KR102283305B1 - Composition, liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The liquid-crystal aligning agent containing the composition containing the at least 1 sort(s) of polymer chosen from the polyimide precursor obtained by making the cellulose polymer which has a specific structure, and a diamine component, and a tetracarboxylic-acid component react, or a polyimide.

Description

A composition, a liquid-crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element {COMPOSITION, LIQUID CRYSTAL ALIGNMENT TREATMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT}

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

DESCRIPTION OF RELATED ART The resin film which consists of organic materials, such as a polymeric material, attracts attention, such as the ease of formation and insulating performance, and is widely used as an interlayer insulating film, a protective film, etc. in an electronic device. Especially, in the liquid crystal display element well-known as a display device, the resin film which consists of an organic material is used as a liquid crystal aligning film.

Currently, as a resin film used industrially, a polyimide-based organic film excellent in durability is used. In particular, this polyimide-type organic film is used also as a liquid crystal aligning film of a liquid crystal display element. The polyimide-based organic film is formed from a composition containing polyamic acid or polyimide as a polyimide precursor. That is, the polyimide-based organic film is formed by applying a composition containing polyamic acid or polyimide to a substrate and passing through a firing process (see, for example, Patent Document 1).

A liquid crystal aligning film is used for the purpose of controlling the alignment state of a liquid crystal. However, with high definition of a liquid crystal display element, from viewpoints such as suppression of the contrast fall of a liquid crystal display element, and reduction of an afterimage phenomenon, also in the liquid crystal aligning film used there, when a thing with high voltage retention and a DC voltage are applied Characteristics such as a small amount of accumulated charge or a rapid relaxation of the accumulated charge by a DC voltage have become important. On the other hand, a compound containing one carboxylic acid group in the molecule in addition to polyamic acid or an imidized polymer thereof, etc., for the purpose of having a high voltage retention rate and shortening the time until the residual image generated by DC voltage disappears; What used the liquid-crystal aligning agent containing a very small amount of the compound chosen from the compound containing one carboxylic anhydride group in a molecule|numerator, and the compound containing one tertiary amino group in a molecule|numerator (for example, refer patent document 2) is known there is.

Japanese Patent Application Laid-Open No. Hei 09-278724 Japanese Patent Laid-Open No. Hei 08-76128

With the recent performance improvement of a liquid crystal display element, a liquid crystal display element is used for vehicle-mounted uses, such as a car navigation system and a meter panel, and by extension, a smartphone and a tablet type PC. In such a use, in order to improve visibility inside a vehicle or outdoors, the case where the light amount of a backlight is made high and it uses, or a backlight with a high calorific value is used in some cases. Moreover, in the use of a smartphone or a tablet PC, since it is used outdoors in many cases, it is easy to hit a liquid crystal display element much external light, such as sunlight containing an ultraviolet-ray.

When a liquid crystal display element is irradiated with light, such as a backlight light and an ultraviolet-ray, the peripheral member in a liquid crystal display element, for example, organic members, such as a color filter and a column spacer, may be decomposed|disassembled. As a result, the voltage retention characteristic is lowered, and line exposure, which is a display defect of the liquid crystal display element, occurs, and the reliability of the liquid crystal display element is lowered.

Therefore, as a liquid crystal aligning film, even if the peripheral member of a liquid crystal display element decomposes|disassembles by irradiation of the light with respect to a liquid crystal display element, it is calculated|required that voltage retention is a favorable characteristic. Even if the insulating film which consists of an organic member especially under a liquid crystal aligning film decomposes|disassembles by irradiation of light, it is calculated|required that this characteristic is favorable.

Moreover, the composition which consists of a normal polyimide-type polymer has low transparency of a resin film, and decomposition|disassembly of a resin film becomes easy to occur when light, such as an ultraviolet-ray, hits by this. Therefore, it is necessary to make transparency of a resin film high, and to suppress decomposition|disassembly.

Therefore, an object of the present invention is to provide a composition having the above characteristics. That is, an object of this invention is to provide the composition which transparency of a resin film is high and can suppress decomposition|disassembly of the resin film by light, such as an ultraviolet-ray.

Moreover, this invention is the liquid-crystal aligning agent using the composition mentioned above WHEREIN: Even if it irradiates light in the state with the insulating film which consists of an organic member under a liquid crystal aligning film, it provides the liquid-crystal aligning agent used as the liquid crystal aligning film excellent in voltage retention. aim to do

Moreover, this invention aims at providing the liquid crystal display element provided with the liquid crystal aligning film corresponding to the above-mentioned request|requirement.

