KR102512108B1 - Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The liquid-crystal aligning agent containing the following (A) component and (B) component.
(A) Component: Heteropoly acid.
(B) Component: Polymer.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNMENT TREATMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT}

This invention relates to the liquid crystal display element using the liquid crystal aligning agent used in manufacture of a liquid crystal display element, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and this liquid crystal aligning film.

BACKGROUND OF THE INVENTION A liquid crystal display element is currently widely used as a display device that realizes a thin shape and a light weight. Usually, a liquid crystal alignment film is used for this liquid crystal display element in order to determine the orientation state of a liquid crystal.

With the high definition of a liquid crystal display element, it is calculated|required that voltage retention is high also in the liquid crystal aligning film used there from a viewpoint of suppression of the contrast fall of a liquid crystal display element, and reduction of an afterimage phenomenon. In contrast to these, compounds containing one carboxylic acid group in the molecule, compounds containing one carboxylic acid anhydride group in the molecule, and compounds containing one tertiary amino group in the molecule, in addition to polyamic acid or its imidized polymer, etc. What used the liquid-crystal aligning agent containing a very small amount of the compound chosen from (for example, refer patent document 1) is known.

Moreover, suppression of the display defect accompanying the contrast fall of a liquid crystal display element and long-term use is calculated|required with high definition of a liquid crystal display element. Regarding these, a liquid crystal aligning film using a liquid crystal aligning agent to which an alkoxysilane compound is added has been proposed as a technique for improving the liquid crystal orientation and making display defects less likely to occur in the periphery of a liquid crystal display screen in a liquid crystal alignment film using polyimide. There is (for example, refer to patent document 2 or patent document 3).

Japanese Unexamined Patent Publication No. 8-76128 Japanese Unexamined Patent Publication No. 61-171762 Japanese Unexamined Patent Publication No. 11-119226

BACKGROUND ART With recent high performance of liquid crystal display elements, liquid crystal display elements are used for large-screen, high-definition liquid crystal televisions and in-vehicle applications, such as car navigation systems and meter panels. In such applications, a backlight having a large calorific value is sometimes used to obtain high luminance. For this reason, high reliability from another viewpoint, ie, high stability with respect to the light from a backlight, was requested|required of the liquid crystal aligning film. In particular, when the voltage retention, which is one of the electrical characteristics of the liquid crystal display element, is lowered by light irradiation from the backlight, burn-in defect (also referred to as wire burn-in), which is one of the display defects of the liquid crystal display element, is likely to occur. A highly reliable liquid crystal display element cannot be obtained. Therefore, in a liquid crystal aligning film, it is calculated|required that voltage retention does not fall easily, for example, even after being exposed to irradiation of light for a long time, in addition to having good initial stage characteristics.

In addition, in mobile applications such as smart phones and mobile phones, the use environment has become harsher than before. That is, in addition to the conventional environment of room temperature and low humidity, there are cases where it is used under high temperature and high humidity. In use under such high-temperature, high-humidity conditions, there is a problem that water tends to mix between the sealant of the liquid crystal display element and the liquid crystal aligning film, and display nonuniformity easily occurs near the frame of the liquid crystal display element. Therefore, it is required that such display defects do not occur even under conditions of high temperature and high humidity.

Then, this invention aims at providing the liquid crystal aligning film which had said characteristic. That is, the objective of this invention aims at providing the liquid crystal aligning film which can suppress the fall of voltage retention even after being exposed to irradiation of light for a long time. Furthermore, it aims at providing the liquid crystal aligning film in which a display nonuniformity does not generate|occur|produce in frame vicinity of a liquid crystal display element also on high temperature, high humidity conditions.

Furthermore, it also aims at providing the liquid-crystal aligning agent which can provide the liquid crystal display element which has said liquid crystal aligning film, said liquid crystal aligning film, and the composition used for this liquid-crystal aligning agent.

As a result of earnest research, this inventor discovered that the liquid-crystal aligning agent containing the compound and polymer of a specific structure was very effective in order to achieve the said objective, and came to complete this invention.

That is, this invention has the following summary.

(1) The liquid-crystal aligning agent containing the following (A) component and (B) component.

(A) Component: Heteropoly acid.

(B) Component: Polymer.

(2) The liquid crystal aligning agent as described in said (1) whose said heteropoly acid is at least 1 sort(s) chosen from the group which consists of phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid.

(3) The liquid-crystal aligning agent as described in said (1) or said (2) in which the said polymer has a nitrogen-containing aromatic heterocyclic ring.

(4) The above ( 1) - The liquid-crystal aligning agent as described in any one of said (3).

(5) The liquid-crystal aligning agent as described in said (4) whose said polymer is the polyimide which imidated the polyimide precursor obtained by reaction of a diamine component and a tetracarboxylic acid component, or this polyimide precursor.

(6) The liquid-crystal aligning agent as described in said (5) containing the diamine compound which the said diamine component has a structure represented by following formula [2].

[Formula 1]

(W ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- and -N(CH represents at least one bonding group selected from the group consisting of ₃ )CO- W ² represents at least one bonding group selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring, and an aromatic ring; W ³ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ ) CO- and -O(CH ₂ ) _m - (m represents an integer of 1 to 5. At least one member selected from the group consisting of W ⁴ represents a nitrogen-containing aromatic heterocycle.)

(7) The liquid-crystal aligning agent as described in said (6) in which the said diamine component contains the diamine compound represented by following formula [2a].

[Formula 2]

(W represents the structure represented by the said formula [2]. m1 represents the integer of 1-4.)

(8) Liquid-crystal aligning agent as described in any one of said (5) - said (7) in which the said diamine component contains the diamine compound which has a structure represented by following formula [3-1] or formula [3-2] .

[Formula 3]

(Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )- represents at least one bonding group selected from the group consisting of -N(CH ₃ )CO-, -COO- and -OCO- Y ² is a single bond or -(CH ₂ ) _b - (b is 1 to 15 Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- Y ⁴ is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton. group, and any hydrogen atom on the cyclic group is substituted with an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom. Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkyl group of 1 to 3 carbon atoms, It may be substituted with an alkoxyl group of 3, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom. n represents an integer of 0 to 4. Y ⁶ is an alkyl group of 1 to 18 carbon atoms , at least one selected from the group consisting of an alkenyl group of 2 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxyl group of 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group of 1 to 18 carbon atoms.)

[Formula 4]

(Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represents at least one bonding group selected from the group consisting of Y ⁸ represents an alkyl group having 8 to 18 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.)

(9) The liquid-crystal aligning agent as described in said (8) in which the said diamine compound is represented by following formula [3a].

[Formula 5]

(Y represents the structure represented by the said formula [3-1] or formula [3-2]. n1 represents the integer of 1-4.)

(10) The liquid-crystal aligning agent in any one of said (5) - said (9) in which the said tetracarboxylic-acid component contains tetracarboxylic dianhydride represented by following formula [4].

[Formula 6]

(Z represents at least one structure selected from the group consisting of structures represented by the following formulas [4a] to formula [4k].)

[Formula 7]

(Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. )

(11) The liquid crystal aligning agent contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone ( 1) - The liquid-crystal aligning agent as described in any one of said (10).

(12) The liquid crystal aligning agent is 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and The liquid-crystal aligning agent in any one of said (1) - said (11) containing at least 1 sort(s) of solvent chosen from the group which consists of solvents represented by following formula [D1] - formula [D3].

[Formula 8]

(D ¹ represents an alkyl group of 1 to 3 carbon atoms. D ² represents an alkyl group of 1 to 3 carbon atoms. D ³ represents an alkyl group of 1 to 4 carbon atoms.)

(13) The liquid crystal aligning agent is selected from the group consisting of a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and an alkoxyalkyl group having 1 to 3 carbon atoms Liquid-crystal aligning agent in any one of said (1) - said (12) containing the crosslinkable compound which becomes, or the crosslinkable compound which has a polymerizable unsaturated bond group.

(14) The liquid crystal aligning film obtained from the liquid-crystal aligning agent in any one of said (1) - said (13).

(15) The liquid crystal aligning film obtained by apply|coating the liquid-crystal aligning agent of any one of said (1) - said (13) by the inkjet method.

(16) The liquid crystal display element which has the liquid crystal aligning film as described in said (14) or said (15).

(17) A liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between a pair of substrates provided with electrodes and having a liquid crystal layer, between the pair of substrates, , The liquid crystal aligning film according to the above (14) or (15), characterized in that it is used for a liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(18) The liquid crystal display element characterized by having the liquid crystal aligning film as described in said (17).

(19) A liquid crystal alignment film comprising a polymerizable group polymerizable by at least one of active energy rays and heat is disposed between a pair of substrates with electrodes and having a liquid crystal layer between the pair of substrates, The liquid crystal aligning film according to the above (14) or (15), characterized in that it is used for a liquid crystal display element manufactured through a step of polymerizing the polymerizable group while applying a voltage between the electrodes.

(20) The liquid crystal display element characterized by having the liquid crystal aligning film as described in said (19).

Even after the liquid-crystal aligning agent containing the specific compound and polymer of this invention is exposed to irradiation of light for a long time, it can obtain the liquid crystal aligning film which can suppress the fall of voltage retention. Furthermore, it becomes a liquid crystal aligning film in which a display nonuniformity does not generate|occur|produce in frame vicinity of a liquid crystal display element also on high temperature, high humidity conditions.

The mechanism why the liquid crystal display element having the above excellent characteristics is obtained by the present invention is not necessarily clear, but is estimated as follows.

This invention relates to the liquid-crystal aligning agent containing the following (A) component and (B) component, the liquid-crystal aligning film obtained using this liquid-crystal aligning agent, and also the liquid crystal display element which has this liquid-crystal aligning film.

(A) Component: Heteropolyacid (also referred to as a specific compound).

(B) Component: Polymer.

