TWI568796B - A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device - Google Patents

Description

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

The present invention relates to a composition for forming a polyimide film, a liquid crystal alignment treatment agent used for producing a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

Polyimide-based organic films have been attracting attention due to their ease of formation and insulating properties, and are widely used in the field of electronic devices, and are used as interlayer insulating films, protective films, liquid crystal alignment films in liquid crystal display devices, and the like.

In recent years, with the increase in the size and definition of liquid crystal display elements, the degree of unevenness of the substrate and substrate used is increased. In this case, a uniform liquid crystal alignment film is required even for a large substrate and a large unevenness step.

In the process of producing a liquid crystal alignment film, when a liquid crystal alignment treatment agent containing polylysine or a solvent-soluble polyimine (also referred to as a resin) is applied to a substrate, industrially, a flexographic printing method or an inkjet method is generally used. The coating method or the like is carried out.

At this time, when the coating property of the liquid crystal alignment agent is poor, cracking may occur or Pinholes, as a result, can cause display defects when used as a liquid crystal display element. Therefore, in the solvent of the liquid crystal alignment treatment agent, in addition to a solvent having a good resin solubility (also referred to as a good solvent), N-methyl-2-pyrrolidone or γ-butyrolactone, and the like, the film of the liquid crystal alignment film is further mixed. A solvent (also referred to as a weak solvent), ethylene glycol monobutyl ether or the like having a low solubility in a resin (for example, refer to Patent Document 1).

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2-37324

However, weak solvents have poor ability to dissolve polyaminic acid or solvent-soluble polyimine, so that a large amount of mixing is required, and as a result, there is a problem of precipitation of the resin.

In addition, in a liquid crystal display device for mobile use such as a smart phone or a mobile phone used in recent years, in order to secure a large number of display surfaces, the sealant used between the substrates for bonding the liquid crystal display elements is close to the end of the liquid crystal alignment film. . Therefore, the coating property of the end portion of the liquid crystal alignment film is lowered, that is, when the end portion of the liquid crystal alignment film is not linear, or when the end portion is in a raised state, the bonding effect between the liquid crystal alignment film and the sealant is lowered, and the liquid crystal display element is lowered. Display characteristics and reliability.

In view of the above, it is an object of the present invention to provide for the formation of poly A composition having an excellent coating property for an amine film. Moreover, the composition of the present invention is used as a liquid crystal alignment treatment agent, and the obtained coating film is improved in wettability with respect to the substrate to obtain uniform coating property, and the liquid crystal alignment film having excellent coating properties at the end portion. . In particular, even if a liquid crystal alignment treatment agent using a polyaminic acid or a solvent-soluble polyimine obtained by using a branched diamine compound is used, a liquid crystal alignment film having such characteristics can be provided, and the liquid crystal having the above-mentioned liquid crystal is provided. A liquid crystal display element of an alignment film.

As a result of intensive research by the present inventors, it has been found that at least one selected from the group consisting of a solvent having a specific structure and a polyimine obtained by polyimine imidization of a polyimide precursor and a polyimide precursor. The composition of the polymer is extremely effective for achieving the above object, and the present invention has been completed.

That is, the present invention has the following gist.

(1) A composition comprising the following component (A) and component (B), and component (A): a solvent represented by the following formula [1],

(In the formula [1], X ₁ represents an alkyl group having 1 to 3 carbon atoms).

Component (B): at least one polymer selected from the group consisting of polyimine precursors and polyimine precursors obtained by hydrazine imidization.

(2) The component (B) is a polyimine which is partially used as a raw material of a diamine compound having a branch represented by the following formula [2]. a polymer of at least one selected from the group consisting of a precursor and a polyimine precursor obtained by quinone imidization of a polyimine.

(In the formula [2], Y ₁ is a single chain, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number 12 to 25 having a nest skeleton The divalent organic group, any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or carbon a fluorine-containing alkoxy group or a fluorine atom substituted by 1 to 3; Y ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and the cyclic groups are Any of the 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or Substituted with a fluorine atom; n is an integer of 0 to 4; Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a carbon number of 1 to 18 fluorine-containing alkoxy group).

(3) The composition according to the above (2), wherein the diamine compound having a branch represented by the formula [2] is a diamine compound represented by the following formula [2a],

(In the formula [2a], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number 12 to 25 having a nest skeleton The divalent organic group, any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, carbon a fluorine-containing alkoxy group or a fluorine atom substituted by 1 to 3; Y ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and the cyclic groups are Any hydrogen atom may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine. Atom substituted; n is an integer from 0 to 4; Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a carbon number of 1 to 18 Fluorinated alkoxy; m is an integer from 1 to 4.

(4) The composition according to the above (2) or (3), wherein the diamine compound represented by the above formula [2] or the diamine compound represented by the formula [2a] is a diamine component. 5 to 80% of the total.

(5) The composition according to any one of the above-mentioned (1), wherein the component (B) is a tetracarboxylic acid containing a tetracarboxylic dianhydride represented by the following formula [3]. a polymer of a dianhydride component,

(In the formula [3], Z _{1 is} a structure of at least one selected from the group consisting of the following formulas [3a] to [3j]).

(In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or a methyl group. Can be the same or different).

(6) The composition according to any one of the above (1) to (5) which contains the component (C), which is composed of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ - at least one solvent selected from the group consisting of butyrolactone.

(7) The composition according to any one of the above (1) to (6) which contains the component (D), which is composed of 1-hexanol, cyclohexanol, 1,2-B. Glycol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether At least one solvent selected from the group consisting of diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether.

The composition according to any one of the above-mentioned items (1), wherein the component (A) is 5 to 60% by mass based on the total amount of the solvent contained in the composition.

(9) The composition according to any one of the above (6), wherein the component (C) is 40 to 80% by mass based on the total amount of the solvent contained in the composition.

(10) The composition according to any one of the above (7), wherein the component (D) is from 1 to 50% by mass based on the total amount of the solvent contained in the composition.

(11) The composition according to any one of the above (1), wherein the component (B) in the composition is from 0.1 to 30% by mass.

(12) A polyimine film obtained by using the composition according to any one of the above (1) to (11).

(13) A liquid crystal alignment treatment agent obtained by using the composition according to any one of the above (1) to (11).

(14) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to (13) above.

(15) A liquid crystal alignment film obtained by an inkjet printing method using the liquid crystal alignment treatment agent according to the above (13).

(16) A liquid crystal display element comprising the liquid crystal alignment film according to (14) or (15) above.

(17) The liquid crystal alignment film according to the above (14) or (15), wherein a liquid crystal layer is provided between a pair of substrates having electrodes, and an active energy ray is disposed between the pair of substrates The liquid crystal composition of the polymerizable compound polymerized by at least one of the heat is applied to the liquid crystal display element produced by the step of applying a voltage between the electrodes and polymerizing the polymer.

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

(19) The liquid crystal alignment film according to the above (14) or (15), wherein a liquid crystal layer is provided between a pair of substrates having electrodes, and an active energy ray is disposed between the pair of substrates. A liquid crystal alignment film of a polymerizable compound polymerized by at least one of the heat is applied to a liquid crystal display element produced by a step of applying a voltage between the electrodes and polymerizing the polymerizable group.

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

The composition of the present invention containing a solvent having a specific structure, and at least one polymer selected from the group consisting of a polyimide and a polyimide, can provide a polyimide having excellent coating properties. A composition for a film. Moreover, when the composition of the present invention is used as a liquid crystal alignment treatment agent It is possible to provide a liquid crystal alignment film which has a coating property which is uniform in the wettability of the coating solution with respect to the substrate, and which has excellent coating properties even at the end portion of the liquid crystal alignment film. In particular, a liquid crystal alignment film having excellent properties can be provided even in the case of using a liquid crystal alignment treatment agent using a polyaminic acid or a solvent-soluble polyimine obtained by using a branched diamine compound. Further, a liquid crystal display element having the above liquid crystal alignment film and a liquid crystal alignment treatment agent capable of providing the above liquid crystal alignment film can be provided.

Fig. 1 is an enlarged schematic view showing an image of a polyimide film on a chromium vapor-deposited substrate observed by an optical microscope at a magnification of 25 times.

Fig. 2 is an enlarged schematic view showing an image of a polyimide film on a chromium vapor-deposited substrate observed by an optical microscope at a magnification of 25 times.

The invention will be described in detail below.

The present invention contains a composition of the following components (A) and (B), a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

Component (A): a solvent (also referred to as a specific solvent) represented by the following formula [1].

(In the formula [1], X ₁ represents an alkyl group having 1 to 3 carbon atoms).

Component (B): at least one polymer selected from the group consisting of polyimine precursors and polyimine precursors obtained by hydrazine imidization.

The specific solvent of the present invention can be used as a weak solvent for improving the coating property of a polyimide film or a liquid crystal alignment film. The particular solvent of the present invention is generally a relatively low solvent surface tension for ethylene glycol monobutyl ether (also known as butyl cellosolve or BCS) used in relatively weak solvents. Therefore, by using a coating solvent of a specific solvent and comparing the coating solution which is not used, the wettability of the coating solution with respect to the substrate can be improved, and even if a weak solvent having a low solubility of a large amount of resin is not used, it can be coated. A polyimide film or a liquid crystal alignment film excellent in film properties. Further, when the polyimine film or the liquid crystal alignment film is formed under the wet expandability of the coating solution, the linearity of the end portion of the polyimide film can be improved.

Further, the specific solvent of the present invention is a polyethylene glycol monobutyl ether which is generally used as a weak solvent and has a relatively high boiling point. Therefore, when a coating solution using a specific solvent is used to form a polyimide film or a liquid crystal alignment film, edge bulging of the polyimide film can be suppressed.

The component (B) of the present invention is at least one polymer selected from the group consisting of polyimine imines and polyimine precursors obtained by hydrazine imidization. Wherein the composition of the present invention is used as a liquid crystal When the alignment agent is used for a liquid crystal alignment film, a polyimine precursor and a polyimine precursor which are branched (also referred to as a specific branched structure) represented by the following formula [2] are used. It is preferred that at least one polymer (also referred to as a specific polymer) selected from the group consisting of polyamidimides obtained by amination.

(In the formula [2], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number 12 to 25 having a nest skeleton The divalent organic group, any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or carbon a fluorine-containing alkoxy group or a fluorine atom substituted by 1 to 3; Y ₅ represents a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, on which the cyclic group is Any of the 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or Substituted by a fluorine atom. n is an integer of 0 to 4. Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a carbon number of 1 to 18 fluorine-containing alkoxy group).

The specific branching structure of the present invention is such that the branched portion has a benzene ring, a cyclohexyl ring or a heterocyclic ring, or has a nest-like skeleton having a carbon number of 12 to 25 The organic base of divalent. The benzene ring, the cyclohexyl ring or the hetero ring, or the divalent organic group having a nest-like skeleton having 12 to 25 carbon atoms is a straight-chain structure compared to the long-chain alkyl group of the prior art. Therefore, the stability of the branch portion with respect to heat and ultraviolet rays can be improved, and a liquid crystal alignment film having a stable pretilt angle with respect to heat and light can be obtained.

From the above, the composition of at least one polymer selected from the group consisting of the specific solvent of the present invention and the polyimine imine obtained by the ruthenium imidization of the polyimide precursor and the polyimide precursor A composition for forming a polyimide film or a liquid crystal alignment film excellent in coating property or a liquid crystal alignment treatment agent can be realized.