As a result of intensive research, the present inventors have found that a composition containing at least one polymer selected from polyimide precursors or polyimides obtained by reacting a cellulose-based polymer having a specific structure and a diamine component with a tetracarboxylic acid component is described above. In order to achieve the object, it was found that it was very effective and came to complete the present invention.

That is, this invention has the following summary.

(1) A composition containing the following component (A) and component (B).

(A) Component: The polymer which has a structure shown by following formula [1].

[Formula 1]

(In formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having a structure selected from the following formulas [1a] to [1m], and n is 100 to represents an integer of 1000000).

[Formula 2]

(In formulas [1c] to [1m], X ⁷ and X ⁸ each independently represent a phenyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a butyl group, and X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a phenylene group, a methylene group, an ethylene group, an n-propylene group, an isopropylene group or a butylene group, in formula [1h], n represents an integer of 0 to 3; In formula [1i], m represents the integer of 0-3).

(B) Component: The at least 1 sort(s) of polymer chosen from the polyimide precursor and polyimide obtained by making a diamine component and a tetracarboxylic-acid component react.

(2) The diamine component in the polymer of the said (B) component contains the diamine compound which has a structure shown by following formula [2a], The composition as described in said (1) characterized by the above-mentioned.

[Formula 3]

(in formula [2a], a represents the integer of 0-4).

(3) The composition according to (1) above, wherein the diamine component in the polymer of the component (B) contains a diamine compound having a structure represented by the following formula [2a-1].

[Formula 4]

(in formula [2a-1], a represents the integer of 0-4, n represents the integer of 1-4).

(4) The diamine component in the polymer of the component (B) contains at least one selected from diamine compounds having a structure represented by the following formula [2b], in (1) to (3) above, characterized in that The composition as described in any one.

[Formula 5]

(In formula [2b], Y is a substituent having a structure selected from the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5] , and m represents an integer of 1 to 4).

[Formula 6]

(in formula [2b-1], a represents an integer of 0 to 4, in formula [2b-2], Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15) , -O-, -CH ₂ O-, -COO- or -OCO-, Y ² is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ is represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ is a benzene ring or a cyclohexane ring or a divalent cyclic group selected from a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, wherein any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms; It may be substituted with a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, and these rings Any hydrogen atom on the type group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is 0 an integer of to 4, Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, formula [2b- In 3], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-, Y ⁸ represents an alkyl group having 8 to 22 carbon atoms, formula [2b In -4], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and in formula [2b-5], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms).

(5) The tetracarboxylic acid component in the polymer of the component (B) contains at least one selected from the compound represented by the following formula [3], in the above (1) to (4) The composition as described in any one.

[Formula 7]

(In formula [3], Z<^1> is group of a structure chosen from following formula [3a] - a formula [3j]).

[Formula 8]

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

(6) (C) Said (1)- containing at least 1 sort(s) of solvent chosen from N-methyl-2-pyrrolidone, N-ethyl-2- pyrrolidone, and (gamma)-butyrolactone as a component The composition according to any one of (5) above.

(7) (D) In any one of said (1) - said (6) containing as a component at least 1 type of solvent chosen from the solvent shown by following formula [D-1] - formula [D-3] described composition.

[Formula 9]

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ represents a C1-C4 alkyl group).

(8) (E) at least one selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether as component (E) The composition according to any one of (1) to (7), which contains a solvent.

(9) A resin film obtained from the composition according to any one of (1) to (8).

(10) Liquid-crystal aligning agent obtained from the composition in any one of said (1) - said (8).

(11) The liquid crystal aligning film obtained using the liquid-crystal aligning agent as described in said (10).

(12) The liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent as described in said (10).

(13) The liquid crystal display element which has a liquid crystal aligning film as described in said (11) or said (12).

(14) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound that polymerizes by at least one of active energy rays and heat is disposed between the pair of substrates; , The liquid crystal aligning film according to the above (11) or (12), wherein the liquid crystal aligning film is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(15) It has the liquid crystal aligning film as described in said (14), The liquid crystal display element characterized by the above-mentioned.

(16) A liquid crystal aligning film comprising a liquid crystal layer between a pair of substrates provided with an electrode and containing a polymerizable group that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates; It is used for the liquid crystal display element manufactured through the process of polymerizing the said polymerizable group, applying a voltage between the said electrodes, The liquid crystal aligning film as described in said (11) or said (12) characterized by the above-mentioned.