As an effect of a specific compound, the following can be considered. As one of the factors for lowering the voltage retention, there may be a large amount of ionic impurity components in the liquid crystal. On the other hand, when the liquid crystal display element is exposed to light irradiation for a long time and decomposition of the liquid crystal occurs, it is thought that the specific compound adsorbs the ionic impurity component generated at that time to suppress the decrease in voltage retention. Moreover, when the polymer which has a nitrogen-containing aromatic heterocycle is used, it is also thought that this heterocycle can further heighten the effect.

Moreover, the polyimide precursor obtained by reaction of the diamine component and the tetracarboxylic acid component or the polyimide obtained by imidating the polyimide precursor is used for the polymer, and the diamine component at that time is of the formula [3-1] or When using a diamine compound having a structure represented by formula [3-2] as a liquid crystal aligning agent for a liquid crystal display element of vertical type (VA: Vertical Alignment) mode, PSA (Polymer Sustained Alignment) mode and SC-PVA mode In particular, since the structure represented by formula [3-1] shows a rigid structure, the liquid crystal display element using the liquid crystal aligning film which has this structure is stable with respect to light, such as an ultraviolet-ray, and is ionic which reduces voltage retention. The generation of impurities can be suppressed.

In this way, the liquid crystal display element provided with the liquid crystal aligning film obtained from the liquid-crystal aligning agent in this invention becomes a thing excellent in reliability, and can be used suitably for a large-screen, high-definition liquid crystal television etc. In particular, when manufacturing a liquid crystal display element, it is useful with respect to a liquid crystal display element using a PSA mode or SC-PVA mode for irradiating high-energy ultraviolet rays.

<specific compound>

The specific compound in this invention is a heteropoly acid.

Heteropolyacid has a structure in which a heteroatom is located at the center of a molecule, typically represented by a Keggin-type chemical structure represented by the following formula [1-1] or a Dawson-type chemical structure represented by the formula [1-2], and contains vanadium ( V), molybdenum (Mo), tungsten (W) is a polyacid formed by the condensation of isopolyacid, which is an oxygen acid, and an oxygen acid of a different element. Examples of oxyacids of such heterogeneous elements include oxyacids of silicon (Si), phosphorus (P), and arsenic (As).

[Formula 9]

Specific examples of the heteropoly acid compound include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid, and it is preferable to use these in the present invention. Moreover, these may be used independently and may be used in combination of 2 or more types. In addition, the heteropolyacid compound in this invention can be obtained as a commercial item, and can also be synthesize|combined by a well-known method.

In quantitative analysis such as elemental analysis, even if the number of elements is large or small from the structure represented by the general formula, as long as it is obtained as a commercial product or appropriately synthesized according to a known synthesis method, the present heteropoly acid can be used in the invention.

That is, for example, in general, phosphotungstic acid is a structure represented by the following formula [1a], and phosphomolybdic acid is a structure represented by the formula [1b].

[Formula 10]

In quantitative analysis, even if the number of P (phosphorus), O (oxygen), W (tungsten), or Mo (molybdenum) in these formulas is large or small, they are obtained as commercially available products, or known As long as it is synthesized appropriately according to the synthesis method, it can be used in the present invention. In this case, the mass of the heteropoly acid defined in the present invention is not the mass of pure phosphotungstic acid (phosphotungstic acid content) in a compound or commercial product, but in a form available as a commercial product and in a form that can be isolated by a known synthetic method. , the total mass in a state including water of hydration and other impurities.

<Polymer>

The polymer in the present invention is at least one selected from the group consisting of acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses, and polysiloxanes. It is preferably a polymer. More preferred is a polyimide precursor, polyimide or polysiloxane. Particularly preferred are polyimide precursors or polyimides (collectively, also referred to as specific polyimide-based polymers).

Moreover, as mentioned above, it is preferable to contain a nitrogen-containing aromatic heterocycle in these polymers for the purpose of further enhancing the effect of this invention.

The nitrogen-containing aromatic heterocycle is a heterocycle containing a structure represented by the following formula [a], formula [b] or formula [c].

[Formula 11]

(Wa represents an alkyl group having 1 to 5 carbon atoms.)

More specifically, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, thia Diazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, cinnoline ring, phenanthroline ring, indole ring, A quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, etc. are mentioned. Especially, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzoimidazole ring is preferable. More preferable is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring from the viewpoint of being able to suppress a decrease in voltage holding ratio after exposure to light irradiation for a long time. Especially preferred is an imidazole ring or a pyridine ring.

<Specific polyimide polymer>

When using a specific polyimide-type polymer for the polymer of this invention, it is preferable that they are a polyimide precursor or polyimide obtained by making a diamine component and a tetracarboxylic-acid component react.

A polyimide precursor has a structure represented by the following formula [A].

[Formula 12]

(R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ and A ⁴ each independently represent , a hydrogen atom, an alkyl group or an acetyl group having 1 to 5 carbon atoms nA represents a positive integer.

Examples of the diamine component include diamines having two primary or secondary amino groups in the molecule. Examples of the tetracarboxylic acid component include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.

A specific polyimide-type polymer is represented by the following formula [D] for the reason that it can be obtained relatively easily by using as raw materials tetracarboxylic dianhydride represented by the following formula [B] and diamine represented by the following formula [C]. A polyamic acid composed of the structural formula of the repeating unit shown or a polyimide obtained by imidizing the polyamic acid is preferred. Especially, in this invention, it is preferable that it is the polyimide which imidated the polyimide precursor from the point of the physical and chemical stability of a liquid crystal aligning film.

[Formula 13]

(R ¹ and R ² have the same meaning as defined in formula [A].)

[Formula 14]

(R ¹ , R ² and nA have the same meaning as defined in formula [A].)

Moreover, by a normal synthesis method, the C1-C8 alkyl group of ^A1 and ^A2 represented by formula [A], and ^A3 and ^A4 represented by formula [A] were added to the polymer of formula [D] obtained above An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

As a diamine component in this invention, a well-known thing can be used.

Especially, as mentioned above, it is preferable to use the diamine compound which has a structure represented by following formula [2] (it is also mentioned specific structure (1)) for the purpose of heightening the effect of this invention more.

[Formula 15]

In Formula [2], W ¹ , W ² , W ³ and W ⁴ are as defined above, but among them, the following are preferable.

W ¹ is preferably -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. More preferable ones are -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO- or -CON(CH ₃ )- from the viewpoint of ease of synthesis. Particularly preferred are -O-, -CONH- or -CH ₂ O-.

W ² represents at least one selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring, and an aromatic ring.

The C1-C20 alkylene group may be linear or branched. Moreover, you may have an unsaturated bond. Among them, an alkylene group having 1 to 10 carbon atoms is preferable from the viewpoint of ease of synthesis.

Specific examples of the non-aromatic ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, and a cyclododecane ring. , Cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecane acid rings, bicycloheptane rings, decahydronaphthalene rings, norbornene rings, adamantane rings, and the like. Especially, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring is preferable.

Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring and a phenalene ring. Especially, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, or an anthracene ring is preferable.

As W ² , a single bond, an alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, or a naphthalene ring. , a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring is preferred. Among them, a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring, or a benzene ring is preferable from the viewpoint of the ease of synthesis and the ability to suppress a decrease in voltage retention after exposure to light irradiation for a long time. .

W ³ is preferably a single bond, -O-, -COO-, -OCO- or -O(CH ₂ ) _m - (m represents an integer of 1 to 5). More preferable is a single bond, -O-, -OCO-, or -O(CH ₂ ) _m - (m represents an integer of 1 to 5) from the viewpoint of ease of synthesis.

W ⁴ represents a nitrogen-containing aromatic heterocyclic ring, and represents a heterocyclic ring containing a structure represented by the formula [a], formula [b] or formula [c] as described above. Specifically, as described above, among others, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or Benzoimidazole rings are preferred. More preferable is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring from the viewpoint of being able to suppress a decrease in voltage holding ratio after exposure to light irradiation for a long time. Especially preferred is an imidazole ring or a pyridine ring.

Moreover, it is preferable that W ³ in formula [2] is bonded to a substituent not adjacent to formula [a], formula [b] and formula [c] contained in W ⁴ .

Preferred combinations of W ¹ , W ² , W ³ and W ⁴ in formula [2] are as shown in Tables 1 to 31 below.

Among them, (a-43) to (a-49), (a-57) to (a-63), (a-218) to (a-224), (a-232) to (a-238) , (a-323) to (a-329), (a-337) to (a-343), (a-428) to (a-434) or a combination of (a-442) to (a-448) this is preferable More preferable is a combination of (a-44), (a-45), (a-58) or (a-59) from the viewpoint of being able to suppress the decrease in voltage retention after exposure to light irradiation for a long time. .

As a diamine compound which has a specific structure (1), it is preferable to use the diamine compound (it is also mentioned specific diamine compound (1)) represented by following formula [2a].

[Formula 16]

In formula [2a], W represents the structure represented by said formula [2].

In addition, the details and preferable combinations of W ¹ , W ² , W ³ and W ⁴ in Formula [2] are as in Formula [2] above.

As for m1, 1 is preferable from the point of synthetic|combination easiness.

1-60 mol% is preferable with respect to the whole diamine component from the point which can suppress the fall of the voltage retention after exposure to irradiation of light for a long time as for the usage ratio of a specific diamine compound (1). More preferred is 1 to 50 mol%, and particularly preferred is 5 to 50 mol%.

Moreover, specific diamine compound (1) is 1 type or 2 or more types according to characteristics, such as the solubility to the solvent of a specific polyimide type polymer, the liquid crystal orientation when it is set as a liquid crystal aligning film, or the electric property of a liquid crystal display element. Can be used in combination.

When using the liquid-crystal aligning agent of this invention for the liquid crystal display element of VA mode, PSA mode, or SC-PVA mode, the structure shown to a diamine component by following formula [3-1] or formula [3-2] It is preferable to use a diamine compound having (also referred to as specific structure (2)).

[Formula 17]

In formula [3-1], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are as defined above, but among them, the following are respectively preferred.

Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO-, from the viewpoint of the availability of raw materials and ease of synthesis. is preferable More preferable is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

Y ² is preferably a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10).

Y ³ is preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO-, from the viewpoint of ease of synthesis. More preferable is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

Y ⁴ is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of ease of synthesis.

Y ⁵ is preferably a benzene ring or a cyclohexane ring.

Y ⁶ is preferably an alkyl group of 1 to 18 carbon atoms, an alkenyl group of 2 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 10 carbon atoms, an alkoxyl group of 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group of 1 to 10 carbon atoms. More preferably, they are a C1-C12 alkyl group, a C2-C18 alkenyl group, or a C1-C12 alkoxyl group. Especially preferably, they are a C1-C9 alkyl group, a C2-C12 alkenyl group, or a C1-C9 alkoxyl group.

n is preferably from 0 to 3, more preferably from 0 to 2, from the viewpoint of the availability of raw materials and ease of synthesis.

Preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are Tables 6 to 47 on pages 13 to 34 of International Publication WO2011/132751 (published on October 27, 2011). The same combination as (2-1) to (2-629) published in . In addition, although ^Y1 - ^Y6 in this invention is shown as Y1-Y6 in each table|surface of international publication gazette, ^Y1 -Y6 shall read it as Y1- ^Y6 . In addition, in (2-605) to (2-629) published in each table of International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention is an organic group having 12 to 25 carbon atoms having a steroid skeleton Although shown as an organic group, an organic group having 12 to 25 carbon atoms having a steroid skeleton is read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.

Among them, (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 (2-483) or a combination of (2-603) to (2-615) is preferable. Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).

[Formula 18]

In formula [3-2], Y ⁷ and Y ⁸ are as defined above, but among them, the following ones are preferred.

Y ⁷ is preferably a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )- or -COO-. More preferably, it is a single bond, -O-, -CONH-, or -COO-.

Y ⁸ is preferably an alkyl group having 8 to 18 carbon atoms.

In this invention, it is preferable that specific structure (2) uses the structure represented by Formula [3-1] from the point from which the vertical alignment property of a highly stable liquid crystal can be obtained.

As a diamine compound which has a specific structure (2), it is preferable to use the diamine compound (it is also mentioned specific diamine compound (2)) represented by following formula [3a].

[Formula 19]

In formula [3a], Y represents the structure represented by said formula [3-1] or formula [3-2].

In addition, the details and preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [3-1] are the same as in the formula [3-1], and the formula [ Details and preferable combinations of Y ⁷ and Y ⁸ in [3-2] are as in the above formula [3-2].

As for n1, 1 is preferable from the point of synthetic|combination easiness.

As a specific diamine compound (2) which has a specific structure represented by formula [3-1], the diamine compound specifically represented by the following formula [3a-1] - formula [3a-31] is mentioned, for example. .

[Formula 20]

(R ¹ represents at least one bonding group selected from the group consisting of -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, and -CH ₂ OCO-, respectively. R ² is each A linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxyl group having 1 to 18 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 18 carbon atoms, or a linear or branched alkyl group having 1 to 18 carbon atoms. represents a linear or branched fluorine-containing alkoxyl group.)

[Formula 21]

(R ³ is each composed of -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - and -CH ₂ - R ⁴ represents at least one bonding group selected from the group consisting of a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxyl group having 1 to 18 carbon atoms, and a linear or branched alkoxyl group having 1 to 18 carbon atoms. represents a chain or branched fluorine-containing alkyl group or a linear or branched fluorine-containing alkoxyl group having 1 to 18 carbon atoms.)

[Formula 22]

(R ⁵ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, - Represents at least one bonding group selected from the group consisting of O- and -NH- R ⁶ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, or an acetoxy group, respectively. At least one selected from the group consisting of a period and a hydroxyl group is shown.)

[Formula 23]

(R ⁷ each represents a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomer of 1,4-cyclohexylene is the trans isomer.)

[Formula 24]

(R ⁸ represents a linear or branched alkyl group having 3 to 12 carbon atoms, respectively, and the cis-trans isomer of 1,4-cyclohexylene is the trans isomer.)

[Formula 25]

(A ₄ represents a linear or branched alkyl group having 3 to 18 carbon atoms which may be substituted with a fluorine atom. A ₃ represents a 1,4-cyclohexylene group or a 1,4-phenylene group. A ₂ represents oxygen represents an atom or -COO-* (provided that the bond attached with "*" binds to A ₃ ) A ₁ represents an oxygen atom or -COO-* (provided that the bond attached with "*" is (CH ₂ ) a ₂ ) and combined). In addition, a ₁ represents an integer of 0 or 1. a ₂ represents an integer of 2 to 10; a ₃ represents an integer of 0 or 1.)

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

Among the above formulas [3a-1] to [3a-31], preferred diamine compounds are formula [3a-1] to formula [3a-6], formula [3a-9] to formula [3a-13] or formula [ 3a-22] to formula [3a-31].

As a specific diamine compound (2) which has a specific structure (2) represented by the said formula [3-2], the diamine compound specifically represented by the following formula [3a-32] - [3a-35], for example can be heard

[Formula 31]

(A ¹ represents an alkyl group having 8 to 18 carbon atoms or a fluorine-containing alkyl group, respectively.)

As for the usage ratio of a specific diamine compound (2), 10-70 mol% is preferable with respect to the whole diamine component, especially when using for the liquid crystal display element of VA mode, PSA mode, or SC-PVA mode. More preferred is 20 to 70 mol%, and particularly preferred is 20 to 60 mol%.

Moreover, the specific diamine compound (2) is 1 type or 2 or more types according to characteristics, such as the solubility to the solvent of a specific polyimide-type polymer, the liquid-crystal orientation when it is set as a liquid crystal aligning film, or the electric property of a liquid crystal display element. Can be used in combination.

In the diamine component in this invention, said specific diamine compound (1) and specific diamine compound (2) are used for the display mode of a liquid crystal display element, ie, TN (Twisted Nematic) mode, IPS (In-plane Switching) mode , depending on VA mode, PSA mode and SC-PVA mode, it can be selected and used appropriately. Moreover, two or more types of these specific diamine compounds, ie, multiple types, can also be used.

As a diamine component for producing a specific polyimide polymer, the following diamine compounds (also referred to as other diamine compounds) can also be used. Specifically, for example, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 2,4-diaminophenol, 3,5 -Diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3 ,5-diaminobenzoic acid, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobi Phenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4, 4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2' -Diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2 ,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl ) silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodi Aniline, 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'-diamino Diphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-dia Minonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1, 8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis(4-aminophenyl)ethane , 1,2-bis (3-aminophenyl) ethane, 1,3-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(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)] Dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1 ,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone] , 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl) )methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-amino Phenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N ,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis( 4-aminophenyl)terephthalamide, N,N'-bis(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)diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-amino Phenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3 -Amino-4-methylphenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane , 1,4-bis (3-aminophenoxy) 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-bis(3-aminophenoxy)heptane, 1 ,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-amino Phenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1, 11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl ) methane, 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-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane, etc. can be heard

Moreover, as another diamine compound, the diamine compound represented by following formula [D1] - formula [DA15] can also be used.

[Formula 32]

[Formula 33]

[Formula 34]

(p represents an integer from 1 to 10.)

[Formula 35]

[Formula 36]

(L ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. n represents an integer of 1 to 5.)

[Formula 37]

Other diamine compounds can be used singly or in combination of two or more depending on properties such as solubility of a specific polyimide polymer in a solvent, liquid crystal orientation when used as a liquid crystal alignment film, or electrical properties of a liquid crystal display element. .

It is preferable to use tetracarboxylic dianhydride (it is also mentioned a specific tetracarboxylic-acid component) represented by following formula [4] for the tetracarboxylic-acid component for manufacturing a specific polyimide-type polymer.

[Formula 38]

In formula [4], Z represents at least 1 sort(s) of structure chosen from the group which consists of structures represented by said formula [4a] - formula [4k].

Z in formula [4] is the ease of synthesis and the easy polymerization reactivity at the time of producing a polymer, formula [4a], formula [4c], formula [4d], formula [4e], formula [4f ], the structure represented by formula [4g] or formula [4k] is preferable. More preferable is a structure represented by formula [4a], formula [4e], formula [4f], formula [4g] or formula [4k]. Particularly preferred is a structure represented by formula [4e], formula [4f], formula [4g] or formula [4k].

It is preferable that the usage ratio of a specific tetracarboxylic acid component is 1 mol% or more with respect to all tetracarboxylic acid components. More preferably, it is 5 mol% or more. Especially preferably, it is 10 mol% or more, and the most preferable is 10 to 90 mol% from the point which can suppress the fall of the voltage retention after exposure to light irradiation for a long time.

Moreover, when using the tetracarboxylic-acid component of the structure represented by the said formula [4e], formula [4f], formula [4g], or formula [4k], the usage-amount is 20 mol% of the whole tetracarboxylic-acid component By making it above, the desired effect is acquired. Preferably it is 30 mol% or more. Moreover, the tetracarboxylic-acid component of the structure shown by formula [4e], formula [4f], formula [4g], or formula [4k] may be sufficient as all the tetracarboxylic-acid components.

As a tetracarboxylic-acid component in this invention, other tetracarboxylic-acid components other than a specific tetracarboxylic-acid component can be used unless the effect of this invention is impaired.

Specifically, for example, pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid boxylic acid, 2,3,6,7-anthracentetracarboxylic acid, 1,2,5,6-anthracentetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2, 3,3',4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4- Dicarboxyphenyl)sulfone, 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)dimethylsilane, bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5 -Pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylsulfotetracarboxylic acid, 3,4,9,10-phenyl rylene tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid; and the like.

The specific tetracarboxylic acid component and other tetracarboxylic acid components are 1 A species or a mixture of two or more species may be used.