Further, the polyimine obtained by the imidization of a specific solvent of the present invention and a polyimide precursor and a polyimine precursor having a specific branched structure represented by the above formula [2] The liquid crystal alignment treatment agent obtained by the composition of at least one of the polymers selected in the group is such that a liquid crystal alignment film which does not change the pretilt angle even when exposed to high temperature and light for a long period of time can be formed. Further, by using the liquid crystal alignment film, a liquid crystal display element having high display performance and excellent display characteristics can be provided.

<specific solvent>

The specific solvent of the present invention is represented by the following formula [1].

In the formula [1], X ₁ represents an alkyl group having 1 to 3 carbon atoms.

Specifically, it is a structure represented by any one of the following formulas [1a] to [1c].

The specific solvent of the present invention is preferably from 5 to 70% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent in order to enhance the effect of improving the wettability of the coating solution with respect to the substrate. Among them, 5 to 65 mass% is preferred. More preferably, it is 5 to 60% by mass, and particularly preferably 10 to 55% by mass.

When the specific solvent content of the present invention is large in the solvent in the composition, the effect of the present invention, that is, the polyimide film having excellent coating property can be obtained by improving the wet expandability of the coating solution with respect to the substrate. Liquid crystal alignment film.

<specific branch structure>

The polymer of the present invention preferably has an effect of improving the drainage property of the polyimide film as a polyimide film and improving the stability of the pretilt angle when used as a liquid crystal alignment film. A specific polymer having a specific branched structure represented by the following formula [2].

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

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

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

In the formula [2], Y ₅ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms. And 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.

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

In the formula [2], Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, preferred are 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. Further, it is preferably 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 [2], preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n are, for example, 13 to 34 of the International Public Commentary WO2011/132751 (2011.10.27 publication). The same combinations of (2-1) to (2-629) are disclosed in Tables 6 to 47. Further, in the tables of the International Publications, Y ₁ to Y ₆ of the present invention are represented by Y1 to Y6, and Y1 to Y6 are another reading of Y ₁ to Y ₆ .

<Specific branched diamine compound>

The specific polymer of the present invention, that is, at least one selected from the group [2] selected from the group consisting of polyimine precursors and polyimine precursors obtained by quinone imidization. The method of the specific branched structure is preferably carried out by using a diamine compound having a specific branched structure as a raw material. It is particularly preferred to use a diamine compound (also referred to as a specific branched diamine compound) represented by the following formula [2a].

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

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

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

In the formula [2a], Y ₅ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms. And 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.

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

In the formula [2a], Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, preferred are 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. Further, it is preferably 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.

A preferred combination of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in the formula [2a] is the same as the formula [2].

Among the combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n, a more preferable combination is 2-25 to 2-96, 2-145 to 2-168, 2-217 to 2-240 , 2-268 to 2-315, 2-364 to 2-387, 2-436 to 2-383 or 2-603 to 2-615, etc., particularly preferred combinations are 1-49 to 1-96, 1-145 to 1-168, 1-217 to 1-240 or 2-603 to 2-606, and the like.

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

Specifically, for example, a compound having the structure represented by the following formula [2-1] to formula [2-31].

(In the formula [2-1] to the formula [2-3], R ₁ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-. R ₂ is a carbon number a linear or branched alkyl group of 1 to 22, a linear or branched alkoxy group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, Or a fluorine-containing alkoxy group having a carbon number of 1 to 22.

(In the formula [2-4] to the formula [2-6], R ₃ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ - or -CH _{2 -.} R ₄ is a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxy group having 1 to 22 carbon atoms, and a carbon number. A linear or branched fluorine-containing alkyl group of 1 to 22, or a fluorine-containing alkoxy group having 1 to 22 carbon atoms).

(In the formula [2-7] and the formula [2-8], 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, an ethyl group, a Alkoxy or hydroxy).

(In the formula [2-9] and the formula [2-10], R ₇ is a linear or branched alkyl group having 3 to 12 carbon atoms, and each of the cis-trans isomers of 1,4-cyclohexene is Anti-isomer).

(In the formula [2-11] and the formula [2-12], R ₈ is a linear or branched alkyl group having 3 to 12 carbon atoms, and each of the cis-trans isomers of 1,4-cyclohexene is Anti-isomer).

(In the formula [2-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom. A ₃ is a 1,4-cyclohexyl group or a 1,4-stretch. Phenyl. A ₂ is an oxygen atom or COO-* (but a "*" bond is bonded to A ₃ ). A ₁ is an oxygen atom or COO-* (but with a "*" bond hand system) Bonded with (CH ₂ )a ₂ )). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.

In the above formulas [2-1] to [2-31], the diamine compound of a particularly preferable structure is a formula [2-1] to a formula [2-6], a formula [2-9] to a formula [2-13]. Or equation [2-22] to formula [2-31] and the like.

The above-mentioned specific branched type diamine compound or the like is used as a liquid crystal alignment film for the solubility of the polymer of the present invention with respect to a solvent, the polyimine film used for the polyimide film, and the liquid crystal alignment film. In the case of the characteristics of the liquid crystal alignment, the voltage holding ratio, and the accumulated electric charge, one type or a mixture of two or more types may be used.

<Other diamine compounds>

In the present invention, the diamine component other than the branched diamine compound (also referred to as another diamine compound) may be used as a raw material diamine component without impairing the effects of the present invention. This is specifically described below.

P-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene Amine, 2,4-dimethyl-m-benzene Diamine, 2,5-diaminomethyl, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-di Aminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl- 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-di Aminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-di Aminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'- Sulfonodiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl - bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4'- Diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-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'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diamine Naphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7 -diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-di Amino naphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl) Ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene , 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-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(methyl)diphenylamine , 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3,4 '-[1,3-Exophenyl bis(methyl))diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[1 , 3-phenylphenyl bis(methyl)diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-amine) Phenyl phenyl) ketone], 1,3-phenylene bis[(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-phenylene bis ( 3-amino benzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl) ) isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminophenylguanamine), N , N'-(1,3-phenylene) bis(4-aminophenylguanamine), N,N'-(1,4-phenylene)bis(3-aminophenylguanamine), N , N'-(1,3-phenylene) bis(3-aminophenylguanamine), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-double (3- Aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-amino group Phenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoro Propane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis ( 4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 3,5- Diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis(4-aminophenoxy)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-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminobenzene Oxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminobenzene Oxy) decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxyl) An aromatic diamine compound such as undecane, 1,12-(4-aminophenoxy)dodecane, 1,12-(3-aminophenoxy)dodecane, or the like -Aminocyclohexyl)methane, alicyclic diamine compound such as bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane 1,5-Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane , An aliphatic diamine compound such as 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

Further, without impairing the effects of the present invention, a diamine compound having a dialkyl branched chain having an alkyl group or a fluorine-containing alkyl group can be used.

Specifically, for example, a diamine compound represented by the following formula [DA1] to formula [DA12].

(In the formula [DA1] to the formula [DA5], A ₁ is a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms; ).

(In the formula [DA6] to the formula [DA11], A ₂ represents -COO-, -OCO-, CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-. A ₃ represents A linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

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

The diamine compound represented by the following formula [DA13] to formula [DA20] can also be used without impairing the effects of the present invention.

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

Further, in addition to the effects of the present invention, a diamine compound having a carboxyl group in the molecule represented by the following formula [DA21] to formula [DA25] can also be used.

(In the formula [DA21], m ₁ is an integer of 1 to 4. In the formula [DA22], A ₄ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, - CF ₂ -, -C(CF ₃ )-, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-.m ₂ and m ₃ are each an integer of 0 to 4, and m ₂ +m ₃ is 1 to 4 In the formula [DA23], m ₄ and m ₅ are each an integer of 1 to 5. In the formula [DA24], A ₅ is a linear or branched alkyl group having 1 to 5 carbon atoms; m ₆ is 1 An integer of 5. In the formula [DA25], A ₆ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ )- , -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH2-, -COO-, -OCO-, -CON( CH ₃ )- or -N(CH ₃ )CO-.m ₇ is an integer from 1 to 4).

Further, the diamine compound represented by the following formula [DA26] can also be used without impairing the effects of the present invention.

(In the formula [DA26], A ₁ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ ) - or -N (CH ₃₎ CO- is selected from a divalent organic group of ₂ .A single bond, a carbon number of aliphatic hydrocarbon group, non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group of ₃ to 20 .A From a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ ) CO- or -O(CH ₂ ) _m - (m is an integer of 1 to 5). A ₄ is a nitrogen-containing aromatic heterocyclic ring. n is an integer of 1 to 4).

Further, without impairing the effects of the present invention, a diamine compound having a nest skeleton represented by the following formula [DA27] or formula [DA28] can also be used.

The above other diamine compound can be used as the solubility of the polymer of the present invention with respect to a solvent, the drainage property of the polyimide film used in the polyimide film, and the liquid crystal alignment when used as a liquid crystal alignment film. The characteristics of the properties, the voltage holding ratio, the accumulated charge, and the like may be used alone or in combination of two or more.

<Specific tetracarboxylic dianhydride>

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

In the formula [3], Z ₁ is a tetravalent group represented by the following formula [3a] to formula [3j].

In the formula [3a], Z ₂ to Z ₅ are groups selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom and a benzene ring, and may be the same or different, in the formula [3g], Z ₆ and Z ₇ The hydrogen atom or the methyl group may be the same or different.

In the formula [3], the excellent structure of Z _{1 is} such that the polymerization reactivity and the easily synthesizable property are the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula [3g]. . Among them, the formula [3a], the formula [3e], the formula [3f] or the formula [3g] is preferred.

<Other tetracarboxylic dianhydride>

In the present invention, other tetracarboxylic dianhydrides (also referred to as other tetracarboxylic dianhydrides) other than the specific tetracarboxylic dianhydride can be used without impairing the effects of the present invention. Other tetracarboxylic anhydride dianhydrides such as the tetracarboxylic dianhydride of the following tetracarboxylic acid.

Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic anhydride, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6, 7-decanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid , bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyl) Phenyl, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro -2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2 ,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4 9,10-dioxatetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydride can be used for the solubility of the polymer of the present invention with respect to a solvent, the drainage property of the polyimide film used in the polyimide film, and The characteristics of the liquid crystal alignment property, the voltage holding ratio, and the accumulated charge when used as the liquid crystal alignment film are used singly or in combination of two or more kinds.

<Polymer ‧ Ding Polymer>

The polymer of the component (B) of the present invention is at least one polymer selected from the group consisting of a polyimide precursor or a polyimine.

The polyimine precursor is a structure represented by the following formula [A].

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

The polymer of the present invention can be easily produced by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as a raw material, and therefore it is preferably of the following formula [ D] The polylysine formed by the structural formula of the repeating unit represented by the above or the polyimine obtained by imidization of the polyglycolic acid.

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

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

The method of synthesizing the polymer in the present invention is not particularly limited. Generally, a diamine component is reacted with a tetracarboxylic acid component. Generally, at least one of the tetracarboxylic acid components selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component formed from one or a plurality of diamine compounds to obtain a polyamic acid. Specifically, a method of polycondensing a tetracarboxylic dianhydride with a diamine component to obtain a poly-proline, a method of dehydrating polycondensation of a tetracarboxylic acid and a diamine component to obtain a poly-proline, or a tetracarboxylic acid can be used. A method in which an acid dihalide is condensed with a diamine component to obtain a polyamic acid.

When the polyalkyl phthalate is produced, a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group can be used by polycondensing a tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group with a diamine component. A method of polycondensing an acid dihalide with a diamine component, or a method of converting a carboxyl group of polylysine to an ester.