(17) It has the liquid crystal aligning film as described in said (16), The liquid crystal display element characterized by the above-mentioned.

A composition containing at least one polymer selected from a polyimide precursor or polyimide obtained by reacting a cellulose-based polymer having a specific structure of the present invention and a diamine component with a tetracarboxylic acid component has high transparency of the resin film, Decomposition of the resin film accompanying irradiation with light can be suppressed.

Moreover, even if the liquid-crystal aligning agent which consists of the composition of this invention irradiates light in the state with the insulating film which consists of an organic member under a liquid crystal aligning film, it can form the liquid crystal aligning film excellent in voltage retention. Therefore, it becomes possible for the liquid crystal display element which has a liquid crystal aligning film obtained by this to have high reliability.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor came to complete this invention by obtaining the following knowledge.

This invention has a composition containing the following (A) component and (B) component, a liquid-crystal aligning agent, the resin film obtained using this composition, the liquid-crystal aligning film obtained using this liquid-crystal aligning agent, Furthermore, this liquid crystal aligning film has It relates to a liquid crystal display element.

(A) Component: The polymer (it is also mentioned a specific cellulosic polymer) which has a structure shown by following formula [1].

[Formula 10]

(In formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represents a group having at least one structure selected from the following formulas [1a] to [1m], n represents an integer of 100 to 1000000).

[Formula 11]

(In formulas [1c] to [1m], X ⁷ and X ⁸ each independently represent a phenyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a butyl group, and X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a phenylene group, a methylene group, an ethylene group, an n-propylene group, an isopropylene group or a butylene group, in formula [1h], n represents an integer of 0 to 3; In formula [1i], m represents the integer of 0-3).

(B) Component: At least 1 type of polymer selected from the polyimide precursor or polyimide obtained by making a diamine component and a tetracarboxylic-acid component react (it is also called a specific polyimide type polymer).

The specific cellulosic polymer of the present invention has higher transparency than the polyimide-based polymer. Therefore, the resin film obtained from the composition of this invention hardly absorbs light, such as an ultraviolet-ray, compared with that obtained from the normal polyimide-type polymer, and decomposition|disassembly of the resin film does not occur easily by this.

Moreover, since the composition of this invention contains the specific polyimide-type polymer excellent in light resistance and heat resistance with a specific cellulosic polymer, the stability of the resin film with respect to light and heat becomes higher.

Since the specific cellulosic polymer of the present invention has many OH groups (hydroxyl groups) and COOH groups (carboxylic acid groups), ionic impurities such as metals and low molecular weight organic compounds can be trapped. Therefore, even if the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention irradiates light in the state with the insulating film which consists of an organic member under a liquid crystal aligning film, it turns into a liquid crystal aligning film excellent in voltage retention.

Moreover, since the liquid-crystal aligning agent of this invention contains a specific polyimide-type polymer, with the characteristic of the voltage retention mentioned above, the ability to orientate a liquid crystal (it is also called liquid-crystal orientation) and the characteristic which gives a pretilt angle It is also possible to form an excellent liquid crystal aligning film.

From the above point, the composition of this invention can form the resin film with high transparency. And even if the liquid-crystal aligning agent obtained from the composition of this invention irradiates light in the state with the insulating film which consists of an organic member under a liquid-crystal aligning film, it is excellent in voltage retention, Furthermore, the characteristic which provides liquid-crystal orientation and a pretilt angle An excellent liquid crystal aligning film can also be formed.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in more detail.

<Specific cellulosic polymer>

The specific cellulosic polymer which is (A) component of this invention is a polymer of the structure shown by following formula [1].

[Formula 12]

In formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having at least one type of structure selected from the following formulas [1a] to [1m].

[Formula 13]

In the formulas [1c] to [1m], X ⁷ and X ⁸ each independently represent a phenyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a butyl group, and X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a phenylene group, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, or a butylene group.

In formula [1h], n represents the integer of 0-3. Especially, the integer of 0 or 1 is preferable.

In formula [1i], m represents the integer of 0-3. Especially, the integer of 0 or 1 is preferable.

In formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a structure selected from formulas [1a] to [1m], but even if these structures are one and two or more types may be used. In particular, it is preferable to use two or more types from the point of the applicability|paintability of the solubility with respect to the solvent of a specific cellulose polymer, a composition, or a liquid-crystal aligning agent. It is especially preferable to use the structure of a formula [1a], and the structure of a formula [1b] - a formula [1m]. Furthermore, it is preferable to use the structure of the formula [1a], the structure of the formula [1c], the structure of the formula [1d], the structure of the formula [1e], the structure of the formula [1h], or the structure of the formula [1i] .