The method for producing a specific polyimide-based polymer is not particularly limited. Usually, it is obtained by reacting a diamine component with a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and its tetracarboxylic acid derivative is reacted with a diamine component composed of one or more diamine compounds, A method for obtaining polyamic acid is exemplified. Specifically, a method of polycondensing tetracarboxylic dianhydride and a primary or secondary diamine compound to obtain a polyamic acid, and a polyamide by subjecting tetracarboxylic acid and a primary or secondary diamine compound to a dehydration polycondensation reaction A method of obtaining an acid or a method of obtaining a polyamic acid by reacting a tetracarboxylic dihalide with a primary or secondary diamine compound is used.

To obtain polyamic acid alkyl ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, or a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and a method of reacting a primary or secondary diamine compound or a method of converting a carboxyl group of polyamic acid into an ester is used.

In order to obtain polyimide, the method of making polyimide by ring-closing the said polyamic acid or polyamic-acid alkylester is used.

Reaction of a diamine component and a tetracarboxylic acid component normally performs a diamine component and a tetracarboxylic acid component in an organic solvent. The organic solvent used in that case is not particularly limited as long as the produced polyimide precursor dissolves therein. Below, although the specific example of the organic solvent used for reaction is given, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone etc. are mentioned. Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] - formula [ D-3] can be used.

[Formula 39]

(D ¹ represents an alkyl group of 1 to 3 carbon atoms. D ² represents an alkyl group of 1 to 3 carbon atoms. D ³ represents an alkyl group of 1 to 4 carbon atoms.)

These may be used independently or may be used in mixture. In addition, even if it is a solvent that does not dissolve the polyimide precursor, you may mix it with the said solvent and use it within the range in which the produced|generated polyimide precursor does not precipitate. Further, since moisture in the organic solvent inhibits the polymerization reaction and causes hydrolysis of the resulting polyimide precursor, it is preferable to use a dehydrated and dried organic solvent.

When reacting the diamine component and the tetracarboxylic acid component in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic acid component is added as it is or added after being dispersed or dissolved in the organic solvent. method, conversely, a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent, a method of adding a diamine component and a tetracarboxylic acid component alternately, and any of these methods. You can also use Moreover, when reacting using multiple types of diamine component and tetracarboxylic acid component, respectively, you may make them react in the state which were mixed beforehand, or may make them react one by one individually, and also mix-react the low-molecular-weight substance reacted individually, and make a polymer can be done with The polymerization temperature at that time can be selected from any temperature of -20°C to 150°C, but is preferably in the range of -5°C to 100°C. In addition, although the reaction can be carried out at any concentration, when the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and when the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the polymerization reaction may be carried out at a high concentration, and then an organic solvent may be added.

In the polymerization reaction of the polyimide precursor, it is preferable that the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is 0.8 to 1.2. Similar to a normal polymerization reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of the polyimide precursor to be produced.

Polyimide is a polyimide obtained by ring closure of the above polyimide precursor, and the ring closure rate of the amic acid group (also referred to as imidization rate) does not necessarily need to be 100%, and can be arbitrarily adjusted depending on the use or purpose. Especially, it is preferable that the specific polyimide-type polymer in this invention is the polyimide which imidated the polyimide precursor. As for the imidation rate at that time, 40 to 90% are preferable. More preferable is 50 to 90%.

As a method of imidating the polyimide precursor, thermal imidation in which the solution of the polyimide precursor is heated as it is or catalyst imidation in which a catalyst is added to the solution of the polyimide precursor is exemplified. The temperature in the case of thermally imidating the polyimide precursor in a solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out the imidation reaction while removing water generated by the reaction to the outside of the system.

Catalytic imidation of the polyimide precursor can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 mole times, preferably 2 to 20 mole times the amount of the amide acid group, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times the amount of the amide acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has a suitable basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Especially, the use of acetic anhydride is preferable because purification after completion of the reaction becomes easy. The imidation rate by catalyst imidation is controllable by adjusting the catalyst amount, reaction temperature, and reaction time.

What is necessary is just to throw in the reaction solution into a solvent and just to precipitate it, when collect|recovering the produced|generated polyimide precursor or polyimide from the polyimide precursor or the reaction solution of a polyimide. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, or water. The polymer precipitated by pouring into the solvent can be collected by filtration and then dried at normal temperature or under reduced pressure by heating. In addition, if the operation of re-dissolving the polymer recovered by precipitation in an organic solvent and recovering by reprecipitation is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more types of solvents selected from these is preferable because the purification efficiency is further increased.

The molecular weight of the polyimide-based polymer is a weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, when the strength of the liquid crystal aligning film obtained therefrom, the workability at the time of forming the liquid crystal aligning film, and the coating property are considered, and it is 5,000 to 1,000,000 desirable. Especially, 10,000 to 150,000 are preferable.

As described above, the specific polyimide-based polymer in the present invention is a polyimide obtained by catalytic imidation of the polyimide precursor from the viewpoint of being able to suppress a decrease in voltage retention even after being exposed to light irradiation for a long time. desirable. The imidation ratio at that time is preferably within the above range.

<liquid crystal aligning agent>

The liquid-crystal aligning agent of this invention is a coating solution for forming a liquid crystal aligning film (it is also mentioned a resin film), and it is preferable to contain a specific compound, a polymer, and a solvent.

As for the usage ratio of the specific compound in a liquid-crystal aligning agent, it is preferable that it is as follows. That is, it is preferable that it is 1 mass part - 30 mass parts with respect to 100 mass parts of all polymers. More preferably, it is 1 part by mass to 20 parts by mass, and particularly preferably 3 parts by mass to 15 parts by mass.

Although it is preferable to use a specific polyimide-type polymer for the polymer component in the liquid-crystal aligning agent, other polymers other than that may be mixed. In that case, it is preferable that content of other polymers other than that is 0.5 mass part - 15 mass parts with respect to 100 mass parts of specific polyimide type polymers. A more preferable thing is 1 mass part - 10 mass parts. As other polymers other than that, the above-mentioned acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrenes, polyamides, polyesters, celluloses, or polysiloxanes are exemplified.

It is preferable that content of the solvent in a liquid-crystal aligning agent is 70-99.9 mass % from the point that the solvent in a liquid-crystal aligning agent forms a uniform liquid crystal aligning film by application|coating. This content can be suitably changed according to the film thickness of the liquid crystal aligning film made into the objective.

The solvent used for the liquid-crystal aligning agent will not be specifically limited if it is a solvent (also referred to as a good solvent) in which a polymer is dissolved. Below, although the specific example of the good solvent at the time of using a specific polyimide type polymer is given, it is not limited to these examples.

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

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone.

Moreover, when the solubility to the solvent of a specific polyimide type polymer is high, it is preferable to use the solvent represented by the said formula [D-1] - formula [D-3].

It is preferable that the usage ratio of the good solvent in a liquid-crystal aligning agent is 10-100 mass % of the whole solvent contained in a liquid-crystal aligning agent. A more preferable thing is 20-90 mass %, and a particularly preferable thing is 30-80 mass %.

Unless the effect of this invention is inhibited for a liquid-crystal aligning agent, the solvent (it is also mentioned a poor solvent) which improves the coating-film property and surface smoothness of the liquid crystal aligning film at the time of apply|coating a liquid-crystal aligning agent can be used. Although the specific example of a poor solvent is given below, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl 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-methyl Cyclohexanol, 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-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol 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, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-( Hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy)propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether , dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol di Acetate, diethylene glycol monoethyl ether acetate diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, lactic acid Ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy methyl ethyl propionate, 3-methoxy ethyl propionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropylpropionic acid, 3-methoxybutylpropionic acid, methyl lactate, ethyl lactate, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, or The solvent etc. represented by said formula [D-1] - formula [D-3] are mentioned.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether or the above formula [D-1 ] - It is preferable to use the solvent represented by formula [D-3].

It is preferable that the usage ratio of these poor solvents is 1-70 mass % of the whole solvent contained in a liquid-crystal aligning agent. A more preferable thing is 1-60 mass %, and a particularly preferable thing is 5-60 mass %.

The liquid crystal aligning agent of the present invention is selected from the group consisting of a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms. It is preferable to introduce a crosslinkable compound or a crosslinkable compound having a polymerizable unsaturated bond group (also collectively referred to as a specific crosslinkable compound). In that case, it is necessary to have two or more of these groups in the compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, and tetraglycidylaminodiphenylene. , tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate Diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis( 2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethaxylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2- (4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1,3-bis(4-(1-(4-(2,3-epoxypro) Poxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

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

[Formula 40]

Specifically, the crosslinkable compound represented by formula [4a] - formula [4k] published on page 58 - page 59 of international publication WO2011/132751 (published on October 27, 2011) is mentioned.

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

[Formula 41]

Specifically, the crosslinkable compound represented by formula [5-1] - formula [5-42] published on page 76 - page 82 of international publication WO2012/014898 (published on February 2, 2012) is mentioned.

Examples of the crosslinkable compound having at least one group selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, and guar namine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, or ethyleneurea-formaldehyde resin; and the like. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group or both thereof can be used. This melamine derivative or benzoguanamine derivative can also exist as a dimer or a trimer. It is preferable that these have an average of 3 or more and 6 or less methylol groups or alkoxymethyl groups per triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 methoxymethyl groups per triazine ring, and 5.8 methoxymethyl groups per triazine ring, which are commercially available. MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.), methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253, 254, etc., butoxymethylated melamine, Cymel 506, 508, etc., carboxyl group-containing methoxymethylated isobutoxymethylated melamine, such as Cymel 1141, methoxymethylated such as Cymel 1123 Ethoxymethylated benzoguanamines, methoxymethylated butoxymethylated benzoguanamines such as Cymel 1123-10, butoxymethylated benzoguanamines such as Cymel 1128, methoxymethylated ethoxys containing carboxyl groups such as Cymel 1125-80 Methylated benzoguanamine (above, Mitsui Cyanamide Co., Ltd. make) is mentioned. Moreover, as an example of a glycoluril, butoxymethylation glycoluril like Cymel 1170, methylolation glycoluril like Cymel 1172, etc., a methoxymethylolation glycoluril like Powder Link 1174, etc. are mentioned.