When the polyimine is produced, a method in which the polylysine or the polyalkyl amide is ring-closed to obtain a polyimine is used.

The specific polymer of the present invention is a polymer of at least one selected from the group consisting of a branched polyimine precursor represented by the above formula [2] or a polyimine.

In the liquid crystal alignment film obtained by using the specific polymer of the present invention, when the content ratio of the specific branched structure represented by the above formula [2] is high in the diamine component, the drainage property as a liquid crystal alignment film can be improved. Pretilt angle with liquid crystal. In this case, the diamine component is preferably a specific branched diamine compound represented by the above formula [2a]. Particularly, a specific branched diamine compound represented by the above formula [2-1] to formula [2-6] or formula [2-9] to formula [2-13] is used. The specific branch represented by the formula [2-1] to the formula [2-6], the formula [2-9] to the formula [2-12] or the formula [2-22] to the formula [2-31] A diamine compound is preferred.

In order to improve this characteristic, it is preferable that 5 mol% or more and 80 mol% or less of the diamine component is a specific branched diamine compound. Among them, from the viewpoint of the coatability of the liquid crystal alignment agent and the electrical properties for the liquid crystal alignment film, a specific branched type diamine compound is preferably 5 mol% or more and 60 mol% or less of the diamine component. More preferably, it is 10 mol% or more and 60 mol% or less of the diamine component.

When the polymer of the present invention is produced, it is preferred to use the specific tetracarboxylic dianhydride represented by the above formula [3] as the tetracarboxylic acid component. Particularly, tetracarboxylic dianhydride in which Z ₁ in the formula [3] is a structural group represented by the above formula [3a] to formula [3j] is used. In this case, it is preferred that 1 mol% or more of the tetracarboxylic acid component is a specific tetracarboxylic dianhydride, more preferably 5 mol% or more, still more preferably 10 mol% or more. Further, 100 mol% of the tetracarboxylic acid component may be tetracarboxylic dianhydride.

The reaction between the diamine component and the tetracarboxylic acid component is generally carried out by allowing the diamine component and the tetracarboxylic acid component to be carried out in an organic solvent. The organic solvent to be used in this case is not particularly limited as long as it can dissolve the produced polyimide precursor. This is specifically described below.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl hydrazine, γ-butyrolactone, 1,3-two Methyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

These may be used alone or in combination. Further, even if it is a solvent in which the polyimide precursor is not dissolved, the above solvent can be used 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 causes hydrolysis of the produced polyimide precursor, it is preferred to use a product obtained by dehydrating and drying the organic solvent.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, the diamine component is stirred or dissolved in an organic solvent to obtain a tetracarboxylic acid component, or dispersed or dissolved in an organic solvent, and then added. method. Or conversely adding the diamine component to the tetracarboxylic acid component to disperse or dissolve Any of these methods can be used as a method of dissolving a solution obtained in an organic solvent, a method of mutually adding a tetracarboxylic acid component and a diamine component, and the like. Further, when a plurality of kinds of the diamine component and the tetracarboxylic acid component are used for the reaction, the reaction may be carried out in a state of being mixed in advance, or the reaction may be carried out in sequence, or the polymer obtained by mixing the low molecular weight substances obtained by the respective reactions may be used. . The polymerization temperature at this time may be any temperature of from -20 to 150 ° C, but preferably from -5 to 100 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, it is difficult to produce a polymer having a high molecular weight. When the concentration is too high, the viscosity of the reaction liquid is increased and it is difficult to uniformly stir. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent is added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably from 0.8 to 1.2. As with the general polycondensation reaction, the molecular weight of the polyimine precursor formed when the molar ratio is close to 1.0 is large.

The polyimine of the present invention is a polyimine obtained by subjecting the polyimine precursor to ring closure, and is suitable for use in a polymer for producing a polyimide film or a liquid crystal alignment film.

In the polyimine of the present invention, the ring closure ratio (also referred to as the oxime imidization ratio) of the amidino group is not required to be 100%, and can be arbitrarily adjusted depending on the purpose and purpose.

A method for imidating a polyimine precursor, for example, by directly heating a solution of a polyimide precursor, or by adding a catalyst to a solution of a polyimide precursor Chemical.

The temperature at which the polyamidene precursor is thermally imidized in solution is It is preferably 100 to 400 ° C, preferably 120 to 250 ° C, and it is preferably carried out while discharging the water formed by the oxime imidization reaction.

The imidization of the quinone imine precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor, and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. get on. 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. The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine, and the like, wherein pyridine is preferably held in an appropriate basic state during the reaction. The acid anhydride is, for example, acetic anhydride, trimellitic anhydride or pyromellitic anhydride. Among them, it is preferred to use an acetic anhydride to complete the reaction and then to refine it. The imidization ratio of the ruthenium imidized by the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, the reaction solution may be added to a solvent to precipitate. The solution for precipitation is, for example, methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. The polymer obtained by the introduction of the solvent and precipitated can be dried by filtration at normal temperature or under heating under reduced pressure or reduced pressure. Further, the re-dissolution of the precipitate-recovered polymer in the organic solvent by repeating 2 to 10 times can be carried out to reduce the impurities in the polymer. In the case of a solvent such as an alcohol, a ketone or a hydrocarbon, etc., when three or more solvents selected from the above are used, the purification efficiency can be further improved.

The molecular weight of the polymer of the present invention is determined by the polyimine obtained therefrom. The weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, more preferably in the case of the strength of the film, the workability at the time of formation of the polyimide film, and the film coating property of the polyimide film. 10,000 to 150,000.

<Composition ‧ Liquid crystal alignment treatment agent>

The composition of the present invention or the liquid crystal alignment treatment agent using the same is a coating solution for forming a polyimide film or a liquid crystal alignment film (also collectively referred to as a resin film), and a resin film containing a specific solvent and a polymer. Coating solution.

In the composition of the present invention or the liquid crystal alignment treatment agent using the same, all of the polymer components may be the polymer of the present invention, or the polymer of the present invention may be mixed with other polymers. In the polymer at this time, the content of the other polymer is from 0.5 to 15% by mass, preferably from 1 to 10% by mass. Other polymers such as polyimine precursors and polymers other than polyimine, such as acrylic based polymers, methacrylic based polymers, polystyrene, polydecylamine or decane based polymers Wait.

Further, when the liquid crystal alignment film is formed by using the composition of the present invention as a liquid crystal alignment treatment agent, it is preferred to use a specific polymer in the polymer. At this time, all of the polymer components may be all of the specific polymers of the present invention, or the specific polymers of the present invention may be mixed with other polymers. The content of the other polymer in the specific polymer at this time is from 0.5 to 15% by mass, preferably from 1 to 10% by mass. Other polymers such as those obtained from a diamine component which does not contain a specific branched diamine compound and a tetracarboxylic acid component which does not contain a specific tetracarboxylic dianhydride Amine precursor or polyimine. Further, the polymer other than the polyimide precursor and the polyimine is, for example, an acrylic polymer, a methacryl polymer, a polystyrene, a polyamine or a siloxane polymer.

The composition of the present invention or the organic solvent in the liquid crystal alignment treatment agent used therein forms a viewpoint of coating a more uniform resin film, and the content of the organic solvent is preferably from 70 to 99.9% by mass, more preferably from 70 to 98% by mass. %. The content can be appropriately changed depending on the film thickness of the intended polyimide film or the liquid crystal alignment film. The organic solvent at this time may be an organic solvent capable of dissolving the polymer of the present invention, and is not particularly limited. This is specifically described below.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl hydrazine, γ- Butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone (hereinafter also referred to as component (C)) is preferably used.

The component (C) is preferably 20 to 90% by mass based on the entire organic solvent contained in the composition or the liquid crystal alignment treatment agent using the same. It is preferably 30 to 80% by mass, more preferably 40 to 80% by mass, still more preferably 40 to 70% by mass.

The composition of the present invention or the liquid crystal alignment treatment agent using the same can be used to improve the coating property and surface smoothness of the resin film when the composition or the liquid crystal alignment treatment agent is used without using the effect of the present invention. Solvent, ie weak solvent.

A weak solvent for improving the coating properties and surface smoothness of a resin film The body is as described below.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, isoamyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl 2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol , cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1 , 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentane Alcohol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, B Diol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl Ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2 -ethylbutyl acetate, 2- Ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-( Methoxymethoxy)ethanol, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol hexyl ether, 2-(hexyloxy)ethanol, Sugar alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol single Methyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diethyl Acid ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol Acid ester, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate Monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-B Oxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, An organic solvent having a low surface tension of a solvent such as n-butyl ester lactate or isoamyl lactate.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl are preferably used. Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether (also referred to above For ingredient (D)).

The weak solvent is preferably from 1 to 60% by mass based on the total of the organic solvent contained in the composition or the liquid crystal alignment treatment agent using the same. Among them, it is preferably from 1 to 50% by mass, more preferably from 5 to 45% by mass.

The composition of the present invention or the liquid crystal alignment treatment agent using the same can be introduced into a crosslinkable compound having an epoxy group, an isocyanate group, an oxypropylene group or a cyclic carbonate group, having a hydroxyl group, without impairing the effects of the present invention. At least one selected from the group consisting of a hydroxyalkyl group and a lower alkoxyalkyl group A crosslinkable compound of a substituent or a crosslinkable compound having a polymerizable unsaturated bond. The substituent or the polymerizable unsaturated bond needs to be two or more of the crosslinkable compounds.

a crosslinkable compound having an epoxy group or an isocyanate group such as bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl trimer isocyanate, tetraglycidylamino group Diphenyl ester, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl shrinkage Glycerol ether, bisphenol hexafluoroacetic acid diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-three Fluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl-m-xylenediamine, 2- (4-(2,3-epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)benzene Propane, 1,3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-) ring) Oxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

The crosslinkable compound having an oxypropylene group is a crosslinkable compound having at least two oxypropylene groups represented by the following formula [4].

Specifically, for example, the formula [4a] to the formula [4k] disclosed in items 58 to 59 of the international publication WO2011/132751 (2011.10.27 publication) A cross-linking compound is shown.

The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5].

Specifically, the crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed in 76 to 82 of the International Publication No. WO2012/014898 (published in 2012.2.2).

a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine-based resin having a hydroxyl group or an alkoxy group, such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril - Formaldehyde resin, butylene amine-formaldehyde resin or ethyl urea-formaldehyde resin. Specifically, 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 can be used. The melamine derivative or the benzoguanamine derivative may exist in the form of a dimer or a trimer. These are preferably those having an average of 3 or more and 6 or less hydroxymethyl groups or alkoxymethyl groups per triazine ring.