In formula [1], n represents the integer of 100-1,000,000. Especially, the point of the handleability at the time of adjusting as the solubility to the solvent of a specific cellulose polymer, a composition, or a liquid-crystal aligning agent to 100-500,000 are preferable. More preferably, it is 100-100,000.

Although the following are mentioned as a specific example of the specific cellulosic polymer of this invention, it is not limited to these examples.

For example, cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, methyl ethyl cellulose, acetyl cellulose, cellulose propionate, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose , ethyl hydroxyethyl cellulose, hydroxybutyl methyl cellulose, hydroxypropyl methyl cellulose phthalate, methyl amino cellulose, ethyl amino cellulose, propyl amino cellulose, benzyl cellulose, tribenzoyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, Carboxymethylcellulose, carboxymethylethylcellulose, or carboxymethylhydroxyethylcellulose is mentioned. Among them, methylcellulose, ethylcellulose, propylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate, benzyl Cellulose, cellulose acetate propionate, carboxymethylethylcellulose or carboxymethylhydroxyethylcellulose is preferable. More preferably, methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose phthalate or carboxymethyl ethyl cellulose. Particularly preferred are methylcellulose, ethylcellulose, acetylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylhydroxyethylcellulose or hydroxypropylmethylcellulose phthalate.

These specific cellulose derivatives are generally available. Moreover, there is no restriction|limiting in particular in the method of introduce|transducing the structure shown by Formula [1b] - Formula [1m], An existing method can be used.

For example, in the case of introducing the structure of formula [1b], a method of reacting cellulose and benzyl chloride in the presence of an alkali. In the case of introducing the structure of formula [1c], cellulose and ^{a halogen compound having X 7} are reacted with an alkali A method of reacting in the presence or introducing the structure of formula [1d], a method of reacting cellulose with ^{an acid chloride compound having a structure of X 8 in} the presence of an alkali, a method of reacting cellulose with acetic anhydride, formula [1e] In the case of introducing the structure of , ^{a method of reacting cellulose with a halogen compound having a structure of X 9} -OH in the presence of an alkali, when introducing the structure of formula [1f], having a structure of ^{cellulose and X 10 -COOH} A method of reacting a halogen compound in the presence of an alkali, a method of reacting ^{a halogen compound having a structure of X 11} -NH ₂ with cellulose in the case of introducing the structure of formula [1g] in the presence of an alkali, a structure of formula [1h] In the case of introduction, a method of reacting cellulose and phthalic acid, in the case of introducing the structure of formula [1i], a method of reacting cellulose with X ¹² and a halogen compound having a phthalic acid skeleton in the presence of an alkali, the structure of formula [1k] In the case of introducing , a method of reacting cellulose with maleic anhydride is exemplified.

These specific cellulosic polymers represented by the said Formula [1] are solubility and applicability|paintability with respect to the solvent of the specific cellulosic polymer of this invention, when it is set as a liquid crystal aligning film, The orientation of the liquid crystal, voltage retention, characteristics, such as an accumulation|storage charge Depending on the type, one type or a mixture of two or more types may be used.

<Specific polyimide-based polymer>

The specific polyimide-based polymer as component (B) of the present invention is a polyimide precursor obtained by reacting a diamine component with a tetracarboxylic acid component or a polymer selected from polyimide.

A polyimide precursor is a structure shown by following formula [A].

[Formula 14]

(In formula [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and may be the same or different, respectively. , A ³ and A ⁴ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, and may be the same or different, respectively, and n represents a positive integer).

As said diamine component, it is a diamine compound which has two primary or secondary amino groups in a molecule|numerator, As a tetracarboxylic-acid component, it is a tetracarboxylic-acid compound, tetracarboxylic dianhydride, and a tetracarboxylic-acid dihalide compound. and a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound.

The specific polymer of this invention is a repeating unit represented by a following formula [D] from the reason that it is obtained comparatively easily by using tetracarboxylic dianhydride represented by a following formula [B], and the diamine compound represented by a following formula [C] as a raw material. A polyamic acid having the structural formula of or a polyimide obtained by imidizing the polyamic acid is preferable.

[Formula 15]

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

[Formula 16]

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

In addition, the polymers of the usual synthesis techniques, equation [D] obtained in the above-mentioned formula [A] represented by A ¹ and A carbon number of alkyl group of 1-8 of Figure ^2, and the equation [A] represented by A ³ and A ⁴ An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

<Diamine component>

A well-known diamine compound can be used as a diamine component for manufacturing the specific polyimide-type polymer which is (B) component of this invention.

