80 ° C. 4 hours. This reaction solution was poured into methanol (300 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (27). This polyimine has a ruthenium iodide ratio of 55%, a number average molecular weight of 20,900, and a weight average molecular weight of 50,200.

<Synthesis Example 28>

TDA (2.25 g, 7.49 mmol), AP18 (2.82 g, 7.49 mmol), p-PDA (1.89 g, 17.5 mmol) were mixed in NMP (17.3 g). After reacting at 80 ° C for 6 hours, CBDA (3.43) was added. g, 17.5 mmol) and NMP (14.2 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 24.8% by mass.

After adding NMP to the obtained polyamic acid solution (20.2 g), and diluting it to 6 mass%, acetic anhydride (4.45g) and pyridine (3.28g) which are a ruthenium-imidation catalyst were added, and reaction was carried out at 90 degreeC. 3 hours. This reaction solution was poured into methanol (370 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (28). The polyamidimide had an oxime imidization ratio of 80%, a number average molecular weight of 17,300, and a weight average molecular weight of 47,900.

The poly-proline and the polyimine of the present invention are shown in Table 43 and Table 44.

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

In the following Examples 1 to 31 and Comparative Examples 1 to 7, the production examples of the liquid crystal alignment treatment agent are described, and the inventions used for the evaluation of the liquid crystal alignment treatment agents are shown in Tables 45 to 47. Liquid crystal alignment treatment agent.

The "production of liquid crystal cell", "evaluation of alignment control of liquid crystal", and "evaluation of electrical characteristics" are as follows. Further, Tables 48 to 53 show the characteristics of the respective liquid crystal alignment treatment agents obtained in Examples 1 to 31 and Comparative Examples 1 to 7.

"The production of liquid crystal cells"

The liquid crystal alignment treatment agent was spin-coated on the ITO surface of the substrate with a 10×10 mm 20 μm pattern spacer attached to the center and the ITO surface of the substrate with the 10×40 mm ITO electrode attached thereto, and 80° C. on the hot plate. The mixture was heat-treated for 5 minutes, and heat-treated at 210 ° C for 30 minutes in a heat cycle type clean 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 clean oven to obtain a substrate with a liquid crystal alignment film.

The substrate on which the liquid crystal alignment film was attached was placed on the inside of the liquid crystal alignment film surface, and the mixture was sandwiched by a spacer of 6 μm, and adhered to the periphery with a sealant to prepare a hollow cell. In this empty cell, a liquid crystal obtained by mixing a polymerizable compound (1) represented by the following formula in MLC-6608 (manufactured by MERCK Japan) is injected by a reduced pressure injection method, which is relative to MLC-6608. 100% by mass of a liquid crystal in which 0.3% by mass of a polymerizable compound was mixed, and the injection port was closed to obtain a liquid crystal cell.

[39]

When a voltage of 5 V was applied to the obtained liquid crystal cell, a metal halide lamp having an illuminance of 60 mW was used, and a wavelength of 350 nm or less was turned off, and ultraviolet rays of 20 J/cm ² in terms of 365 nm were irradiated to obtain a liquid crystal alignment direction. Liquid crystal cell. The temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was 50 °C.

"Evaluation of alignment control of liquid crystals"

The liquid crystal response speed of the liquid crystal cell before ultraviolet irradiation and the liquid crystal cell after ultraviolet irradiation obtained by the above-mentioned "liquid crystal cell production" was measured. The time taken to change the transmittance from 90% to 10% (described as "T90 → T10" in the table) is taken as the response speed. When the direction of alignment of the liquid crystal is controlled, the response time of the liquid crystal cell after ultraviolet irradiation (described as "after treatment" in the table) is confirmed as compared with the liquid crystal cell before ultraviolet irradiation (described as "before processing" in the table). Faster.

"Evaluation of electrical characteristics"

The liquid crystal cell before ultraviolet irradiation and the liquid crystal cell after ultraviolet irradiation obtained by the above-mentioned "production of liquid crystal cell" were applied with a voltage of 4 V at a temperature of 80 ° C for 60 μm, and a voltage of 16.67 ms and 1667 ms was measured to convert the voltage. How many are kept as voltage holding ratio calculations.

<Example 1>

The polyamic acid solution (1) (10.5 g), NMP (11.8 g), and BCS (22.3 g) obtained by synthesizing the resin having a resin solid concentration of 25.5% by mass were mixed at 25 ° C for 8 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 it was a uniform solution.

<Example 2>

The polyamic acid solution (2) (10.0 g), NMP (11.0 g), and BCS (21.0 g) obtained by synthesizing the resin having a resin solid concentration of 25.2% by mass were mixed at 25 ° C for 8 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 it was a uniform solution.