Such melamine derivatives or benzoguanamine derivatives such as MX-750 in which each triazine ring of the commercial product is substituted with an average of 3.7 methoxymethyl groups, and an average of 5.8 methoxy groups per triazine ring Methyl substituted MW-30 (hereinafter referred to as Sanwa Chemical Co., Ltd.), or Semel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Oxyoxymethylated melamine, SEMEL 235, 236, 238, 212, 253, 254, etc. methoxymethylated butoxymethylated melamine, Semel 506, 508, etc. Melamine, Semel 1141-containing methoxymethylated isobutoxymethylated melamine, Semel 1123-like methoxymethylated ethoxymethylated benzoguanamine, race Meier 1123-10-like methoxymethylated butoxymethylated benzoguanamine, Semel 1128-butoxymethylated benzoguanamine, Semel 1125-80 contains carboxyl Methoxymethylated ethoxymethylated benzoguanamine (above is manufactured by Mitsui Saina Honey Co., Ltd.). Further, glycoluril such as Semel 1170-butoxymethylated glycoluril, Semel 1172-like methylolated glycoluril, and Pardarin 1174-like methoxymethylolated glycoluril.

a benzene or phenolic compound having a hydroxyl group or an alkoxy group such as 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1,4 - bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, the crosslinkable compound represented by the formula [6-1] to the formula [6-48] disclosed on pages 62 to 66 of International Publication WO2011/132751 (2011.10.27 publication).

a crosslinkable compound having a polymerizable unsaturated bond such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tris(methyl) a cross-linking compound having three polymerizable unsaturated groups in the molecule such as propylene methoxy ethoxy trimethylolpropane or glycerol polyglycidyl ether poly(meth) acrylate, and, for example, ethylene glycol (meth) acrylate, diethylene glycol Di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate , butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A di(meth)acrylate, propylene oxide bisphenol A type II Acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(methyl) Acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, decanoic acid diglycidyl ether di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, etc. a crosslinkable compound having two polymerizable unsaturated groups in the molecule, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy butyl ( Methyl) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, 3-chloro-2- Hydroxypropyl (meth) acrylate A glycerol mono(meth)acrylate, 2-(meth)acryloyloxyethyl phosphate, N-hydroxymethyl(meth)acrylamide or the like having one polymerizable unsaturated group in the molecule A combination compound.

Further, a compound represented by the following formula [7] can be used.

(In the formula (7), E _{1 is a group} consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring, and a phenanthrene ring. The selected group, E ₂ is a group selected from the group consisting of the following formulas [7a] and [7b], and n is an integer of 1 to 4).

The above compound is an example of a crosslinkable compound, but is not limited thereto. Further, the cross-linking compound used in the composition of the present invention or the liquid crystal alignment treatment agent using the same may be used alone or in combination of two or more.

In the composition of the present invention or the liquid crystal alignment treatment agent using the same, the content of the crosslinkable compound is preferably from 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. The effect of the purpose of the crosslinking reaction is preferably from 0.1 to 100 parts by mass, preferably from 1 to 50 parts by mass, per 100 parts by mass of the total of the polymer component.

When a liquid crystal alignment agent obtained from the composition of the present invention is used as a liquid crystal alignment film, a charge shift in a liquid crystal alignment film can be promoted, and a compound which removes a charge using a liquid crystal cell of the liquid crystal alignment film can be promoted. For example, International Publication WO2011/132751 The nitrogen-containing heterocyclic amine compound represented by the formulas [M1] to [M156] disclosed on pages 69 to 73 of (2011.10.27).

Preferably, it is a formula [M1], a formula [M7], a formula [M16] to a formula [20], a formula [M24], a formula [M35], a formula [M36], a formula [M40], a formula [M49], and a formula. [M50], formula [M52], formula [M60] to formula [M62], formula [M68], formula [M69], formula [M76], formula [M77], formula [M82], formula [M100], formula [M101], formula [M108], formula [M109], formula [M118] to Formula [M121], formula [M128], formula [M134] to formula [M136] or formula [M140].

These amine compounds may be directly added to the composition, but may be added to a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass, in a suitable solvent. The solvent may be an organic solvent capable of dissolving the above polymer, and is not particularly limited.

In the composition of the present invention or the liquid crystal alignment treatment agent using the same, the film thickness uniformity and surface smoothness of the resin film obtained by using the coating composition or the liquid crystal alignment treatment agent using the coating composition can be used without impairing the effects of the present invention. compound of. Further, a compound for improving the adhesion between the resin film and the substrate can be used.

A compound for improving the film thickness uniformity and surface smoothness of the resin film, for example, a fluorine-based surfactant, a polyoxyxide-based surfactant, a nonionic surfactant, or the like.

More specifically, Yvette EF301, EF303, EF352 (made by Tekken Co., Ltd.), Mikafa F171, F173, R-30 (made by Dainippon Ink Co., Ltd.), Flora FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Isaishi AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by the company). The content 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 total polymer component contained in the composition or the liquid crystal alignment treatment agent.

Specific examples of the compound for improving the adhesion between the resin film and the substrate are, for example, the following compounds containing a functional decane or containing an epoxy group. Compound.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, 3-ureidopropyl Trimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxydecane, N-triethoxydecylpropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1,4,7 - triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9 -triethoxydecyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethyl Oxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide)-3-aminopropyl Trimethoxy decane, N-bis(ethylene oxide)-3- Aminopropyl triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl Base-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl) Cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When using these compounds in close contact with the substrate, the content of the compound It is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the composition or the liquid crystal alignment treatment agent using the same. When the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and when it is more than 30 parts by mass, the storage stability of the composition or the liquid crystal alignment treatment agent using the same may be deteriorated.

In the composition of the present invention or the liquid crystal alignment treatment agent using the same, the weak solvent, the crosslinkable compound, the compound for improving the film thickness uniformity and surface smoothness of the resin film, and the compound for the adhesion substrate are not destructive. Within the range of the effects of the invention, a dielectric or a conductive material for changing the electrical properties such as the permittivity and conductivity of the polyimide film or the liquid crystal alignment film may be added.

<Polyimide film>

The composition of the present invention is applied onto a substrate and, after firing, can be used as a polyimide film. In the substrate to be used at this time, a glass substrate, a tantalum board, an acrylic substrate, a plastic substrate such as polycarbonate, or the like can be used depending on the intended device. The coating method of the composition is not particularly limited, and is generally industrially carried out by dipping, roll coating, slit coating, spin coating, spray, screen printing, offset printing, flexographic printing or ink jet printing. The method. These may be used for the purpose.

After the composition is applied to the substrate, the resin film is obtained by evaporating the solvent at 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a heat cycle type oven or an IR (infrared) type oven. The thickness of the resin film after baking can be adjusted to 0.01 to 50 μm in accordance with the purpose.

<Liquid alignment film, liquid crystal display element>

The liquid crystal alignment treatment agent obtained by using the composition of the present invention is applied onto a substrate, and after firing, it is subjected to alignment treatment by rubbing treatment or light irradiation, and can be used as a liquid crystal alignment film. Further, in the vertical alignment use, it can be used as a liquid crystal alignment film even without alignment treatment. The substrate to be used at this time is not particularly limited as long as the substrate having high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used as the glass substrate. From the viewpoint of simplification of the steps, it is preferred to use a substrate on which an ITO electrode or the like for driving a liquid crystal is used. Further, in the reflective liquid crystal display device, an opaque substrate such as a ruthenium circuit board may be used as the substrate on one side, and a material such as aluminum or the like may be used as the electrode.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and is generally a method which is industrially carried out by screen printing, offset printing, flexographic printing or ink jet printing. Other coating methods such as a dipping method, a roll coating method, a slit coating method, a spin coating method, or a spray method can be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied to the substrate, the liquid crystal alignment can be obtained by evaporating the solvent at 50 to 300 ° C, preferably 80 to 250 ° C by heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven. membrane. When the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and when it is too thin, the reliability of the liquid crystal display element is lowered, so it is preferably 5 to 300 nm, more preferably 10 to 100 nm. In order to align the liquid crystal horizontally or obliquely, the liquid crystal alignment film may be treated by rubbing or polarized ultraviolet irradiation or the like after baking.

The liquid crystal display element of the present invention is obtained by a known method from the substrate to which the liquid crystal alignment film is attached by the liquid crystal alignment treatment agent of the present invention. A liquid crystal display element obtained by using a liquid crystal cell.

In the liquid crystal cell manufacturing method, for example, a pair of substrates for forming a liquid crystal alignment film are prepared, and the distance adjustment substance is spread on the liquid crystal alignment film of the single substrate, and the other substrate is bonded to the inner side of the liquid crystal alignment film surface, and then the liquid crystal is injected under reduced pressure. A method of sealing, or a method of re-sealing a liquid crystal by dropping a liquid crystal into a liquid crystal alignment film surface on which a distance adjustment object has been dispensed.

Moreover, it is preferable that the liquid crystal alignment treatment agent of the present invention has a liquid crystal layer between a pair of substrates having electrodes, and a polymerizable compound which is polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates. A liquid crystal display device produced by a step of applying a voltage to a polymer and irradiating a polymerizable compound by at least one of an active energy ray and a heating. The active energy ray at this time is preferably ultraviolet ray. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating can be simultaneously performed.

The liquid crystal display element is a pre-dip object for controlling liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is added to the liquid crystal material, and after the liquid crystal cell is assembled, ultraviolet rays or the like is applied to the photopolymerizable compound while being applied to the liquid crystal layer with a constant voltage. The resulting polymer controls the pretilt of the liquid crystal molecules. Since the alignment state of the liquid crystal molecules at the time of polymer formation can be memorized after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer or the like. Moreover, there is no need for friction treatment in the PSA method, so it is suitable for forming difficult to control by friction treatment. Pre-tilted vertical alignment type liquid crystal layer.

In the liquid crystal display device of the present invention, the liquid crystal cell is produced by the liquid crystal alignment film of the liquid crystal alignment agent of the present invention, and the polymerizable compound is polymerized by irradiating at least one of ultraviolet rays and heating. And controlling the alignment of the liquid crystal molecules.

In the case of the PSA liquid crystal cell fabrication example, a pair of substrates for forming a liquid crystal alignment film may be prepared, and the distance adjustment substance may be spread on the liquid crystal alignment film of the single substrate, and the other side of the liquid crystal alignment film surface may be attached to the other side. After the substrate, the liquid crystal is re-sealed by decompression, or the liquid crystal is dropped into the liquid crystal alignment film surface on which the distance adjustment object has been dispensed, and the substrate is resealed.

A polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays is mixed in the liquid crystal. The polymerizable compound is a compound having one or more polymerizable unsaturated groups such as acrylate or methacrylate 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 cannot be polymerized, and the alignment of the liquid crystal cannot be controlled. When the amount is more than 10 parts by mass, the unreacted polymerizable compound is increased, and the sintering characteristics of the liquid crystal display element are lowered.

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

Moreover, it is preferable that the liquid crystal alignment treatment agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerization polymerization of at least one of an active energy ray and heat is disposed between the pair of substrates. Sex-based fluid A liquid crystal display element produced by a step of applying a voltage to a film via a voltage. The active energy ray at this time is preferably ultraviolet ray. The ultraviolet light has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating can be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, for example, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or a polymerization containing a polymerizable group may be used. Method of composition of matter.

Since the liquid crystal alignment agent of the present invention contains a specific compound having a double bond site which is reacted by heat or ultraviolet irradiation, at least one of ultraviolet light irradiation and heating can control the alignment of liquid crystal molecules.

In the liquid crystal cell production example, a pair of substrates for forming a liquid crystal alignment film may be prepared, and the distance adjustment substance may be spread on the liquid crystal alignment film of the single substrate, and the other substrate may be bonded to the inner side of the liquid crystal alignment film surface, and then decompressed. A method of injecting liquid crystal and resealing, or a method of re-sealing a liquid crystal by dropping a liquid crystal into a liquid crystal alignment film surface on which a distance adjustment object has been dispensed.

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

The liquid crystal display element produced by the liquid crystal alignment treatment agent of the present invention has excellent reliability and is suitable for a large-screen and high-definition liquid crystal television.

Example

The invention will now be described in more detail by way of examples, without limitation.