Especially, it is preferable to use the diamine compound which has a structure shown by following formula [2a].

[Formula 17]

In formula [2a], a represents the integer of 0-4. Among them, an integer of 0 or 1 is preferable from the viewpoints of availability of raw materials and easiness of synthesis.

As a diamine compound which has a structure shown by a formula [2a], the diamine compound specifically shown by a following formula [2a-1] is mentioned.

[Formula 18]

In formula [2a-1], a represents the integer of 0-4. Among them, 0 or 1 is preferable from the viewpoints of availability of raw materials and easiness of synthesis.

In formula [2a-1], n represents the integer of 1-4. Especially, 1 is preferable at the point of synthesis|combination easiness.

Although the method of manufacturing the diamine compound shown by Formula [2a] of this invention is not specifically limited, What is shown below as a preferable method is mentioned. As an example, the diamine compound represented by a formula [2a-1] is obtained by synthesizing a dinitro body compound represented by a following formula [2a-A], further reducing the nitro group and converting it into an amino group.

[Formula 19]

(in formula [2a-A], a represents the integer of 0-4, n represents the integer of 1-4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [2a-A] is not particularly limited, and is usually palladium-carbon in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcoholic solvent. , platinum oxide, Raney nickel, platinum black, rhodium-alumina or platinum carbon sulfide, etc. as a catalyst, and the reaction is carried out under hydrogen gas, hydrazine or hydrogen chloride.

As a diamine compound shown by Formula [2a] of this invention, the diamine compound further shown by a following formula [2a-2] - a formula [2a-5] is also mentioned.

[Formula 20]

In formula [2a-2], A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, single bonds, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH- , -NHCO-, -COO- or -OCO- are preferable. More preferably, they are a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, or -N(CH ₃ )-.

Formula [2a-2] from, m ¹ and m ² represents an integer of 0 to 4, respectively, and m ¹ + m ² is an integer of 1-4. In particular, m ¹ + m ² is 1 or 2 are preferred.

In the formula ^[2a-3], m 3 and m ⁴ represents an integer of 1-5, respectively. Among these, 1 or 2 is preferable from the point of synthesis|combination easiness.

In the formula [2a-4], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. Especially, a C1-C3 linear alkyl group is preferable.

In formula [2a-4], m<^5> represents the integer of 1-5. Especially, 1 or 2 is preferable.

In formula [2a-5], A ³ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO- or -OCO- is preferable. More preferable are -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-.

In formula [2a-5], m<^6> represents the integer of 1-4. Among them, 1 is preferable from the viewpoint of synthesis easiness.

It is preferable that the diamine compounds shown by the said formula [2a-1] - a formula [2a-5] are 20 mol% - 100 mol% in all the diamine components, It is preferable that they are 30 mol% - 80 mol% more preferably .

When the diamine compound shown by the said Formula [2a-1] - a formula [2a-5] sets it as the solubility to the solvent of the specific polyimide-type polymer of this invention, the applicability|paintability of a composition, and a liquid crystal aligning film, the orientation of a liquid crystal , one type or a mixture of two or more types may be used depending on characteristics such as , voltage retention, and accumulated charge.

It is preferable to use the diamine compound shown by a following formula [2b] as a diamine component for manufacturing the specific polyimide-type polymer of this invention.

[Formula 21]

In formula [2b], Y is at least one structure selected from the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5] represents the substituent of, and m represents the integer of 0-4.

[Formula 22]

In formula [2b-1], a represents the integer of 0-4. Among them, an integer of 0 or 1 is preferable from the viewpoints of availability of raw materials and easiness of synthesis.

In formula [2b-2], Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or -OCO- indicates. Among them, from the viewpoint of availability of raw materials and ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- desirable. More preferable are a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-.

In the formula ^[2b-2], Y 2 represents a single bond or - represents a (b is an integer of _{1 ~ 15) - (CH 2} ) b. Among these, a single bond or - (CH _{2) b} - a (b is an integer of 1 to 10) are preferred.

In formula [2b-2], Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or -OCO- indicates. Among these, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- is preferable from the point of synthesis easiness. More preferably, they are a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-.

In the formula [2b-2], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. You may be substituted with an alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom. Further, Y ⁴ may be a divalent organic group selected from an organic group having 12 to 25 carbon atoms and having a steroid skeleton. Especially, a C12-C25 organic group which has a benzene ring, a cyclohexane ring, or a steroid skeleton from the point of synthetic|combination easiness is preferable.