<Example 3>

The polyamic acid solution (3) (11.0 g), NMP (12.0 g), and BCS (23.0 g) obtained by synthesizing the resin having a resin solid concentration of 25.1% by mass were mixed at 25 ° C for 8 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 it was a uniform solution.

<Example 4>

The polyimine powder (4) (2.50 g), NMP (18.3 g) and BCS (20.8 g) obtained in Synthesis Example 4 were mixed at 25 ° 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 it was a uniform solution.

<Example 5>

The polyimine powder (5) (2.51 g), NMP (22.6 g) and BCS (16.7 g) obtained in Synthesis Example 5 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 6>

The polyimine powder (6) (2.48 g), NMP (18.2 g) and BCS (20.7 g) obtained in Synthesis Example 6 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 7>

The polyimine powder (7) (2.50 g), NMP (22.5 g) and BCS (16.7 g) obtained in Synthesis Example 7 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 8>

The polyimine powder (8) (2.50 g), NMP (18.3 g) and BCS (20.8 g) obtained in Synthesis Example 8 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 9>

The polyimine powder (9) (2.51 g), NMP (24.7 g) and BCS (14.6 g) obtained in Synthesis Example 9 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 10>

The polyimine powder (10) (2.50 g), NMP (24.6 g) and BCS (14.6 g) obtained in Synthesis Example 10 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 11>

The polyaminic acid solution (11) (10.5 g), NMP (11.5 g), and BCS (22.0 g) obtained in Synthesis Example 11 at a resin solid concentration of 25.1% by mass were mixed at 25 ° C for 8 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 it was a uniform solution.

<Example 12>

The polyimine powder (12) (2.51 g), NMP (22.6 g) and BCS (16.7 g) obtained in Synthesis Example 12 were mixed at 25 ° 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 it was a uniform solution.

<Example 13>

The polyimine powder (13) (2.50 g), NMP (18.3 g) and BCS (20.8 g) obtained in Synthesis Example 13 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 14>

The polyimine powder (14) (2.50 g), NMP (18.3 g) and BCS (20.8 g) obtained in Synthesis Example 14 were mixed at 25 ° 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 it was a uniform solution.

<Example 15>

The polyimine powder (15) (2.41 g), NMP (21.7 g) and BCS (16.1 g) obtained in Synthesis Example 15 were mixed at 25 ° C for 12 hours to obtain a 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 it was a uniform solution.

<Example 16>

The polyimine powder (16) (2.50 g), NMP (16.3 g) and BCS (22.9 g) obtained in Synthesis Example 16 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 17>

The polyimine powder (17) (2.47 g) obtained in Synthesis Example 17, NMP (18.1 g) and BCS (20.6 g) were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 18>

The polyimine powder (18) (2.50 g), NMP (18.3 g) and BCS (20.8 g) obtained in Synthesis Example 18 were mixed at 25 ° C for 12 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 it was a uniform solution.

<Example 19>

The polyimine powder (19) (2.50 g) obtained in Synthesis Example 19, NMP (18.3 g) and BCS (20.8 g) were mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (19). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 20>

The polyimine powder (20) (2.46 g) obtained in Synthesis Example 20, NMP (22.1 g) and BCS (16.4 g) were mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (20). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 21>

The polyimine powder (21) (2.50 g) obtained in Synthesis Example 21, NMP (18.3 g) and BCS (20.8 g) were mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (21). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 22>

The polyamic acid solution (2) (10.5 g), NMP (11.6 g), BCS (22.1 g) and crosslinkable compound (1) (0.27 g) of the resin solid content concentration of 25.2% by mass obtained in Synthesis Example 2. The mixture was mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (22). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 23>

The polyamic acid solution (2) (10.0 g), NMP (11.0 g), BCS (21.0 g) and cross-linking compound (4) (0.25 g) of the resin solid content concentration of 25.2% by mass obtained in Synthesis Example 2. The mixture was mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (23). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 24>

The polyimine powder (4) (2.50 g), NMP (18.3 g), BCS (20.8 g) and the crosslinkable compound (2) (0.50 g) obtained in Synthesis Example 4 were mixed at 25 ° C for 15 hours. A liquid crystal alignment treatment agent (24) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 25>

The polyimine powder (4) (2.51 g), NMP (18.4 g), BCS (20.9 g) and the crosslinkable compound (4) (0.50 g) obtained in Synthesis Example 4 were mixed at 25 ° C for 15 hours. A liquid crystal alignment treatment agent (25) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 26>