The symbols of the compounds used in the examples are as follows.

(tetracarboxylic dianhydride)

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

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

TCA: tetracarboxylic dianhydride represented by the following formula

TDA: tetracarboxylic dianhydride represented by the following formula

(diamine compound)

p-PDA: p-phenylenediamine

m-PDA: m-phenylene diamine

DBA: 3,5-diaminobenzoic acid

AP18: 1,3-diamino-4-octadecyloxybenzene

(specific branched 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-diamine-5-{4-[4-(trans-4-n-pentylcyclohexyl)phenyl]phenoxymethyl}benzene

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

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

(Specific solvent (ingredient (A))

Dipropylene glycol dimethyl ether represented by the following formula [1a]

(ingredient (C))

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

(ingredient (D))

BCS: ethylene glycol monobutyl ether

MC: diethylene glycol monomethyl ether

EC: diethylene glycol monoethyl ether

(Measurement of molecular weight of polyimide precursors and polyimine)

Using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101, manufactured by Showa Denko Co., Ltd.) and a column (KD-803, KD-805) (manufactured by Shodex Co., Ltd.), the measurement was carried out by the following method.

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (additive is lithium bromide-hydrate (LiBr‧H ₂ O) 30 mmol/L (liter), phosphoric acid ‧ anhydride crystal (o-phosphoric acid) 30 mmol/L, tetrahydrofuran ( THF) 10ml/L)

Flow rate: 1.0ml/min

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

(Measurement of hydrazine imidation rate)

20 mg of polyimine powder was placed in an NMR sample tube (NMR sampling tube standard, 5 (manufactured by Kusano Scientific Co., Ltd.) was added with deuterated dimethyl hydrazine (DMSO-d6, 0.05% TMS (tetramethyl decane) mixture) (0.53 ml), and ultrasonic waves were applied thereto to completely dissolve. This solution was measured by a proton NMR of 500 MHz using an NMR measuring machine (JNW-ECA500, manufactured by JEOL Ltd.). The ruthenium imidization rate is determined by protons derived from unstructured structures before and after imidization, using the peak product of the protons and NH from proline at 9.5 ppm to 10.0 ppm. The proton peak product value of the base is obtained by the following formula.

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

In the above formula, x is the proton peak product value of the NH group derived from proline, y is the peak product calculation value of the reference proton, and α is the polyamine acid (the imidization ratio is 0%) relative to the proline acid. The ratio of the number of reference protons of one NH matrix.

<Synthesis Example 1>

BODA (5.74 g, 22.9 mmol), DBA (2.79 g, 18.3 mmol) and m-PDA (2.98 g, 27.6 mmol) were mixed in NMP (28.8 g), and reacted at 60 ° C for 2 hours, then CBDA (4.50 g) was added. , 23.0 mmol) and NMP (19.2 g), reacted at 40 ° C for 4 hours to obtain a tree A polyamic acid solution (1) having a lipid solid content concentration of 25.0% by mass. The polyamic acid had a number average molecular weight of 28,800 and a weight average molecular weight of 82,400.

<Synthesis Example 2>

After the NMP was added to the polyamic acid solution (1) (45.0 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 1 and diluted to 6 mass%, acetic anhydride (5.75 g) for the ruthenium catalyst was added. And pyridine (4.20 g), and reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (900 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (2). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 24,600, and a weight average molecular weight of 60,100.

<Synthesis Example 3>

CBDA (4.32 g, 22.0 mmol), PCH7DAB (4.19 g, 11.0 mmol) and p-PDA (1.19 g, 11.0 mmol) were mixed with NMP (29.1 g), and reacted at 40 ° C for 6 hours to obtain a solid concentration of the resin. 25.0% by mass of a polyaminic acid solution (3). The polyamic acid had a number average molecular weight of 25,800 and a weight average molecular weight of 72,200.

<Synthesis Example 4>

BODA (7.14g, 28.5mmol), PCH7DAB (4.08g, 10.7mmol) and DBA were mixed in NMP (29.5g) (3.79 g, 24.9 mmol), after reacting at 80 ° C for 5 hours, CBDA (1.40 g, 7.1 mmol) and NMP (19.7 g) were added and reacted at 40 ° C for 6 hours to obtain a solid concentration of the resin of 25.0% by mass. Proline solution.

After the NMP was added to the obtained polyamic acid solution (40.0 g) to be diluted to 6 mass%, acetic anhydride (4.84 g) and pyridine (3.78 g) for the ruthenium catalyst were added, and the mixture was reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyimine had a hydrazine imidation ratio of 54%, a number average molecular weight of 22,500, and a weight average molecular weight of 53,900.

<Synthesis Example 5>

BODA (7.14 g, 28.5 mmol), PCH7DAB (6.79 g, 17.8 mmol) and DBA (2.71 g, 17.8 mmol) were mixed in NMP (32.5 g), and reacted at 80 ° C for 5 hours, then CBDA (1.40 g, 7.1) was added. Methyl) was reacted with NMP (21.7 g) at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After the NMP was added to the obtained polyamic acid solution (40.0 g) to be diluted to 6 mass%, acetic anhydride (9.02 g) and pyridine (6.52 g) for the ruthenium catalyst were added, and the mixture was reacted at 90 ° C for 3.5 hours. The reaction solution was poured into methanol (800 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimine had a hydrazine imidation ratio of 80%, a number average molecular weight of 20,100, and a weight average molecular weight of 50,100.

<Synthesis Example 6>

BODA (4.91 g, 19.6 mmol), PBCH5DAB (4.25 g, 9.8 mmol) and DBA (2.77 g, 18.2 mmol) were mixed in NMP (24.4 g), and reacted at 80 ° C for 5 hours, then CBDA (1.65 g, 8.4) was added. Methyl) was reacted with NMP (16.3 g) at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After the NMP was added to the obtained polyamic acid solution (40.0 g) to be diluted to 6 mass%, acetic anhydride (9.00 g) and pyridine (6.50) for the ruthenium catalyst were added, and the mixture was reacted at 90 ° C for 3 hours. The reaction solution was poured into methanol (800 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimine had a hydrazine imidation ratio of 79%, a number average molecular weight of 19,500, and a weight average molecular weight of 48,800.

<Synthesis Example 7>

BODA (4.61 g, 18.4 mmol), m-PBCH5DABz (3.53 g, 7.9 mmol) and m-PDA (1.99 g, 18.4 mmol) were mixed in NMP (21.0 g), and reacted at 80 ° C for 4.5 hours, then added CBDA ( 1.55 g, 7.9 mmol) and NMP (14.0 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

After the NMP was added to the obtained polyamic acid solution (40.5 g) to be diluted to 6 mass%, acetic anhydride (9.05 g) and pyridine for the ruthenium catalyst were added. (6.50 g), the reaction was carried out at 90 ° C for 3 hours. The reaction solution was poured into methanol (900 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyimine had a hydrazine imidation ratio of 80%, a number average molecular weight of 21,900, and a weight average molecular weight of 55,100.

<Synthesis Example 8>

BODA (7.65 g, 30.6 mmol), CoIDAB-1 (3.00 g, 5.7 mmol) and DBA (4.96 g, 32.6 mmol) were mixed in NMP (30.8 g), and reacted at 80 ° C for 5.5 hours, then CBDA (1.50 g) was added. 7.7 mmol) and NMP (20.5 g) were reacted at 40 ° C for 7 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

After the NMP was added to the obtained polyamic acid solution (40.0 g) to be diluted to 6 mass%, acetic anhydride (4.90 g) and pyridine (3.70 g) for the ruthenium catalyst were added, and the mixture was reacted at 80 ° C for 3.5 hours. The reaction solution was poured into methanol (1000 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 20,500, and a weight average molecular weight of 57,300.

<Synthesis Example 9>

BODA (7.65g, 30.6mmol), CoIDAB-2 (1.88g, 3.8mmol) and p-PDA were mixed in NMP (26.6g) (3.73 g, 34.5 mmol), after reacting at 80 ° C for 5.5 hours, CBDA (1.50 g, 7.7 mmol) and NMP (17.7 g) were added and reacted at 40 ° C for 7 hours to obtain a solid concentration of the resin of 25.0% by mass. Proline solution.

After the NMP was added to the obtained polyamic acid solution (40.0 g) to be diluted to 6 mass%, acetic anhydride (4.91 g) and pyridine (3.70 g) for the ruthenium catalyst were added, and the mixture was reacted at 80 ° C for 3.5 hours. The reaction solution was poured into methanol (1000 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9) having a ruthenium imidization ratio of 53% and a number average molecular weight of 17,800. The weight average molecular weight was 48,900.

<Synthesis Example 10>

BODA (7.91 g, 31.6 mmol), AP18 (4.47 g, 11.9 mmol) and DBA (4.20 g, 27.6 mmol) were mixed in NMP. After reacting at 80 ° C for 4.5 hours, CBDA (1.55 g, 7.9 mmol) and NMP were added. (21.8 g), the reaction was carried out at 40 ° C for 6.5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

After the NMP was added to the obtained polyamic acid solution (40.0 g) to be diluted to 6 mass%, acetic anhydride (5.00 g) and pyridine (3.71 g) for the ruthenium catalyst were added, and the mixture was reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (800 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyamidimide has a ruthenium iodide ratio of 54%, a number average molecular weight of 17,100, and a flat weight. The average molecular weight was 44,800.

<Synthesis Example 11>

TCA (5.50 g, 24.8 mmol), PBCH5DAB (3.21 g, 7.4 mmol) and DBA (2.64 g, 17.4 mmol) were mixed in NMP, and reacted at 40 ° C for 6 hours to obtain a polythene having a resin solid concentration of 25.0% by mass. Amino acid solution.

After the NMP was added to the obtained polyamic acid solution (40.0 g) to be diluted to 6 mass%, acetic anhydride (4.80 g) and pyridine (3.71 g) for the ruthenium catalyst were added, and the mixture was reacted at 80 ° C for 4 hours. The reaction solution was poured into methanol (900 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 22,200, and a weight average molecular weight of 57,900.

<Synthesis Example 12>

TDA (5.36 g, 17.9 mmol), PCH7DAB (4.08 g, 10.7 mmol) and m-PDA (2.70 g, 25.0 mmol) were mixed in NMP, and reacted at 80 ° C for 5 hours, then CBDA (3.50 g, 17.8 mmol) was added. The mixture was reacted with NMP (18.8 g) at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

After the NMP was added to the obtained polyamic acid solution (40.0 g) to be diluted to 6 mass%, acetic anhydride (8.85 g) and pyridine (6.45 g) for the ruthenium catalyst were added, and the mixture was reacted at 90 ° C for 3 hours. The reaction solution is put into methanol In (1000 ml), the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (12). The polyimine had a hydrazine imidation ratio of 78%, a number average molecular weight of 20,500, and a weight average molecular weight of 51,600.

The composition of the polyamic acid and the polyimine obtained in the synthesis example and the composition of each component for synthesis were combined with the ruthenium imidation ratio as shown in Table 1.

[Modulation Composition and Liquid Crystal Alignment Treatment Agent]

Examples 1 to 34, and Comparative Examples 1 to 8 are preparation examples of the composition. Further, the obtained composition was also used to evaluate various characteristics of the liquid crystal alignment treatment agent.

The compositions obtained in the examples and the comparative examples, the liquid crystal alignment treatment agent, and the components for preparation were combined as shown in Tables 2 to 4.