In the formula [2b-2], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atoms on these cyclic groups are an alkyl group having 1 to 3 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. You may be substituted with an alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferable.

In formula [2b-2], n represents the integer of 0-4. Especially, the point of the availability of a raw material and the easiness of a synthesis|combination to 0-3 are preferable. More preferably, it is 0-2.

In formula [2b-2], Y<^6> represents a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group. Especially, a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, it is a C1-C12 alkyl group or a C1-C12 alkoxyl group. Especially preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxyl group.

^{As a preferable combination of Y 1} , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in Formula [2b-2] for constituting the substituent Y in Formula [2b], International Publication WO2011/ Combinations similar to those of (2-1) to (2-629) disclosed in Tables 6 to 47 of paragraphs 13 to 34 of 132751 (published on October 27, 2011) are exemplified. In addition, in each table of International Publication, there is Y ¹ ~ Y ⁶ of the present invention shown as Y1 ~ Y6, Y1 ~ Y6 are changed by reading the Y ¹ ~ Y ^6.

In formula [2b-3], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH-, or -NHCO-. Especially, -O-, -CH ₂ O-, -COO-, or -CONH- is preferable. More preferably, they are -O-, -COO-, or -CONH-.

In formula [2b-3], Y<^8> represents a C8-C22 alkyl group.

In formula [2b-4], Y ⁹ and Y ¹⁰ each independently represent a C1-C12 hydrocarbon group.

In the formula [2b-5], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms.

Although the method of manufacturing the diamine compound shown by Formula [2b] of this invention is not specifically limited, What is shown below is mentioned as a preferable method. As an example, the diamine compound shown by Formula [2b] is obtained by synthesize|combining the dinitro body compound shown by following formula [2b-A], reducing the nitro group further, and converting it into an amino group.

[Formula 23]

(In formula [2b-A], Y is at least selected from formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5] It represents the substituent of one structure, and m represents the integer of 0-4).

There is no restriction|limiting in particular in the method of reducing the dinitro group of the dinitro body compound represented by Formula [2b-A], Usually, palladium-carbon in solvent, such as ethyl acetate, toluene, tetrahydrofuran, dioxane, or an alcoholic solvent. , platinum oxide, Raney nickel, platinum black, rhodium-alumina or platinum carbon sulfide, etc. as a catalyst, and the reaction is carried out under hydrogen gas, hydrazine or hydrogen chloride.

Although the specific structure of the diamine compound shown by Formula [2b] of this invention is mentioned below, it is not limited to these examples.

That is, as a diamine compound shown by Formula [2b], m-phenylenediamine, 2, 4- dimethyl- m-phenylenediamine, 2, 6- diaminotoluene, 2, 4- diamino phenol, 3,5 -Diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol other than a structure shown by following formula [2b-6] - [2b-46] of diamine compounds.

[Formula 24]

(In formula [2b-6] - formula [2b-9], A ¹ represents a C1-C22 alkyl group or a fluorine-containing alkyl group).

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

(In formulas [2b-34] to [2b-36], R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² represents carbon number 1 to 22 alkyl group, alkoxy group, fluorine-containing alkyl group or fluorine-containing alkoxy group).

[Formula 37]

(In formulas [2b-37] to [2b-39], R ³ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -, and R ⁴ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

[Formula 38]

(In formulas [2b-40] and [2b-41], R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ - or -O-, and R ⁶ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group).

[Formula 39]

(In formulas [2b-42] and [2b-43], R ⁷ represents an alkyl group having 3 to 12 carbon atoms. The cis-trans isomerism of 1,4-cyclohexylene is preferably a trans isomer, respectively).

[Formula 40]

(In formulas [2b-44] and [2b-45], R ⁸ represents an alkyl group having 3 to 12 carbon atoms. The cis-trans isomerism of 1,4-cyclohexylene is preferably a trans isomer, respectively).

[Formula 41]

(In formula [2b-46], B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and B ² represents an oxygen atom or -COO-* (however, the bond to which "*" is attached is bonded to B ³ ), B ¹ is an oxygen atom or -COO-* (provided that the bond to which "*" is attached is ( CH ₂₎ engages with a ²⁾ represents a. in addition, a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 ~ 10, a ³ represents an integer of 0 or 1).