The polyimine powder (7) (2.50 g), NMP (18.3 g), BCS (20.8 g) and the crosslinkable compound (2) (0.25 g) obtained in Synthesis Example 7 were mixed at 25 ° C for 15 hours. A liquid crystal alignment treatment agent (26) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 27>

The polyimine powder (7) (2.50 g), NMP (18.3 g), BCS (20.8 g) and the crosslinkable compound (4) (0.25 g) obtained in Synthesis Example 7 were mixed at 25 ° C for 15 hours. A liquid crystal alignment treatment agent (27) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 28>

The polyimine powder (9) (2.50 g), NMP (18.3 g), BCS (20.8 g) and the crosslinkable compound (1) (0.25 g) obtained in Synthesis Example 9 were mixed at 25 ° C for 15 hours. A liquid crystal alignment treatment agent (28) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 29>

The polyimine powder (9) (2.47 g), NMP (18.1 g), BCS (20.6 g) and the crosslinkable compound (4) (0.47 g) obtained in Synthesis Example 9 were mixed at 25 ° C for 15 hours. A liquid crystal alignment treatment agent (29) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 30>

The polyimine powder (15) (2.50 g), NMP (18.3 g), BCS (20.8 g) and the crosslinkable compound (3) (0.08 g) obtained in Synthesis Example 15 were mixed at 25 ° C for 15 hours. A liquid crystal alignment treatment agent (30) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Example 31>

The polyimine powder (17) (2.49 g), NMP (18.3 g), BCS (20.8 g) and the crosslinkable compound (5) (0.08 g) obtained in Synthesis Example 17 were mixed at 25 ° C for 15 hours. A liquid crystal alignment treatment agent (31) was obtained. In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Comparative Example 1>

The polyamic acid solution (22) (10.5 g), NMP (11.4 g), and BCS (21.9 g) obtained in Synthesis Example 22 at a resin solid concentration of 25.0% by mass were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment. Agent (32). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Comparative Example 2>

The polyamic acid solution (23) (10.0 g), NMP (10.9 g), and BCS (20.9 g) obtained in Synthesis Example 23 at a resin solid concentration of 25.1% by mass were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment. Agent (33). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Comparative Example 3>

The polyimine powder (24) (2.50 g) obtained in Synthesis Example 24, NMP (26.7 g), and BCS (12.5 g) were mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (34). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Comparative Example 4>

The polyimine powder (25) (2.52 g), NMP (22.7 g) and BCS (16.8 g) obtained in Synthesis Example 25 were mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (35). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Comparative Example 5>

The polyimine powder (26) (2.50 g), NMP (24.6 g) and BCS (14.6 g) obtained in Synthesis Example 26 were mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (36). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Comparative Example 6>

The polyimine powder (27) (2.45 g), NMP (24.1 g) and BCS (14.3 g) obtained in Synthesis Example 27 were mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (37). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

<Comparative Example 7>

The polyimine powder (28) (2.48 g), NMP (20.3 g) and BCS (18.6 g) obtained in Synthesis Example 28 were mixed at 25 ° C for 12 hours to obtain a liquid crystal alignment treatment agent (38). In the liquid crystal alignment treatment agent, no abnormality such as turbidity or precipitation was observed, and it was confirmed that it was a uniform solution.

From Tables 48 to 50, it was confirmed that the liquid crystal cells obtained in Examples 1 to 31 and Comparative Examples 1 to 7 controlled the alignment direction of the liquid crystal by ultraviolet irradiation.

As a result of the above, it is understood that the liquid crystal alignment film obtained by the liquid crystal alignment treatment agents of Examples 1 to 31 can suppress the decrease in the voltage holding ratio even when ultraviolet irradiation is performed. On the other hand, in the liquid crystal alignment film obtained from the liquid crystal alignment treatment agents of Comparative Examples 1 to 7, the decrease in the voltage holding ratio was large.

Further, comparisons between Examples 1 to 3, Example 11 and Comparative Example 1 and Comparative Example 2, and comparisons between Examples 4 to 10, Examples 11 to 21, and Comparative Examples 3 to 7 In the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example, it is possible to suppress a decrease in the voltage holding ratio even when ultraviolet irradiation is performed. Therefore, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present embodiment can provide a liquid crystal display element which is highly reliable without causing a line-like afterimage of display failure of the liquid crystal display element.

Further, according to Examples 22 to 31, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent containing a crosslinkable compound can further suppress the decrease in the voltage holding ratio due to ultraviolet irradiation.