"Evaluation of the printability of the composition and the liquid crystal alignment treatment agent", "Evaluation of the inkjet printing coating property of the liquid crystal alignment treatment agent", and "Production of the liquid crystal cell" were carried out using the composition obtained in the examples and the comparative examples or the liquid crystal alignment treatment agent. "General Units", "Liquid Crystal Alignment Evaluation (General Unit)", "Pretilt Evaluation (General Unit)", "Production Liquid Crystal Cell (PSA Unit)", and "Liquid Crystal Alignment Evaluation (PSA Unit)". The conditions are as follows.

"Evaluation of the printability of the composition and liquid crystal alignment agent"

The composition obtained in the examples and the comparative examples was used for the evaluation of printability. The printing machine used was a simple printing machine S15 type (manufactured by Nippon Photo Printing Co., Ltd.). On the unwashed chrome-vapor-deposited substrate, the printing area was 80 mm × 80 mm, the printing pressure was 0.2 mm, the discarded substrate was 5 pieces, the printing to false drying time was 90 seconds, and the hot plate was 70 ° C. Fake drying was carried out for 5 minutes.

The pinhole evaluation of the obtained polyimide film, the linearity evaluation of the end of the polyimide film, and the evaluation of the end ridge of the polyimide film were carried out.

The pinhole evaluation of the polyimide film was carried out by visually observing the polyimide film under the sodium lamp. Specifically, the number of pinholes confirmed on the polyimide film was counted, and those having a small number of pinholes were regarded as excellent.

The linearity evaluation of the end portion of the polyimide film was carried out by observing the polyimine with respect to the right end portion in the printing direction by an optical microscope. Specifically, the difference between (1) and (2) in Fig. 1 of the image of the polyimine film observed by the optical microscope magnification is 25 times, that is, the polyimine film of the length of A in Fig. 1 The images were measured at the same magnification. When the length of the A is short, the linearity of the end portion of the polyimide film is excellent.

The evaluation of the end bulge of the polyimide film was carried out by observing the polyimide film on the right end of the printing direction with an optical microscope. Specifically, the length of B in FIG. 2 of the polyimine film image observed by the optical microscope magnification is 25 times. All of the polyimine film images were obtained at the same magnification. When the length of B is short, the end portion of the polyimide film is excellent in bulging.

Further, since the compositions obtained in the examples and the comparative examples can be used for preparing a liquid crystal alignment treatment agent, the results of evaluation of the printability of the polyimide film obtained in the examples and the comparative examples are the same as those of the liquid crystal alignment film. .

The number of pinholes, the length of A, and the length of B of the polyimide film (liquid crystal alignment film) obtained in the examples and the comparative examples are shown in Tables 5 to 7.

[Evaluation of inkjet printing coatability of liquid crystal alignment treatment agent]

Using the liquid crystal alignment treatment agent (4) obtained in Example 4, examples 9 obtained liquid crystal alignment treatment agent (9), liquid crystal alignment agent (12) obtained in Example 12, liquid crystal alignment agent (18) obtained in Example 18, and liquid crystal alignment treatment agent (27) obtained in Example 27 were ink-jetted. Printability evaluation. The inkjet printing coater used was HIS-200 (manufactured by Nippon Denso Co., Ltd.). The coating was applied to the ITO (Indium Tin Oxide) vapor-deposited substrate after washing, and the coating area was 70 mm × 70 mm, the nozzle pitch was 0.423 mm, the scanning pitch was 0.5 mm, and the coating speed was 40 mm/sec. The coating was applied to a pseudo-drying time of 60 seconds, and a hot plate was dried at 70 ° C for 5 minutes.

Moreover, when evaluating the inkjet printing coatability, the number of pinholes of the obtained liquid crystal alignment film can be easily matched.

The pinhole of the obtained liquid crystal alignment film can be evaluated under the same conditions as the "evaluation of the printability of the composition and the liquid crystal alignment agent".

The number of pinholes of the liquid crystal alignment film obtained in the examples is shown in Tables 5 and 6.

"Making a Liquid Crystal Cell (General Unit)"

The liquid crystal alignment treatment agents obtained in the examples and the comparative examples were spin-coated on the ITO surface of a substrate having a 30 mm × 40 mm ITO electrode, and then subjected to a hot plate at 80 ° C for 5 minutes, and in a heat cycle type purification oven at 220 ° C. After a minute of heat treatment, an ITO substrate of an agglomerated quinone liquid crystal alignment film having a film thickness of 100 nm was obtained. The rayon was rubbed with a friction device having a roll diameter of 120 mm, and subjected to rubbing treatment under the conditions of a roll rotation number of 1000 rpm, a roll travel speed of 50 mm/sec, and an extrusion amount of 0.1 mm.

Prepare two pieces of the obtained ITO substrate with liquid crystal alignment film to match the liquid crystal After the 6 μm-positioned object was held in such a manner that the film surface was inside, an empty unit was formed by bonding the sealant around. The liquid crystal is injected into the empty cell by a vacuum injection method, and the liquid crystal cell (general cell) is sealed by the injection port.

Further, in the liquid crystal cells of the liquid crystal alignment treatment agents (1) to (3) obtained in Examples 1 to 3 and the liquid crystal alignment treatment agents (35) to (36) obtained in Comparative Examples 1 to 2, the liquid crystal system used MLC. -2003 (Merku Japan Co., Ltd.).

Further, the liquid crystal alignment treatment agents (5) to (8) obtained in Examples 5 to 8 and the liquid crystal alignment treatment agents (10) to (11) obtained in Examples 10 to 11 and the liquid crystal alignment treatments obtained in Examples 13 to 17 were used. Liquid crystal alignment treatment agents (28) to (26) obtained in Examples (13) to (17), and liquid crystal alignment treatment agents (28) to (34) obtained in Examples 19 to 26, and liquid crystal alignment treatment agents (28) to (34) obtained in Examples 28 to 34 and Comparative Example 3 In the liquid crystal cell of the liquid crystal alignment treatment agents (37) to (42) obtained in the above, the liquid crystal system was MLC-6608 (manufactured by Mercury Japan Co., Ltd.).

"Liquid alignment evaluation (general unit)"

The liquid crystal alignment was evaluated using the obtained liquid crystal cell. In the liquid crystal alignment, the liquid crystal cell was observed with a polarizing microscope to confirm the presence or absence of an alignment defect.

The evaluation results of the liquid crystal alignment obtained in the examples and the comparative examples are shown in Tables 8 to 10.

"Pretilt assessment (general unit)"

The pre-tilt evaluation was performed using the obtained liquid crystal cell. The pretilt angle was measured by injecting liquid crystal, heat treatment at 95 ° C for 5 minutes, and heat treatment at 120 ° C for 5 hours. Further, after the liquid crystal was injected, the film was heat-treated at 95 ° C for 5 minutes, and the obtained liquid crystal cell was irradiated with ultraviolet rays of 10 J/cm ^{2 in terms} of 365 nm, and then measured.

The pretilt angle after heat treatment at 95 ° C for 5 minutes, the heat treatment at 120 ° C for 5 hours or the change in the pretilt angle after irradiation with ultraviolet rays is small, and the stability with respect to the pretilt angle of heat or ultraviolet rays is high.

Further, the pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON Co., Ltd.). In addition, ultraviolet irradiation was performed using a desktop type UV curing device (HCT3B28HEX-1, manufactured by Moritech Co., Ltd.).

The evaluation results of the pretilt angles obtained in the examples and comparative examples are shown in Tables 8 to 10.

"Making LCD Units and Evaluating Liquid Crystal Alignment (PSA Units)"

The liquid crystal alignment treatment agent (8) obtained in Example 8, the liquid crystal alignment treatment agent (10) obtained in Example 10, the liquid crystal alignment treatment agent (17) obtained in Example 17, and the liquid crystal alignment treatment agent obtained in Example 26 ( 26) Spin-coated on a substrate with an ITO electrode of 10 mm × 10 mm with a pattern interval of 20 μm, and an ITO surface of a substrate with a 10 mm × 40 mm ITO electrode attached to the center, followed by heat treatment at 80 ° C for 5 minutes on a hot plate. The film was heat-treated at 220 ° C for 30 minutes in a heat cycle type purification oven to obtain a polyimide film having a film thickness of 100 nm. After washing the surface of the coating film with pure water, it was heat-treated at 100 ° C for 15 minutes in the center of the heat cycle type purification oven to obtain a substrate with a liquid crystal alignment film.

The substrate with the liquid crystal alignment film was placed on the substrate with the liquid crystal alignment film surface inside, and a distance of 6 μm was adjusted. Then, an empty cell was formed by bonding the sealing agent. Into the MLC-6608 (manufactured by Mercury Co., Ltd.), a liquid crystal obtained by mixing 0.3% by mass of the polymerizable compound (1) represented by the following formula with respect to MLC-6608 was injected into the mold by a vacuum injection method. In the empty cell, the injection port is sealed to obtain a liquid crystal cell.

A voltage of 5 V was applied to the obtained liquid crystal cell, and a metal halide lamp having a brightness of 60 mW was used to intercept ultraviolet light of 20 J/cm ² at a wavelength of 350 nm or less at a wavelength of 350 nm or less to obtain a liquid crystal alignment direction controlled. Liquid crystal cell (PSA unit). The temperature of the irradiation device when ultraviolet rays were irradiated to the liquid crystal cell was 50 °C.

The liquid crystal response speed of the liquid crystal cell before ultraviolet irradiation and after ultraviolet irradiation was measured. The response speed was determined by measuring T90→T10 from a light transmittance of 90% to a light transmittance of 10%.

When the PSA unit obtained in the examples was compared with the liquid crystal cell before the ultraviolet irradiation, the response speed of the liquid crystal cell after the ultraviolet irradiation was faster, and it was confirmed that the alignment direction of the liquid crystal was controlled. Further, it was confirmed by a polarizing microscope that the liquid crystal of any liquid crystal cell was uniformly uniformly aligned.

<Example 1>

NMP (19.2 g) and [1a] (12.5 g) were added to a polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained by the synthesis method of Synthesis Example 1, and stirred at 25 ° C. The composition of the hour (1). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (1) was also used as the liquid crystal alignment treatment agent (1) for evaluation.

Using the obtained composition (1) or the liquid crystal alignment treatment agent (1), the unit was produced under the above conditions and various evaluations were carried out.

<Example 2>

NMP (22.5 g) was added to the polyimine powder (2) (2.50 g) obtained by the synthesis method of Synthesis Example 2, and the mixture was stirred at 70 ° C for 24 hours to dissolve. [1a] (8.30 g) and BCS (8.30 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (2). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (2) was also used as the liquid crystal alignment treatment agent (2) for evaluation.

Using the obtained composition (2) or the liquid crystal alignment treatment agent (2), the unit was produced under the above conditions and various evaluations were carried out.

<Example 3>

NEP (20.4 g) was added to the polyimine powder (2) (2.50 g) obtained by the synthesis method of Synthesis Example 2, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (14.6 g) and BCS (4.20 g) were added to the solution. The composition (3) was obtained by stirring at 50 ° C for 10 hours. No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (3) was also used as the liquid crystal alignment treatment agent (3) for evaluation.

Using the obtained composition (3) or the liquid crystal alignment treatment agent (3), the unit was produced under the above conditions and various evaluations were carried out.

<Example 4>

NEP (22.8 g) was added to the polyimine powder (2) (1.55 g) obtained by the synthesis method of Synthesis Example 2, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (15.5 g) and BCS (4.40 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (4). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (4) was used as a liquid crystal alignment treatment agent (4) for evaluation.