The composition using the diamine compound of the structure in which the substituent Y in a formula [2b] is represented by a formula [2b-2] among the diamine compounds shown by the said formula [2b] can make the hydrophobicity of a resin film high. Moreover, when it is set as a liquid crystal aligning film, the pretilt angle of a liquid crystal can be made high. In that case, for the purpose of enhancing these effects, among the above diamine compounds, diamine compounds represented by formulas [2b-28] to [2b-39] or [2b-42] to [2b-46] are used. it is preferable A more preferable thing is a diamine compound shown by a formula [2b-24] - a formula [2b-39] or a formula [2b-42] - a formula [2b-46]. Moreover, in order to heighten these effects more, it is preferable that these diamine compounds are 5 mol% or more and 80 mol% or less of the whole diamine component. More preferably, these diamine compounds are 5 mol% or more and 60 mol% of the whole diamine component from the point of the applicability|paintability of a composition and a liquid-crystal aligning agent, and the electrical characteristic as a liquid crystal aligning film.

The diamine compound represented by the said Formula [2b] depends on characteristics, such as solubility and applicability|paintability with respect to the solvent of the specific polyimide-type polymer of this invention, the orientation of the liquid crystal in setting it as a liquid crystal aligning film, voltage retention, accumulated electric charge, etc. , one type or a mixture of two or more types can be used.

As a diamine component for manufacturing the specific polyimide-type polymer of this invention, diamine compounds other than the diamine compound shown by a formula [2a-1] - a formula [2a-5], and a diamine compound shown by a formula [2b] (other Also referred to as a diamine compound) can be used as the diamine component. Although the specific example of another diamine compound is given below, it is not limited to these examples.

For example, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3 , 3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'- Biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diamino Biphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2' -diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether , 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl 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'-thiodianiline, 4 ,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diamino Diphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) Amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-dia Minobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2, 8-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-phenyl Lenbis(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-aminophenyl)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-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3- Aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoro lopropane, 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-amino) Phenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane 1,6- bis(3-aminophenoxy)hexane 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-(4-amino) Phenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, 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-dia and minononane, 1,10-diaminodecane, 1,11-diaminoundecane, or 1,12-diaminododecane.

Moreover, as another diamine compound, what has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, or a heterocyclic ring in a diamine side chain, and what has a macrocyclic substituent which consists of these can also be mentioned. The diamine compound specifically, shown by following formula [DA1] - [DA13] can be illustrated.

[Formula 42]

[Formula 43]

[Formula 44]

(In formulas [DA1] to [DA6], A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-; A ² represents a C1-C22 linear or branched alkyl group or a C1-C22 linear or branched fluorine-containing alkyl group).

[Formula 45]

(in formula [DA7], p represents the integer of 1-10).

Unless the effect of this invention is impaired, the diamine compound shown by a following formula [DA8] - a formula [DA13] can also be used as another diamine compound.

[Formula 46]

[Formula 47]

(in formula [DA10], m represents the integer of 0-3, and in formula [DA13], n represents the integer of 1-5).

Moreover, unless the effect of this invention is impaired, the diamine compound shown by a following formula [DA14] can also be used.

[Formula 48]

(in formula [DA14], A ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ ) - or a divalent organic group selected from _{-N(CH 3} ^{)CO-, A 2} is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group, and A ³ is bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO- or -O(CH ₂ ) _m - (m is an integer of 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4).

Moreover, as another diamine compound, the diamine compound shown by a following formula [DA15] and a formula [DA16] can also be used.

[Formula 49]

The other diamine compounds described above, depending on the solubility of the specific polyimide-based polymer of the present invention in the solvent, the coating properties of the composition, the orientation of the liquid crystal in the case of a liquid crystal aligning film, the voltage retention, the accumulated charge, etc. You may use 1 type or in mixture of 2 or more types.

<Tetracarboxylic acid component>

As a tetracarboxylic-acid component for manufacturing the specific polyimide-type polymer which is (B) component of this invention, the tetracarboxylic acid which is tetracarboxylic dianhydride shown by following formula [3], and its tetracarboxylic-acid derivative. , It is preferable to use a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound (all of which are collectively referred to as a specific tetracarboxylic acid component).

[Formula 50]

In formula [3], Z<^1> is group of a structure chosen from a following formula [3a] - a formula [3j].

[Formula 51]

The formula ^{[3a], Z 2 ~ Z} 5 is may be a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, respectively, be the same or different.

In formula [3g], Z<^6> and Z<^7> represent a hydrogen atom or a methyl group, and may be same or different, respectively.