Examples of the benzene having a hydroxyl group or an alkoxyl group or a phenolic compound include 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; and the like. More specifically, the crosslinkable compound represented by formula [6-1] - formula [6-48] published on page 62 - page 66 of International Publication WO2011/132751 (published on October 27, 2011) is mentioned. there is.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tri(meth)acrylate. ) A crosslinkable compound having three polymerizable unsaturated groups in a molecule such as acryloyloxyethoxytrimethylolpropane or glycerin polyglycidyl ether poly(meth)acrylate, ethylene glycol di(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, butylene glycol di( Meth)acrylate, neopentylglycoldi(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate , Glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid di and crosslinkable compounds having two polymerizable unsaturated groups in the molecule, such as glycidyl ester di(meth)acrylate or hydroxypivalic acid neopentyl glycol di(meth)acrylate.

It is preferable that content of the specific crosslinkable compound in a liquid-crystal aligning agent is 1-50 mass parts with respect to 100 mass parts of all polymer components. More preferably, it is 1 to 30 parts by mass, and particularly preferably 1 to 10 parts by mass, in order to promote the crosslinking reaction and express the desired effect.

The compound which improves the uniformity of the film thickness and surface smoothness of the liquid crystal aligning film at the time of apply|coating a liquid-crystal aligning agent can be used for a liquid-crystal aligning agent, unless the effect of this invention is impaired. Moreover, the compound etc. which improve the adhesiveness of a liquid crystal aligning film and a board|substrate can also be used.

As a compound which improves the uniformity or surface smoothness of the film thickness of a liquid crystal aligning film, a fluorochemical surfactant, silicone type surfactant, or nonionic surfactant, etc. are mentioned. Specifically, for example, Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafac F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (above) , manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.), and the like. As for the usage ratio of these surfactant, 0.01-2 mass parts is preferable with respect to 100 mass parts of all the polymer components contained in a liquid-crystal aligning agent. More preferably, it is 0.01-1 part by mass.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board|substrate, a functional silane containing compound and an epoxy group containing compound are mentioned. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidpropyltrimethoxysilane, 3-ureidpropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltri Ethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol di Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglyceride Cydyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclo hexane or N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane; and the like.

It is preferable that the use ratio of the compound made to adhere with these board|substrates is 0.1-30 mass parts with respect to 100 mass parts of all the polymer components contained in a liquid-crystal aligning agent. More preferably, it is 1-20 mass parts. When the effect of an adhesive improvement cannot be expected as it is less than 0.1 mass part, and it increases more than 30 mass parts, the storage stability of a liquid-crystal aligning agent may worsen.

To the liquid crystal aligning agent, other than compounds other than the above, as long as the effect of the present invention is not impaired, a dielectric or conductive material for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal aligning film may be added.

<Liquid crystal alignment film/liquid crystal display element>

After apply|coating and baking the liquid-crystal aligning agent of this invention on a board|substrate, it can carry out orientation processing by a rubbing process, light irradiation, etc., and can be used as a liquid crystal aligning film. Moreover, in the case of a liquid crystal display element for VA mode, etc., it can be used as a liquid crystal aligning film even without orientation processing. The substrate used at this time is not particularly limited as long as it is a substrate having high transparency, and plastic substrates such as acrylic substrates and polycarbonate substrates can be used in addition to glass substrates. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving the liquid crystal is formed. In addition, in the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as it is only a substrate on one side, and a material that reflects light such as aluminum can be used as an electrode in this case.

Although the coating method of a liquid-crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, an inkjet method, etc. is common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, or a spray method, and these may be used depending on the purpose.

After applying the liquid-crystal aligning agent on the substrate, by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared ray) type oven, depending on the solvent used for the liquid-crystal aligning agent, 30 to 300 ° C., preferably can evaporate a solvent at the temperature of 30-250 degreeC, and can be set as a liquid crystal aligning film. If the thickness of the liquid crystal aligning film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may decrease. Therefore, it is preferably 5 to 300 nm, more preferably Preferably, it is 10 to 100 nm. When tilting or horizontally aligning a liquid crystal like the liquid crystal display element for TN mode or IPS mode, the liquid crystal aligning film after baking is processed by rubbing, polarization|polarized-light ultraviolet irradiation, etc.

After the liquid crystal display element of this invention obtained the board|substrate with a liquid crystal aligning film from the liquid crystal aligning agent of this invention by the above-mentioned method, it manufactured the liquid crystal cell by a well-known method, and used it as a liquid crystal display element.

As a manufacturing method of a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are spread on the liquid crystal alignment film of one substrate, the liquid crystal alignment film surface is turned inside, and the other substrate A method of bonding and injecting liquid crystal under reduced pressure to seal, or a method of dropping a liquid crystal on a surface of a liquid crystal aligning film spread with a spacer, followed by bonding a substrate to seal (ODF: One Drop Filling Also referred to as the law), etc. can be exemplified.

The liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and contains a polymerizable compound polymerizable by at least one of active energy rays and heat between the pair of substrates. It is also suitably used also for a liquid crystal display element manufactured through the process of polymerizing a polymeric compound by at least one of irradiation of an active energy ray and heating, disposing a composition and applying a voltage between electrodes. Here, as an active energy ray, an ultraviolet-ray is suitable. As ultraviolet rays, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. Moreover, you may perform ultraviolet rays and heating simultaneously.

In the above liquid crystal display element, the pretilt of the liquid crystal molecules is controlled by a PSA mode system. In the PSA mode, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, a liquid crystal cell is assembled, and then a predetermined voltage is applied to the liquid crystal layer, and then the photopolymerizable compound is irradiated with ultraviolet rays. etc. are irradiated, and the pretilt of liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Moreover, since rubbing processing is not required in PSA mode, it is suitable for formation of the liquid crystal layer of the vertical alignment type in which it is difficult to control a pretilt by a rubbing process. That is, after obtaining the board|substrate with a liquid crystal aligning film from a liquid-crystal aligning agent by the above-mentioned method, the liquid crystal display element of this invention manufactures a liquid crystal cell, and polymerizes a polymeric compound by irradiation of an ultraviolet-ray and at least one of heating. By doing so, it is possible to control the orientation of the liquid crystal molecules.

An example of manufacturing a liquid crystal cell in PSA mode is given, for example, as follows. That is, a liquid crystal cell is manufactured by the manufacturing method mentioned above. A polymerizable compound that polymerizes by heat or ultraviolet irradiation is mixed with the liquid crystal at that time. Examples of the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in a molecule. In that case, it is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of a liquid crystal component, and, as for a polymeric compound, it is more preferable that it is 0.1-5 mass parts. If the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound does not polymerize and orientation control of the liquid crystal becomes impossible. If the amount exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases and the burn-in property of the liquid crystal display device deteriorates. do. After manufacturing the liquid crystal cell, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Accordingly, the orientation of liquid crystal molecules can be controlled.

Moreover, the liquid-crystal aligning agent of this invention has a liquid crystal layer between a pair of board|substrates provided with an electrode, and contains the polymeric group which superpose|polymerizes with at least one of an active energy ray and heat between said pair of board|substrates. It can also be used also for the liquid crystal display element manufactured through the process of arrange|positioning the liquid crystal aligning film which does, and applying a voltage between electrodes, ie, SC-PVA mode. Here, as an active energy ray, an ultraviolet-ray is suitable. As an ultraviolet-ray, a wavelength is 300-400 nm, More preferably, it is 310-360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, more preferably 60 to 80°C. Moreover, you may perform ultraviolet rays and heating simultaneously.

In order to obtain a liquid crystal aligning film containing a polymerizable group that polymerizes from at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent or a method of using a polymer component containing a polymerizable group can be heard

An example of SC-PVA mode liquid crystal cell production is given, for example, as follows. That is, a liquid crystal cell is manufactured by the manufacturing method mentioned above. After that, the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet light while applying an AC or DC voltage to the liquid crystal cell.

As described above, by using the liquid-crystal aligning agent of the present invention, even after being exposed to light irradiation for a long time, the decrease in voltage retention is suppressed, and display unevenness does not occur near the frame of the liquid crystal display element even under high temperature and high humidity conditions. It is possible to provide a liquid crystal alignment film that does not. Therefore, the liquid crystal display element manufactured using the liquid-crystal aligning agent of this invention becomes a thing excellent in reliability, and can be used suitably for a large liquid crystal television, a small and medium-sized car navigation system, a smart phone, etc. In particular, the liquid-crystal aligning agent of this invention is useful with respect to the liquid crystal aligning film of the liquid crystal display element using VA mode, PSA mode, and SC-PVA mode.

Example

The present invention will be described in more detail by way of examples below, but it is not limited thereto.

Abbreviations used in Synthesis Examples, Examples and Comparative Examples are as follows.

(specific compounds)

S1: Phosphorus tungstic acid (manufactured by Nippon Shinmetal Co., Ltd.)

S2: Phosphomolybdic acid (12 molybdic acid (IV) phosphoric acid n hydrate) (manufactured by Kanto Chemical Co., Ltd.)

(Specific diamine compound (1))

A1: Diamine compound represented by the following formula [A1]

A2: diamine compound represented by the following formula [A2]

[Formula 42]

(Specific diamine compound (2))

B1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene

B2: 1,3-diamino-5-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene

B3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

B4: Diamine compound represented by the following formula [B4]

B5: 1,3-diamino-4-octadecyloxybenzene

[Formula 43]

(other diamine compounds)

C1: p-phenylenediamine

C2: m-phenylenediamine

C3: diamine compound represented by the following formula [C3]

C4: 4,4'-diaminodiphenylamine

C5: 3,5-diaminobenzoic acid

[Formula 44]

(Specific tetracarboxylic dianhydride)

D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

D3: Tetracarboxylic dianhydride represented by the following formula [D3]

D4: Tetracarboxylic dianhydride represented by the following formula [D4]

D5: Tetracarboxylic dianhydride represented by the following formula [D5]

[Formula 45]

(Crosslinkable compound)

M1: Crosslinkable compound represented by the following formula [M1]

[Formula 46]

(menstruum)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: Ethylene glycol monobutyl ether

PB: Propylene glycol monobutyl ether

DME: Dipropylene glycol dimethyl ether

"Measurement of Molecular Weight of Polyimide Polymers"

It was measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101, manufactured by Showa Denko) and a column (KD-803, KD-805, manufactured by Shodex).