Using the obtained liquid crystal alignment treatment agent (4), "evaluation of inkjet printing coatability of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 5>

NMP (17.9 g) and [1a] (15.3 g) were added to a polyamic acid solution (3) (10.5 g) having a resin solid content concentration of 25.0% by mass obtained by the synthesis method of Synthesis Example 3, and stirred at 25 ° C. The composition of the hour (5). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (5) was also used as a liquid crystal alignment treatment agent (5) for evaluation.

Using the obtained composition (5) or liquid crystal alignment treatment agent (5), The above conditions are produced by the unit and various evaluations are performed.

<Example 6>

NMP (20.7 g) was added to the polyimine powder (4) (2.54 g) obtained by the synthesis method of Synthesis Example 4, and the solution was stirred at 70 ° C for 24 hours. [1a] (19.1 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (6). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (6) was also used as a liquid crystal alignment treatment agent (6) for evaluation.

Using the obtained composition (6) or the liquid crystal alignment treatment agent (6), the unit was produced under the above conditions and various evaluations were carried out.

<Example 7>

NMP (16.3 g) was added to the polyimine powder (4) (2.50 g) obtained by the synthesis method of Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (8.30 g) and BCS (14.6 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (7). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (7) was also used as a liquid crystal alignment treatment agent (7) for evaluation.

Using the obtained composition (7) or the liquid crystal alignment treatment agent (7), the unit was produced under the above conditions and various evaluations were carried out.

<Example 8>

Addition of NEP (16.6 g) to the synthesis method of Synthesis Example 4 The quinone imine powder (4) (2.55 g) was stirred at 70 ° C for 24 hours to be dissolved. [1a] (6.40 g) and BCS (17.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (8). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (8) was also used as a liquid crystal alignment treatment agent (8) for evaluation.

Using the obtained composition (8) or the liquid crystal alignment treatment agent (8), the unit was produced under the above conditions and various evaluations were carried out.

<Example 9>

NMP (4.90 g) and NEP (12.9 g) were added to the polyimine powder (4) (1.50 g) obtained by the synthesis method of Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (6.40 g) and BCS (17.1 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (9). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (9) was used as a liquid crystal alignment treatment agent (9) for evaluation.

Using the obtained liquid crystal alignment treatment agent (9), "evaluation of inkjet printing coatability of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 10>

NMP (20.8 g) was added to the polyimine powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (12.8 g) and BCS (6.40 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (10). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Again, the composition (10) It is also used as a liquid crystal alignment treatment agent (10) for evaluation.

Using the obtained composition (10) or the liquid crystal alignment treatment agent (10), the unit was produced under the above conditions and various evaluations were carried out.

<Example 11>

NMP (14.5 g) and NEP (8.50 g) were added to the polyimine powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (12.8 g) and BCS (4.30 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (11). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (11) was also used as a liquid crystal alignment treatment agent (11) for evaluation.

Using the obtained composition (11) or liquid crystal alignment treatment agent (11), the unit was produced under the above conditions and various evaluations were carried out.

<Example 12>

NMP (16.2 g) and NEP (8.90 g) were added to the polyimine powder (5) (1.55 g) obtained by the synthesis method of Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (13.3 g) and BCS (4.40 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (12). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (12) was used as a liquid crystal alignment treatment agent (12) for evaluation.

Using the obtained liquid crystal alignment treatment agent (12), under the above conditions "Evaluation of inkjet printing coatability of liquid crystal alignment agent".

<Example 13>

NMP (20.8 g) was added to the polyimine powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (8.50 g), BCS (8.50 g) and MC (2.10 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (13). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (13) was also used as a liquid crystal alignment treatment agent (13) for evaluation.

Using the obtained composition (13) or the liquid crystal alignment treatment agent (13), the unit was produced under the above conditions and various evaluations were carried out.

<Example 14>

NMP (23.0 g) was added to the polyimine powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (6.40 g), BCS (8.50 g) and EC (2.10 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (14). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (14) was also used as a liquid crystal alignment treatment agent (14) for evaluation.

Using the obtained composition (14) or the liquid crystal alignment treatment agent (14), the unit was produced under the above conditions and various evaluations were carried out.

<Example 15>

NMP (21.0 g) was added to the polyimine powder (6) (2.57 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (12.9 g) and BCS (6.40 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (15). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (15) was also used as a liquid crystal alignment treatment agent (15) for evaluation.

Using the obtained composition (15) or the liquid crystal alignment treatment agent (15), the unit was produced under the above conditions and various evaluations were carried out.

<Example 16>

NEP (16.4 g) was added to the polyimine powder (6) (2.53 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (4.20 g) and BCS (19.0 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (16). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (16) was also used as a liquid crystal alignment treatment agent (16) for evaluation.

Using the obtained composition (16) or liquid crystal alignment treatment agent (16), the unit was produced under the above conditions and various evaluations were carried out.

<Example 17>

NMP (14.5 g) and NEP (8.50 g) were added to the polyimine powder (6) (2.55 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (4.30g) and BCS (12.8g) The solution was added to the solution and stirred at 50 ° C for 10 hours to obtain a composition (17). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (17) was also used as a liquid crystal alignment treatment agent (17) for evaluation.

Using the obtained composition (17) or liquid crystal alignment treatment agent (17), the unit was produced under the above conditions and various evaluations were carried out.

<Example 18>

NMP (13.5 g) and NEP (8.60 g) were added to the polyimine powder (6) (1.50 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (10.7 g) and BCS (8.60 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (18). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (18) was used as a liquid crystal alignment treatment agent (18) for evaluation.

Using the obtained liquid crystal alignment treatment agent (18), "evaluation of inkjet printing coatability of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 19>

γ-BL (16.6 g) was added to the polyimine powder (7) (2.55 g) obtained by the synthesis method of Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (8.50 g) and BCS (14.9 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (19). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Again, the composition (19) It is also used as a liquid crystal alignment treatment agent (19) for evaluation.

Using the obtained composition (19) or liquid crystal alignment treatment agent (19), the unit was produced under the above conditions and various evaluations were carried out.

<Example 20>

NMP (14.5 g) and γ-BL (2.10 g) were added to the polyimine powder (7) (2.56 g) obtained by the synthesis method of Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (6.40 g) and BCS (17.1 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (20). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (20) was also used as a liquid crystal alignment treatment agent (20) for evaluation.

Using the obtained composition (20) or liquid crystal alignment treatment agent (20), the unit was produced under the above conditions and various evaluations were carried out.

<Example 21>

NMP (20.8 g) was added to the polyimine powder (7) (2.55 g) obtained by the synthesis method of Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (12.8 g) and BCS (6.40 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (21). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (21) was also used as a liquid crystal alignment treatment agent (21) for evaluation.

Using the obtained composition (21) or liquid crystal alignment treatment agent (21), the unit was produced under the above conditions and various evaluations were carried out.

<Example 22>

NMP (20.8 g) was added to the polyimine powder (7) (2.55 g) obtained by the synthesis method of Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (19.1 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (22). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (22) was also used as a liquid crystal alignment treatment agent (22) for evaluation.

Using the obtained composition (22) or liquid crystal alignment treatment agent (22), the unit was produced under the above conditions and various evaluations were carried out.

<Example 23>

NMP (22.5 g) was added to the polyimine powder (8) (2.50 g) obtained by the synthesis method of Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (8.30 g) and BCS (8.30 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (23). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (23) was also used as a liquid crystal alignment treatment agent (23) for evaluation.

Using the obtained composition (23) or liquid crystal alignment treatment agent (23), the unit was produced under the above conditions and various evaluations were carried out.

<Example 24>

NMP (12.2 g) and NEP (8.40 g) were added to the polyimine powder (8) (2.52 g) obtained by the synthesis method of Synthesis Example 8, and stirred at 70 ° C. Mix for 24 hours to dissolve. [1a] (10.5 g) and BCS (8.40 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (24). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (24) was also used as a liquid crystal alignment treatment agent (24) for evaluation.

Using the obtained composition (24) or liquid crystal alignment treatment agent (24), the unit was produced under the above conditions and various evaluations were carried out.

<Example 25>

NMP (20.7 g) was added to the polyimine powder (9) (2.54 g) obtained by the synthesis method of Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (10.6 g) and BCS (8.50 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (25). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (25) was also used as a liquid crystal alignment treatment agent (25) for evaluation.

Using the obtained composition (25) or the liquid crystal alignment treatment agent (25), the unit was produced under the above conditions and various evaluations were carried out.

<Example 26>

NMP (5.90 g) and NEP (12.8 g) were added to the polyimine powder (9) (2.55 g) obtained by the synthesis method of Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (10.6 g) and BCS (10.6 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (26). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (26) was also used as a liquid crystal alignment treatment agent (26) for evaluation.

Using the obtained composition (26) or liquid crystal alignment treatment agent (26), the unit was produced under the above conditions and various evaluations were carried out.

<Example 27>

NMP (11.4 g) and NEP (12.9 g) were added to the polyimine powder (9) (1.50 g) obtained by the synthesis method of Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (8.60 g) and BCS (8.60 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (27). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (27) was used as a liquid crystal alignment treatment agent (27) for evaluation.

Using the obtained liquid crystal alignment treatment agent (27), "evaluation of inkjet printing coatability of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 28>

NEP (16.3 g) was added to the polyimine powder (10) (2.50 g) obtained by the synthesis method of Synthesis Example 10, and stirred at 70 ° C for 24 hours to dissolve [1a] (6.30 g) and BCS ( 16.7 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (28). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (28) was also used as a liquid crystal alignment treatment agent (28) for evaluation.

Using the obtained composition (28) or liquid crystal alignment treatment agent (28), The unit was fabricated under the above conditions and various evaluations were performed.

<Example 29>

NMP (18.7 g) was added to the polyimine powder (10) (2.55 g) obtained by the synthesis method of Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (10.6 g) and BCS (10.6 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (29). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (29) was also used as a liquid crystal alignment treatment agent (29) for evaluation.

Using the obtained composition (29) or liquid crystal alignment treatment agent (29), the unit was produced under the above conditions and various evaluations were carried out.

<Example 30>

NMP (23.0 g) was added to the polyimine powder (11) (2.56 g) obtained by the synthesis method of Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (8.50 g) and MC (8.50 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (30). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (30) was also used as a liquid crystal alignment treatment agent (30) for evaluation.

Using the obtained composition (30) or liquid crystal alignment treatment agent (30), the unit was produced under the above conditions and various evaluations were carried out.

<Example 31>

Addition of NEP (16.6 g) to the synthesis method of Synthesis Example 11 The quinone imine powder (11) (2.55 g) was stirred at 70 ° C for 24 hours to be dissolved. [1a] (17.0 g) and BCS (6.40 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (31). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (31) was also used as a liquid crystal alignment treatment agent (31) for evaluation.

Using the obtained composition (31) or the liquid crystal alignment treatment agent (31), the unit was produced under the above conditions and various evaluations were carried out.

<Example 32>

NEP (16.6 g) and γ-BL (2.10 g) were added to the polyimine powder (11) (2.55 g) obtained by the synthesis method of Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (12.8 g) and BCS (8.50 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (32). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (32) was also used for evaluation as a liquid crystal alignment treatment agent (32).

Using the obtained composition (32) or liquid crystal alignment treatment agent (32), the unit was produced under the above conditions and various evaluations were carried out.