[Industry use possibility]

The liquid crystal alignment treatment agent of the present invention can be used in a liquid crystal display device which uses a liquid crystal material in which a polymerizable compound polymerized by heat or ultraviolet irradiation is mixed in a liquid crystal to apply a voltage to the liquid crystal layer. The polymer obtained by polymerizing the above polymerizable compound is obtained by a method of controlling the alignment direction of the liquid crystal during driving. Moreover, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can suppress a decrease in the voltage holding ratio due to ultraviolet irradiation. Therefore, the liquid crystal display element having such a liquid crystal alignment film is excellent in reliability, and can be suitably used for a large-screen, high-definition liquid crystal television or the like.

Claims (11)

A liquid crystal alignment agent which is used for a liquid crystal display element and which contains at least one of a polyimine precursor having a side chain represented by the following formula [1] and a polyimine, the liquid crystal display element A liquid crystal material obtained by mixing a polymerizable compound which is polymerized by heat or ultraviolet irradiation in a liquid crystal, and a polymer obtained by polymerizing the polymerizable compound while applying a voltage to the liquid crystal layer, and controlling the alignment direction of the liquid crystal during driving. Method of getting, (In the formula [1], X _{1 is} derived from -O-, -CH ₂ O-, -COO-, -(CH ₂ ) _a - (a is an integer of 1 to 10), -NH-, -N(CH) ₃ ) -, -CONH-, -NHCO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or a divalent organic group selected from a single bond, X ₂ is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) selected from a divalent organic group, and X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O -, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ ) a divalent organic group selected from CO-, and X ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on the above cyclic group may be derived from 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, or the fluorine-containing alkoxy group having 1 to 3 carbon atoms, and the fluorine atom are substituted, and X ₅ represents a ring. a divalent cyclic group selected from a hexyl ring, a benzene ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms or 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, and n is an integer of 0 to 4, and X ₆ is an alkyl group having 1 to 18 carbon atoms. , Fluorine-containing alkyl group having 1 to 18 carbons, alkoxy having 1 to 18 carbon atoms or a hydrogen atom-containing alkoxy group of 1 to 18). The liquid crystal alignment treatment agent according to claim 1, wherein the polymer is a polymer obtained by using a diamine compound having a side chain of the formula [1] as a part of a raw material. The liquid crystal alignment treatment agent of the second aspect of the invention, wherein the diamine compound having a side chain of the formula [1] is a structure represented by the following formula [1a], (In the formula [1a], X ₁ is -O-, -CH ₂ O-, -COO-, -(CH ₂ ) _a - (a is an integer of 1 to 10), -NH-, -N(CH) ₃ ) -, -CONH-, -NHCO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or a divalent organic group selected from a single bond, X ₂ is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) selected from a divalent organic group, and X ₃ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O -, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ ) a divalent organic group selected from CO-, and X ₄ represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring or a heterocyclic ring, and any hydrogen atom on the above cyclic group may be derived from 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, or the fluorine-containing alkoxy group having 1 to 3 carbon atoms, and the fluorine atom are substituted, and X ₅ represents a ring. a divalent cyclic group selected from a hexyl ring, a benzene ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms or 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, and n is an integer of 0 to 4, and X 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, a fluorine-containing alkoxy group having 1 to 18 carbon atoms or a hydrogen atom, and m is an integer of 1 to 4). The liquid crystal alignment treatment agent of claim 3, wherein the diamine compound of the structure represented by the formula [1a] accounts for 5 to 80 mol% of the diamine component. The liquid crystal alignment treatment agent according to the first aspect of the invention, wherein the polymer is a polymer obtained by using a tetracarboxylic dianhydride represented by the following formula [2], (In the formula [2], Y 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). The liquid crystal alignment treatment agent of claim 5, wherein Y ₁ is a structure represented by the following formula [2a] to formula [2j], (In the formula [2a], Y ₂ to Y ₅ are groups selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different, and in the formula [2g], Y ₆ and Y ₇ are hydrogen. Atoms or methyl groups, each of which may be the same or different). The liquid crystal alignment treatment agent according to claim 1, wherein the liquid crystal alignment treatment agent has at least one selected from the group consisting of an epoxy group, an oxetane group, an isocyanate group, and a cyclic carbonate group. a crosslinkable compound of a substituent; having crosslinkability of at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, an alkoxy group, and a lower alkoxyalkyl group a compound; or a crosslinkable compound having a polymerizable unsaturated bond. The liquid crystal alignment treatment agent of claim 1, wherein the polymer in the liquid crystal alignment treatment agent is a polyimine obtained by dehydrating a poly-proline. 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 a liquid crystal alignment treatment agent according to any one of claims 1 to 9. A liquid crystal display element having a liquid crystal alignment film according to claim 10 of the patent application.