Column temperature: 50 ° C

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L , tetrahydrofuran (THF) at 10 mL/L)

Flow rate: 1.0 ml/min

Standard samples for calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

"Measurement of imidation rate of polyimide polymer"

20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Science Co., Ltd.)), and deuterated dimethylsulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)) was mixed product) (0.53 ml) was added and ultrasonic was applied to dissolve completely. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500, manufactured by JEOL Datum Co., Ltd.). For the imidation rate, a proton derived from a structure that does not change before and after imidization is determined as a standard proton, and the peak integrated value of this proton and the proton peak integrated value derived from the NH group of amic acid appearing around 9.5 ppm to 10.0 ppm It was obtained by the following formula using

Imidization rate (%) = (1 - α x / y) × 100

(x is the peak integration value of protons derived from the NH group of amide acid, y is the peak integration value of standard protons, α is 1 NH group proton of amide acid in the case of polyamic acid (imidization rate is 0%) It is the ratio of the number of reference protons to

"Synthesis of Polyimide Polymers"

<Synthesis Example 1>

After mixing D4 (9.65 g, 32.1 mmol), B5 (1.36 g, 3.61 mmol) and C1 (3.52 g, 32.6 mmol) in NMP (30.5 g) and reacting at 40 ° C. for 6 hours, D1 ( 0.70 g, 3.57 mmol) and NMP (15.2 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (3.90 g) and pyridine (2.40 g) were added as an imidation catalyst, and it was made to react at 70 degreeC for 4 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (1). The imidation rate of this polyimide was 85%, the number average molecular weight was 19,800, and the weight average molecular weight was 51,800.

<Synthesis Example 2>

D2 (5.95 g, 23.8 mmol), B3 (4.47 g, 10.3 mmol), C1 (1.49 g, 13.8 mmol) and C3 (2.10 g, 10.3 mmol) were mixed in NEP (32.0 g) and 80 After reacting at °C for 5 hours, D1 (2.00 g, 10.2 mmol) and NEP (16.0 g) were added, followed by reaction at 40 °C for 6 hours, and a polyamic acid solution having a resin solid content concentration of 25% by mass (2) got The number average molecular weight of this polyamic acid was 20,200, and the weight average molecular weight was 68,300.

<Synthesis Example 3>

After adding NEP to the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2 and diluting to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst, It was made to react at 80 degreeC for 4 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (3). The imidation ratio of this polyimide was 80%, the number average molecular weight was 18,300, and the weight average molecular weight was 46,800.

<Synthesis Example 4>

D2 (2.98 g, 11.9 mmol), A1 (1.25 g, 5.16 mmol), B3 (2.23 g, 5.15 mmol) and C1 (0.74 g, 6.84 mmol) were mixed in NEP (16.4 g) and 80 After making it react at degreeC for 5 hours, D1 (1.00g, 5.10 mmol) and NEP (8.21g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 4 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (4). The imidation ratio of this polyimide was 81%, the number average molecular weight was 17,800, and the weight average molecular weight was 44,900.

<Synthesis Example 5>

D2 (2.17 g, 8.67 mmol), A1 (1.28 g, 5.28 mmol), B1 (2.67 g, 7.02 mmol) and C1 (0.57 g, 5.27 mmol) were mixed in NMP (16.8 g) and 80 After making it react at degreeC for 5 hours, D1 (1.70g, 8.67 mmol) and NMP (8.39g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.80g) and pyridine (2.40g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (5). The imidation rate of this polyimide was 56%, the number average molecular weight was 17,000, and the weight average molecular weight was 43,200.

<Synthesis Example 6>

D2 (2.17 g, 8.67 mmol), A1 (1.28 g, 5.28 mmol), B5 (2.65 g, 7.04 mmol) and C1 (0.57 g, 5.27 mmol) were mixed in NMP (16.7 g) and 80 After making it react at degreeC for 5 hours, D1 (1.70g, 8.67 mmol) and NMP (8.36g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.80g) and pyridine (2.40g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (6). The imidation rate of this polyimide was 55%, the number average molecular weight was 16,300, and the weight average molecular weight was 41,100.

<Synthesis Example 7>

D2 (1.31 g, 5.24 mmol), A1 (0.86 g, 3.55 mmol), B2 (2.80 g, 7.10 mmol), C1 (0.57 g, 5.27 mmol) and C4 (0.35 g, 1.76 mmol) After mixing in NMP (16.6 g) and reacting at 80 ° C. for 5 hours, D1 (2.40 g, 12.2 mmol) and NMP (8.29 g) were added and reacted at 40 ° C. for 6 hours to obtain a resin solid content concentration of 25 A polyamic acid solution in mass % was obtained.

After adding NMP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (3.80 g) and pyridine (2.40 g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 2.5 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (7). The imidation ratio of this polyimide was 60%, the number average molecular weight was 17,500, and the weight average molecular weight was 43,800.

<Synthesis Example 8>

D2 (2.04 g, 8.15 mmol), A2 (1.07 g, 4.13 mmol), B2 (2.94 g, 7.45 mmol), C1 (0.36 g, 3.33 mmol) and C5 (0.25 g, 1.64 mmol) After mixing in NEP (16.5 g) and reacting at 80 ° C. for 5 hours, D1 (1.60 g, 8.16 mmol) and NEP (8.26 g) were added and reacted at 40 ° C. for 6 hours to obtain a resin solid content concentration of 25 A polyamic acid solution in mass % was obtained.

After adding NMP to the obtained polyamic acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (8). The imidation ratio of this polyimide was 72%, the number average molecular weight was 16,800, and the weight average molecular weight was 41,900.

<Synthesis Example 9>

D2 (2.30 g, 9.19 mmol), A1 (0.90 g, 3.71 mmol), B4 (2.29 g, 4.65 mmol) and C2 (1.11 g, 10.3 mmol) were mixed in NMP (16.8 g) and 80 After making it react at degreeC for 5 hours, D1 (1.80g, 9.18 mmol) and NMP (8.39g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.80g) and pyridine (2.40g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (9). The imidation rate of this polyimide was 52%, the number average molecular weight was 15,300, and the weight average molecular weight was 39,700.

<Synthesis Example 10>

D3 (7.10 g, 31.7 mmol), A1 (3.11 g, 12.8 mmol), B2 (5.06 g, 12.8 mmol) and C1 (0.69 g, 6.38 mmol) were mixed in NMP (47.9 g) and 40 It was made to react at degreeC for 8 hours, and the polyamic acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (10). The imidation rate of this polyimide was 73%, the number average molecular weight was 18,600, and the weight average molecular weight was 48,400.

<Synthesis Example 11>

D4 (3.22 g, 10.7 mmol), A1 (0.38 g, 1.57 mmol), B1 (2.95 g, 7.75 mmol), C2 (0.34 g, 3.14 mmol) and C4 (0.62 g, 3.11 mmol) After mixing in NMP (16.8 g) and reacting at 80°C for 5 hours, D1 (0.90 g, 4.59 mmol) and NMP (8.39 g) were added and reacted at 40°C for 6 hours to obtain a resin solid content concentration of 25 A polyamic acid solution in mass % was obtained.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 4 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (11). The imidation ratio of this polyimide was 85%, the number average molecular weight was 16,200, and the weight average molecular weight was 41,500.

<Synthesis Example 12>

D4 (3.67 g, 12.2 mmol), A2 (1.00 g, 3.86 mmol), B3 (2.35 g, 5.43 mmol), C1 (0.50 g, 4.62 mmol) and C3 (0.32 g, 1.57 mmol) After mixing in NMP (16.9 g) and reacting at 80 ° C. for 5 hours, D1 (0.60 g, 3.06 mmol) and NMP (8.44 g) were added and reacted at 40 ° C. for 6 hours. The resin solid content concentration was 25 A polyamic acid solution in mass % was obtained.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (12). The imidation rate of this polyimide was 72%, the number average molecular weight was 17,500, and the weight average molecular weight was 43,100.

<Synthesis Example 13>

D2 (2.48 g, 9.91 mmol), A1 (1.62 g, 6.69 mmol), B2 (2.64 g, 6.69 mmol) and C1 (0.36 g, 3.33 mmol) were mixed in NMP (17.0 g) and 80 After making it react at degreeC for 5 hours, D5 (1.40g, 6.60 mmol) and NMP (8.50g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NEP to the obtained polyamic acid solution (30.0 g) and diluting to 6 mass %, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3.5 hours. . This reaction solution was poured into methanol (460 ml), and the resulting precipitate was separated by filtration. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide powder (13). The imidation rate of this polyimide was 74%, the number average molecular weight was 16,200, and the weight average molecular weight was 41,500.

Table 32 and Table 33 show the polyimide-type polymer obtained by the synthesis example.

*1: Polyamic acid.

"Manufacture of liquid crystal aligning agent"

In Examples and Comparative Examples to be described later, the production example of the liquid-crystal aligning agent is described. Moreover, this liquid-crystal aligning agent is used also for manufacture of a liquid crystal display element and its evaluation. Each liquid-crystal aligning agent obtained by the Example and the comparative example is shown to Table 34 - Table 36.