<Example 33>

NMP (22.5 g) was added to the polyimine powder (12) (2.50 g) obtained by the synthesis method of Synthesis Example 12, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (14.6 g) and EC (2.10 g) were added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (33). The composition was not found to be mixed An abnormality such as turbidity or precipitation was confirmed as a homogeneous solution. Further, this composition (33) was also used as a liquid crystal alignment treatment agent (33) for evaluation.

Using the obtained composition (33) and the liquid crystal alignment treatment agent (33), various evaluations were carried out under the above conditions.

<Example 34>

NEP (18.7 g) was added to the polyimine powder (12) (2.55 g) obtained by the synthesis method of Synthesis Example 12, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. [1a] (21.3 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (34). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (34) was also used as a liquid crystal alignment treatment agent (34) for evaluation.

Using the obtained composition (34) or liquid crystal alignment treatment agent (34), the unit was produced under the above conditions and various evaluations were carried out.

<Comparative Example 1>

NMP (19.2 g) and BCS (12.5 g) were added to a polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25.0% by mass obtained by the synthesis method of Synthesis Example 1, and stirred at 25 ° C for 2 hours. Composition (35). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (35) was also used as a liquid crystal alignment treatment agent (35) for evaluation.

Using the obtained composition (35) or liquid crystal alignment treatment agent (35), the unit was produced under the above conditions and various evaluations were carried out.

<Comparative Example 2>

NMP (22.5 g) was added to the polyimine powder (2) (2.50 g) obtained by the synthesis method of Synthesis Example 2, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (16.7 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (36). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (36) was also used as a liquid crystal alignment treatment agent (36) for evaluation.

Using the obtained composition (36) or liquid crystal alignment treatment agent (36), the unit was produced under the above conditions and various evaluations were carried out.

<Comparative Example 3>

NMP (17.2 g) and BCS (14.7 g) were added to a polyamic acid solution (3) (10.1 g) having a resin solid content concentration of 25.0% by mass obtained by the synthesis method of Synthesis Example 3, and stirred at 25 ° C for 2 hours. Composition (37). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (37) was also used as a liquid crystal alignment treatment agent (37) for evaluation.

Using the obtained composition (37) or liquid crystal alignment treatment agent (37), the unit was produced under the above conditions and various evaluations were carried out.

<Comparative Example 4>

NMP (20.6 g) was added to the polyimine powder (4) (2.52 g) obtained by the synthesis method of Synthesis Example 4, and stirred at 70 ° C for 24 hours to dissolve. solution. BCS (18.9 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (38). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (38) was also used as a liquid crystal alignment treatment agent (38) for evaluation.

Using the obtained composition (38) or liquid crystal alignment treatment agent (38), the unit was produced under the above conditions and various evaluations were carried out.

<Comparative Example 5>

NMP (20.4 g) was added to the polyimine powder (5) (2.50 g) obtained by the synthesis method of Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (18.8 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (39). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (39) was also used as a liquid crystal alignment treatment agent (39) for evaluation.

Using the obtained composition (39) or liquid crystal alignment treatment agent (39), the unit was produced under the above conditions and various evaluations were carried out.

<Comparative Example 6>

NMP (20.8 g) was added to the polyimine powder (6) (2.55 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (19.1 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (40). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (40) was also used as a liquid crystal alignment treatment agent (40) for evaluation.

Using the obtained composition (40) or liquid crystal alignment treatment agent (40), the unit was produced under the above conditions and various evaluations were carried out.

<Comparative Example 7>

γ-BL (16.4 g) was added to the polyimine powder (7) (2.53 g) obtained by the synthesis method of Synthesis Example 7, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (23.2 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (41). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, this composition (41) was also used as a liquid crystal alignment treatment agent (41) for evaluation.

Using the obtained composition (41) or liquid crystal alignment treatment agent (41), the unit was produced under the above conditions and various evaluations were carried out.

<Comparative Example 8>

NMP (18.3 g) was added to the polyimine powder (10) (2.50 g) obtained by the synthesis method of Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (20.8 g) was added to the solution, and the mixture was stirred at 50 ° C for 10 hours to obtain a composition (42). No abnormality such as turbidity or precipitation was observed in the composition, and it was confirmed to be a homogeneous solution. Further, the composition (42) was also used as a liquid crystal alignment treatment agent (42) for evaluation.

Using the obtained composition (42) or liquid crystal alignment treatment agent (42), the unit was produced under the above conditions and various evaluations were carried out.

The evaluation results obtained in the examples and comparative examples are combined as shown in Tables 5 to 10.

From the above results, it was found that when the polyimide film obtained from the composition of the present invention was compared with the polyimide film obtained from the composition of the comparative example, uniform coating property of pinholes did not occur. Further, the linearity of the end portion of the formed polyimide film can be improved, and the end portion of the polyimide film can be reduced.

Further, the same results were obtained from the liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent of the composition of the present invention. In particular, by using a liquid crystal alignment agent obtained from a polyamine or a solvent-soluble polyimine obtained by a branched diamine compound, the linearity of the end portion of the polyimide film can be improved as described above. The end of the polyimide film is raised.

For the results of the printability evaluation using the composition of the same polylysine or polyimine, the comparative example containing the specific solvent of the present invention and the comparative example containing no specific solvent were compared, and the comparative example containing no specific solvent was The polyimine film will generate more pinholes, reduce the linearity of the end of the polyimide film, and increase the end bulge of the polyimide film.

Specifically, Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 5 and Comparative Example 3, Example 6 and Comparative Example 4, Example 10 and Comparative Example 5, Example 15 and Comparative Example 6 Example 19 was compared with Comparative Example 7, and Example 29 and Comparative Example 8.

Further, as a result of performing liquid crystal alignment evaluation on a liquid crystal cell using a liquid crystal alignment treatment agent using the same polyaminic acid or polyimine, a comparison example of the specific solvent-containing embodiment of the present invention and a specific solvent-free example was compared. Comparative examples containing no specific solvent may cause more alignment defects due to pinholes.

Specifically, Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 5 and Comparative Example 3, Example 6 and Comparative Example 4, Example 10 and Comparative Example 5, Example 15 and Comparative Example 6 Example 19 was compared with Comparative Example 7, and Example 29 and Comparative Example 8.

Further, as a result of pre-tilt evaluation of the liquid crystal cell, the liquid crystal alignment treatment agent having a specific branched structure of the present invention and the liquid crystal alignment treatment agent having no specific branched structure are compared, and the liquid crystal alignment treatment agent having no specific branched structure is contained. The pretilt angle stability is low, that is, the change with respect to heating or ultraviolet rays is large.

Specifically, Example 8 is compared with Example 28.

Industrial use possibility

The composition of the present invention has a uniform coating property in which pinholes do not occur, and a polyimine film having a high linearity at the end portion and a small amount of end bulging can be formed. Further, the liquid crystal alignment treatment agent using the composition of the present invention in the same manner also has uniform coating property without pinholes, and the linearity of the end portion can be formed high, and the end portion can be raised less, and the needle does not occur. The liquid crystal alignment film of the alignment of the holes.

In other words, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention has excellent reliability and is suitable for a high-definition liquid crystal television of a large screen, and is suitable for a TN element, an STN element, or a TFT liquid crystal. Components, especially vertical alignment type liquid crystal display elements.

Further, when a liquid crystal display element is produced by using a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention, a liquid crystal display is required to be irradiated with ultraviolet rays. The components are also suitable.

In addition, the entire contents of the specification, the patent application, the drawings and the abstract of the Japanese Patent Application No. 2012-035918, filed on Feb. 22, 2012, are hereby incorporated by reference.

Claims (16)

A liquid crystal alignment treatment agent comprising the following component (A) and component (B), wherein component (A) is 5 to 70% by mass of the solvent contained in the liquid crystal alignment treatment agent, and component (B) is 0.1. To 30% by mass, the component (A): a solvent represented by the following formula [1], (In the formula [1], X ₁ represents an alkyl group having 1 to 3 carbon atoms), and the component (B): a branched diamine compound represented by the following formula [2] is used as a part of a raw material. a polymer of at least one selected from the group consisting of a precursor and a polyimine precursor obtained by quinone imidization of a polyimine. (In the formula [2], Y ₁ is a single chain, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number 12 to 25 having a nest skeleton The divalent organic group, any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or carbon a fluorine-containing alkoxy group or a fluorine atom substituted by 1 to 3; Y ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a hetero ring, and the cyclic groups are Any hydrogen atom may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine. Atom substituted; n is an integer from 0 to 4; Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a carbon number of 1 to 18 Fluorinated alkoxy). The liquid crystal alignment treatment agent of the first aspect of the invention, wherein the branched diamine compound represented by the formula [2] is a diamine compound represented by the following formula [2a], (In the formula [2a], Y ₁ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₂ Is a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15); Y ₃ is a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-; Y ₄ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number 12 to 25 having a nest skeleton The divalent organic group, any hydrogen atom on the above cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or carbon a fluorine-containing alkoxy group or a fluorine atom substituted by 1 to 3; Y ₅ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and the cyclic groups are Any hydrogen atom may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine. Atom substituted; n is an integer from 0 to 4; Y ₆ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a carbon number of 1 to 18 Fluorinated alkoxy; m is an integer from 1 to 4. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the branched diamine compound represented by the formula [2] or the diamine compound represented by the formula [2a] is 5 of the diamine component. Up to 80% by mole. The liquid crystal alignment treatment agent of the third aspect of the invention, wherein the component (B) is a polymer containing a tetracarboxylic dianhydride component of a tetracarboxylic dianhydride represented by the following formula [3], (In the formula [3], Z _{1 is} a structure of at least one selected from the group consisting of the following formulas [3a] to [3j]) (In the formula [3a], Z ₂ to Z ₅ are a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different. In the formula [3g], Z ₆ and Z ₇ are a hydrogen atom or a methyl group. Can be the same or different). A liquid crystal alignment treatment agent according to claim 1 or 2, which comprises component (C), which is grouped by N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. At least one solvent selected. The liquid crystal alignment treatment agent of claim 5, which comprises the component (D), which is composed of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl A solvent selected from the group consisting of ether, propylene glycol monoethyl ether, and propylene glycol monobutyl ether. The liquid crystal alignment treatment agent according to claim 1 or 2, wherein the component (A) is 5 to 60% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. The liquid crystal alignment treatment agent according to claim 5, wherein the component (C) is a solvent of the liquid crystal alignment treatment agent 80% by mass. The liquid crystal alignment treatment agent of the sixth aspect of the invention, wherein the component (D) is from 1 to 50% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. 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 alignment film obtained by an inkjet printing method using a liquid crystal alignment treatment agent according to any one of claims 1 to 9. A liquid crystal display element which is a liquid crystal alignment film having a 10th or 11th aspect of the patent application. The liquid crystal alignment element according to claim 10 or 11, which is used for a liquid crystal display element having a liquid crystal layer between a pair of electrodes provided with electrodes, and the arrangement between the pair of substrates is included A liquid crystal composition of a polymerizable compound polymerized by at least one of an active energy ray and a heat is produced by a step of polymerizing the polymerizable compound while applying a voltage between the electrodes. A liquid crystal display element which is a liquid crystal alignment film having a thirteenth aspect of the patent application. The liquid crystal alignment element according to claim 10 or 11, which is used for a liquid crystal display element having a liquid crystal layer between a pair of electrodes provided with electrodes, and the arrangement between the pair of substrates is included A liquid crystal alignment film of a polymerizable group polymerized by at least one of an active energy ray and a heat is applied to the electrode while applying a voltage therebetween Manufactured by the step of synthesizing the base. A liquid crystal display element which is a liquid crystal alignment film having a fifteenth item of the patent application.