"Evaluation of inkjet coating property of liquid crystal aligning agent"

Inkjet coatability was evaluated using the liquid-crystal aligning agent obtained in Example 7 and Example 11 to be described later. Specifically, these liquid crystal aligning agents were filtered under pressure with a membrane filter having a pore diameter of 1 µm, and washed with pure water and IPA (isopropyl alcohol). 100 mm long × 100 mm wide, 0.7 mm thick) on the ITO surface, the application area was 70 × 70 mm, the nozzle pitch was 0.423 mm, the scan pitch was 0.5 mm, and the coating speed was applied under the conditions of 40 mm / sec. . At that time, HIS-200 (manufactured by Hitachi Plant Technology Co., Ltd.) was used for the inkjet coating machine. In addition, the time from application to temporary drying was 60 seconds, and temporary drying was performed on a hot plate at 70°C for 5 minutes.

Evaluation of applicability was performed by visually observing the coating-film surface of the board|substrate with a liquid crystal aligning film obtained above. Specifically, the coated film surface was visually observed under a sodium lamp to confirm the presence or absence of pinholes. As a result, as for the liquid crystal aligning film obtained in any Example, the pinhole was not seen on the coating film surface, but the liquid crystal aligning film excellent in coating film property was obtained.

"Evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell (normal cell)"

A substrate with an ITO electrode (40 mm in length x 30 mm in width, 0.7 mm in thickness) obtained by filtering the liquid crystal aligning agent obtained in Examples and Comparative Examples described later under pressure with a membrane filter having a pore diameter of 1 µm and washing with pure water and IPA. was spin-coated on the ITO surface, and heat treatment was performed on a hot plate at 100°C for 5 minutes and at 230°C for 30 minutes in a heat circulation type clean oven to obtain an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm. In addition, the liquid-crystal aligning agent of Example 7 and Example 11 prepared a board|substrate under the same conditions as the said "evaluation of the inkjet coatability of a liquid-crystal aligning agent" (in the board|substrate, ITO which washed with pure water and IPA similar to the above) A board|substrate with an electrode (40 mm in length x 30 mm in width, thickness 0.7 mm) was used), and then heat-processed at 230 degreeC for 30 minutes in a heat circulation type clean oven, and a liquid crystal aligning film with a film thickness of 100 nm adhered was used as an ITO substrate.

Next, the coated film surface of this substrate was rubbed with a rubbing device having a roll diameter of 120 mm using a rayon cloth under conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm/sec, and a press-in amount of 0.1 mm. .

Then, two substrates after the rubbing treatment were prepared, the coated film side was placed inside, and they were sandwiched between 6 µm spacers, and the periphery was adhered with a sealant to prepare an empty cell. A liquid crystal was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell. In Example 1 and Comparative Example 1, MLC-3018U (manufactured by Merck Japan) was used for the liquid crystal, and in Examples and Comparative Examples other than that, MLC-6608 (manufactured by Merck Japan) was used for the liquid crystal. did

Using the obtained liquid crystal cell, evaluation of the display nonuniformity characteristic of frame vicinity of the liquid crystal cell was performed. Specifically, the liquid-crystal orientation of sealing compound vicinity was evaluated by visual observation using a polarizing plate and a backlight. As a result, all liquid crystal cells obtained in Examples and Comparative Examples exhibited uniform liquid crystal orientation.

Then, the liquid crystal cell was stored in a high-temperature, high-humidity tank at a temperature of 80°C and a humidity of 90% for 96 hours, and the liquid-crystal orientation of sealing agent vicinity was evaluated on the same conditions as the above. Evaluation said that it was excellent in this evaluation, so that the disorder of the liquid-crystal orientation was not seen in sealing compound vicinity after storage in a high-temperature, high-humidity tank (good display in Tables 37-39). In Table 37 - Table 39, the result of the display nonuniformity characteristic of frame vicinity of the liquid crystal cell after storage in a high-temperature, high-humidity tank is shown.

"Evaluation of voltage holding ratio (normal cell)"

The voltage retention was evaluated using a liquid crystal cell manufactured under the same conditions as in the above "evaluation of display nonuniformity characteristics near frame of liquid crystal cell (normal cell)". Specifically, a voltage of 1 V is applied to the liquid crystal cell obtained by the above method at a temperature of 80 ° C. for 60 μs, the voltage after 50 ms is measured, and how much voltage can be maintained is voltage retention (also referred to as VHR). ) was calculated as In addition, the measurement was performed using a voltage retention rate measuring device (VHR-1) (manufactured by Toyo Technica Co., Ltd.) under the settings of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 50 ms.

In addition, using a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlight Co., Ltd.), ultraviolet rays of 50 J/cm After irradiation, the voltage holding ratio was measured under the same conditions as above.

In this evaluation, the value of the voltage retention immediately after liquid crystal cell production is high, and the value after ultraviolet irradiation (also referred to as after ultraviolet irradiation) decreases with respect to the value of voltage retention immediately after liquid crystal cell production (also referred to as initial stage). It was said that the smaller one was, the more excellent it was in this evaluation. In Table 37 - Table 39, the value of each VHR is shown.

<Example 1>

NMP (7.83 g) and (gamma)-BL (23.5 g) were added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1, and it stirred and dissolved at 70 degreeC for 24 hours. S1 (0.25g) and BCS (7.83g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (1). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Example 2>

S1 (0.125 g), NEP (14.0 g), and PB (17.6 g) were added to the polyamic acid solution (2) (10.0 g) having a resin solid content concentration of 25.0 mass% obtained in Synthesis Example 2, and 6 at 25 ° C. It stirred for time and obtained the liquid-crystal aligning agent (2). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Example 3>

NEP (23.5 g) was added to the polyimide powder (3) (2.50 g) obtained in the synthesis example 3, and it stirred and dissolved at 70 degreeC for 24 hours. S1 (0.25g), BCS (3.92g) and PB (11.8g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (3). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Regarding the "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell (normal cell)", as an intensive test together with the above standard test, when stored in a high-temperature, high-humidity chamber at a temperature of 80°C and a humidity of 90% for 144 hours. was also evaluated (other conditions were the same as the above conditions). As a result, disorder of the liquid-crystal orientation was seen from the sealing compound to the area|region of the width to 0.5 cm among liquid crystal cells.

<Example 4>

NEP (23.5 g) was added to the polyimide powder (4) (2.50 g) obtained in the synthesis example 4, and it stirred and dissolved at 70 degreeC for 24 hours. S1 (0.25g), BCS (3.92g) and PB (11.8g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (4). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Regarding the "evaluation of display non-uniformity characteristics near the frame of a liquid crystal cell (normal cell)", as an intensive test together with the above standard test, when stored in a high-temperature, high-humidity chamber at a temperature of 80°C and a humidity of 90% for 144 hours. was also evaluated (other conditions were the same as the above conditions). As a result, disorder of the liquid-crystal orientation was not seen in sealing compound vicinity among liquid crystal cells.

<Example 5>

NEP (23.5 g) was added to the polyimide powder (5) (2.50 g) obtained in Synthesis Example 5, and it was stirred and dissolved at 70 degreeC for 24 hours. S1 (0.175g) and PB (15.7g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (5). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Regarding the "evaluation of the display nonuniformity characteristic near the frame of the liquid crystal cell (normal cell)", as an emphasis test together with the above standard test, when stored in a high-temperature, high-humidity chamber at a temperature of 80 ° C. and a humidity of 90% for 168 hours was also evaluated (other conditions were the same as the above conditions). As a result, disorder of the liquid-crystal orientation was not seen in sealing compound vicinity among liquid crystal cells.

<Example 6>

NEP (23.5 g) was added to the polyimide powder (6) (2.50 g) obtained in the synthesis example 6, and it stirred and dissolved at 70 degreeC for 24 hours. S1 (0.175g) and PB (15.7g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (6). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

Regarding the "evaluation of the display nonuniformity characteristic near the frame of the liquid crystal cell (normal cell)", as an emphasis test together with the above standard test, when stored in a high-temperature, high-humidity chamber at a temperature of 80 ° C. and a humidity of 90% for 168 hours was also evaluated (other conditions were the same as the above conditions). As a result, disorder of the liquid-crystal orientation was seen in sealing compound vicinity among liquid crystal cells.

<Example 7>

NEP (20.7 g) was added to the polyimide powder (7) (1.50 g) obtained in Synthesis Example 7, and it was stirred and dissolved at 70 degreeC for 24 hours. S2 (0.105g), PB (16.5g) and DME (4.14g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (7). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Example 8>

NMP (23.5 g) was added to the polyimide powder (8) (2.50 g) obtained in the synthesis example 8, and it stirred and dissolved at 70 degreeC for 24 hours. S1 (0.075g), M1 (0.125g), BCS (7.83g) and PB (7.83g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (8). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Example 9>

NEP (25.5 g) was added to the polyimide powder (9) (2.50 g) obtained in the synthesis example 9, and it stirred and dissolved at 70 degreeC for 24 hours. S1 (0.30g), BCS (5.88g) and PB (7.83g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (9). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Example 10>

NEP (23.5 g) was added to the polyimide powder (10) (2.50 g) obtained in the synthesis example 10, and it stirred and dissolved at 70 degreeC for 24 hours. S2 (0.125g) and PB (15.7g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (10). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Example 11>

NEP (16.5 g) and γ-BL (4.14 g) were added to the polyimide powder (11) (1.50 g) obtained in Synthesis Example 11, and stirred at 70°C for 24 hours to dissolve. S1 (0.105g), BCS (8.27g) and PB (12.4g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (11). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Example 12>

NMP (19.6 g) was added to the polyimide powder (12) (2.50 g) obtained in the synthesis example 12, and it stirred and dissolved at 70 degreeC for 24 hours. S1 (0.25g), M1 (0.175g), BCS (15.7g) and DME (3.92g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (12). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Example 13>

NEP (23.5 g) was added to the polyimide powder (13) (2.50 g) obtained in Synthesis Example 13, and it was stirred and dissolved at 70 degreeC for 24 hours. S2 (0.175g), BCS (7.83g) and PB (7.83g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (13). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Comparative Example 1>

NMP (7.83 g) and (gamma)-BL (23.5 g) were added to the polyimide powder (1) (2.50 g) obtained in Synthesis Example 1, and it stirred and dissolved at 70 degreeC for 24 hours. BCS (7.83g) was added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (14). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

<Comparative Example 2>

NEP (23.5 g) was added to the polyimide powder (3) (2.50 g) obtained in the synthesis example 3, and it stirred and dissolved at 70 degreeC for 24 hours. BCS (3.92g) and PB (11.8g) were added to this solution, and it stirred at 25 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (15). Abnormality, such as muddiness and precipitation, was not looked at by this liquid-crystal aligning agent, but it was confirmed that it is a uniform solution.

*1: shows the introduced amount (parts by mass) of a specific compound with respect to 100 parts by mass of the polyimide polymer.

*2: The ratio occupied by the polyimide polymer in the liquid crystal aligning agent is shown.

*1: Disorder of the liquid-crystal orientation was seen in sealing compound vicinity among liquid crystal cells.

*2: Disorder of the liquid-crystal orientation was seen from sealing compound to the area|region of the width from sealing agent to 0.5 cm among liquid crystal cells (the width|variety in which disorder of liquid-crystal orientation is seen is wider than *1).

As can be seen from the above results, the liquid-crystal aligning agent of Examples of the present invention was able to suppress the decrease in voltage retention even if the liquid crystal cell was irradiated with ultraviolet rays compared to the liquid-crystal aligning agent of the comparative example. Moreover, even if it stored a liquid crystal cell in a high-temperature, high-humidity tank for a long time, disorder of the liquid-crystal orientation was not seen near sealing compound. That is, even after the liquid-crystal aligning agent of this invention is exposed to light irradiation for a long time, the liquid crystal which can suppress the fall of voltage retention, and can also suppress generation|occurrence|production of the display nonuniformity of the frame vicinity of a liquid crystal display element under high temperature, high humidity conditions. It becomes an alignment film.

Specifically, in the Example of the liquid-crystal aligning agent using the specific compound and specific polyimide polymer in the present invention and the comparative example of the liquid-crystal aligning agent not using the specific compound, the liquid-crystal aligning agent of the comparative example is described above It was found that the characteristics were degraded. More specifically, it is a comparison between Example 1 and Comparative Example 1, and a comparison between Example 3 and Comparative Example 3.

Moreover, compared with the liquid-crystal aligning agent which does not use the liquid-crystal aligning agent using the specific diamine compound (1) which has a specific structure (1) in this invention, in an emphasizing test, a liquid crystal cell for a long time, high temperature, high humidity Even if it stored in a tank, disorder of the liquid-crystal orientation was not seen near sealing compound. More specifically, it is a comparison between Example 3 and Example 4 in the comparison on the same conditions in the stress test.

Furthermore, in the specific structure (2) in this invention, the liquid-crystal aligning agent using the specific diamine compound (2) which has the specific structure of said formula [3-1] has the specific structure of said formula [3-2] Compared with the liquid-crystal aligning agent using the diamine compound which has, in an emphasizing test, even if it stored a liquid crystal cell in a high-temperature, high-humidity tank for a long time, disorder of the liquid-crystal orientation was not seen in sealing compound vicinity. More specifically, it is a comparison between Example 5 and Example 6 in the comparison on the same conditions in the stress test.

industrial applicability

Even after the liquid-crystal aligning agent of this invention is exposed to light irradiation for a long time, it suppresses the fall of a voltage retention, and also improves the adhesiveness of a sealing compound and a liquid crystal aligning film, and displays near the frame of a liquid crystal display element under high-temperature, high-humidity conditions. The liquid crystal aligning film which can suppress generation|occurrence|production of a nonuniformity can be provided. Furthermore, the liquid crystal aligning agent which can provide the liquid crystal display element which has said liquid crystal aligning film and said liquid crystal aligning film can be provided.

Therefore, the liquid crystal display element having a liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention is excellent in reliability and can be suitably used for a large-screen, high-definition liquid crystal television or the like, and is suitable for TN elements, STN elements, TFT liquid crystal elements, especially vertical It is useful for alignment-type liquid crystal display elements.

Moreover, when manufacturing a liquid crystal display element, the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention is useful also to the liquid crystal display element which needs to irradiate an ultraviolet-ray. That is, a liquid crystal composition comprising a liquid crystal layer formed between a pair of substrates equipped with electrodes and polymerizable by at least one of active energy rays and heat is disposed between the pair of substrates, A liquid crystal display element manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes, further comprising a liquid crystal layer between a pair of substrates provided with electrodes, and between the pair of substrates. It is particularly useful for a liquid crystal display device manufactured through a step of arranging a liquid crystal aligning film containing a polymerizable group that polymerizes with at least one of active energy rays and heat, and polymerizing the polymerizable group while applying a voltage between the electrodes.

Claims (20)

The liquid-crystal aligning agent containing the following (A) component and (B) component.
(A) Component: The heteropoly acid which is at least 1 sort(s) chosen from the group which consists of phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicotungstic acid, and phosphotungstomolybdic acid.
Component (B): at least one polymer selected from the group consisting of acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses, and polysiloxanes. According to claim 1,
The liquid-crystal aligning agent in which the said polymer has a nitrogen-containing aromatic heterocycle. According to claim 1,
The liquid-crystal aligning agent whose said polymer is the polyimide which imidated the polyimide precursor obtained by reaction of a diamine component and a tetracarboxylic acid component, or this polyimide precursor. According to claim 3,
The liquid-crystal aligning agent containing the diamine compound which the said diamine component has the structure shown by following formula [2].

(W ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- and -N(CH represents at least one bonding group selected from the group consisting of ₃ )CO- W ² represents at least one bonding group selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring, and an aromatic ring; W ³ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ ) CO- and -O(CH ₂ ) _m - (m represents an integer of 1 to 5. At least one member selected from the group consisting of W ⁴ represents a nitrogen-containing aromatic heterocycle.) According to claim 4,
The liquid-crystal aligning agent in which the said diamine component contains the diamine compound represented by following formula [2a].

(W represents the structure represented by the said formula [2]. m1 represents the integer of 1-4.) According to claim 3,
The liquid-crystal aligning agent containing the diamine compound which the said diamine component has the structure shown by following formula [3-1] or formula [3-2].

(Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )- represents at least one bonding group selected from the group consisting of -N(CH ₃ )CO-, -COO- and -OCO- Y ² is a single bond or -(CH ₂ ) _b - (b is 1 to 15 Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- Y ⁴ is at least one divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton. group, and any hydrogen atom on the cyclic group is substituted with an alkyl group of 1 to 3 carbon atoms, an alkoxyl group of 1 to 3 carbon atoms, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom. Y ⁵ represents at least one cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group of 1 to 3 carbon atoms, an alkyl group of 1 to 3 carbon atoms, It may be substituted with an alkoxyl group of 3, a fluorine-containing alkyl group of 1 to 3 carbon atoms, a fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or a fluorine atom. n represents an integer of 0 to 4. Y ⁶ is an alkyl group of 1 to 18 carbon atoms , at least one selected from the group consisting of an alkenyl group of 2 to 18 carbon atoms, a fluorine-containing alkyl group of 1 to 18 carbon atoms, an alkoxyl group of 1 to 18 carbon atoms, and a fluorine-containing alkoxyl group of 1 to 18 carbon atoms.)

(Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represents at least one bonding group selected from the group consisting of Y ⁸ represents an alkyl group having 8 to 18 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms.) According to claim 6,
The liquid-crystal aligning agent in which the said diamine compound is represented by following formula [3a].

(Y represents the structure represented by the said formula [3-1] or formula [3-2]. n1 represents the integer of 1-4.) According to claim 3,
The liquid-crystal aligning agent in which the said tetracarboxylic-acid component contains tetracarboxylic dianhydride represented by following formula [4].

(Z represents at least one structure selected from the group consisting of structures represented by the following formulas [4a] to formula [4k].)

(Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring. Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group. ) According to any one of claims 1 to 8,
The liquid-crystal aligning agent containing at least 1 sort(s) of solvent chosen from the group which the said liquid-crystal aligning agent consists of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and (gamma)-butyrolactone. According to any one of claims 1 to 8,
The liquid crystal aligning agent is 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and the following formula [D1] - Liquid-crystal aligning agent containing the at least 1 sort(s) of solvent chosen from the group which consists of solvents represented by a formula [D3].

(D ¹ represents an alkyl group of 1 to 3 carbon atoms. D ² represents an alkyl group of 1 to 3 carbon atoms. D ³ represents an alkyl group of 1 to 4 carbon atoms.) According to any one of claims 1 to 8,
The liquid crystal aligning agent is selected from the group consisting of a crosslinkable compound having a substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and an alkoxyalkyl group having 1 to 3 carbon atoms A liquid crystal aligning agent containing a crosslinkable compound having a substituent or a crosslinkable compound having a polymerizable unsaturated bond group. The liquid crystal aligning film obtained from the liquid-crystal aligning agent in any one of Claims 1-8. The liquid crystal aligning film obtained by apply|coating the liquid-crystal aligning agent in any one of Claims 1-8 by the inkjet method. The liquid crystal display element which has the liquid crystal aligning film of Claim 12. According to claim 12,
A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, the electrodes A liquid crystal aligning film characterized in that it is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage between them. According to claim 13,
A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, the electrodes A liquid crystal aligning film characterized in that it is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage between them. The liquid crystal display element characterized by having the liquid crystal aligning film of Claim 16. According to claim 12,
A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable group that polymerizes with at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes A liquid crystal aligning film characterized by being used for a liquid crystal display element manufactured through a step of polymerizing the polymerizable group while applying a voltage. According to claim 13,
A liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable group that polymerizes with at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes A liquid crystal aligning film characterized by being used for a liquid crystal display element manufactured through a step of polymerizing the polymerizable group while applying a voltage. The liquid crystal display element characterized by having the liquid crystal aligning film of Claim 18.