In the structure shown in Formula [3] which is a specific tetracarboxylic-acid component of this invention, Z<^1> is a point of the ease of synthesis|combination or the ease of polymerization reactivity at the time of manufacturing a polymer, Formula [3a], Formula [3c] , a structure represented by a formula [3d], a formula [3e], a formula [3f], or a formula [3g] is preferable. A more preferable structure is a structure shown by a formula [3a], a formula [3e], a formula [3f], or a formula [3g], Especially preferable is a formula [3e], a formula [3f], or a formula [3g].

It is preferable that the specific tetracarboxylic-acid component of this invention is 1 mol% or more in all the tetracarboxylic-acid components. More preferably, it is 5 mol% or more, and especially preferable is 10 mol% or more.

Moreover, when using the specific tetracarboxylic-acid component of the structure of a formula [3e], a formula [3f], or a formula [3g], the usage-amount shall be 20 mol% or more of the whole tetracarboxylic-acid component, and the desired effect is obtained Preferably it is 30 mol% or more. Moreover, the tetracarboxylic-acid component of the structure of a formula [3e], a formula [3f], or a formula [3g] may be sufficient as all the tetracarboxylic-acid components.

As long as the effect of this invention is not impaired for the specific polyimide-type polymer of this invention, other tetracarboxylic-acid components other than a specific tetracarboxylic-acid component can be used. As another tetracarboxylic-acid component, the tetracarboxylic-acid compound shown below, tetracarboxylic dianhydride, a tetracarboxylic-acid dihalide compound, a tetracarboxylic-acid dialkyl ester compound, or a tetracarboxylic-acid dialkyl ester dihalide compound can be heard

That is, as the other tetracarboxylic acid component, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5, 8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3′,4,4′-biphenyltetracarboxylic acid 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'-diphenylsulfonetetracarboxylic acid, 3,4,9 , 10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

A specific tetracarboxylic-acid component and another tetracarboxylic-acid component are the solubility to the solvent of the specific polyimide-type polymer of this invention, the applicability|paintability of a composition, the orientation of the liquid crystal in setting it as a liquid crystal aligning film, voltage retention, According to characteristics, such as an accumulation|storage electric charge, you may use 1 type or in mixture of 2 or more types.

<Method for producing specific polyimide-based polymer>

In the present invention, the method for synthesizing a specific polyimide-based polymer is not particularly limited. Usually, it is obtained by making a diamine component and a tetracarboxylic-acid component react. In general, polyamic acid is obtained by reacting at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acid and derivatives thereof with a diamine component composed of one or more diamine compounds. Specifically, a method of polycondensing tetracarboxylic dianhydride and a primary or secondary diamine compound to obtain polyamic acid, a method of dehydrating polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound to polyamide A method of obtaining an acid or a method of obtaining a polyamic acid by polycondensing a tetracarboxylic acid dihalide and a primary or secondary diamine compound is used.

In order to obtain polyamic-acid alkylester, the method of polycondensing the tetracarboxylic acid which dialkylesterified the carboxylic acid group, and the primary or secondary diamine compound, The tetracarboxylic-acid dihalide which carried out the dialkylesterification of the carboxylic acid group. and a method of polycondensing a primary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.

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

Reaction of a diamine component and a tetracarboxylic-acid component is normally performed by carrying out a diamine component and a tetracarboxylic-acid component in an organic solvent. It will not specifically limit, if the produced|generated polyimide precursor melt|dissolves as an organic solvent used in that case. Although the specific example of the organic solvent used for reaction is given below, 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, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formulas [D-1] to [D-3] ], and the like.

[Formula 52]

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents a C1-C4 alkyl group).

These may be used independently and may be mixed and used. Moreover, even if it is a solvent in which a polyimide precursor is not dissolved, you may use it in the range in which the produced|generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since moisture in an organic solvent inhibits a polymerization reaction and becomes a cause to hydrolyze the produced|generated polyimide precursor by extension, it is preferable to use the thing which dehydrated and dried the organic solvent.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a 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 by dispersing or dissolving it in the organic solvent. , conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc., any of these methods You may use it. In the case of reacting using a plurality of diamine components or tetracarboxylic acid components, respectively, they may be reacted in a pre-mixed state, may be individually and sequentially reacted, or individually reacted low molecular weight substances may be mixed and reacted to form a polymer. You can do it. Although the polymerization temperature in that case can select arbitrary temperatures of -20 degreeC - 150 degreeC, Preferably it is the range of -5 degreeC - 100 degreeC. In addition, although the reaction can be carried out at any concentration, when the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, Preferably it is 1-50 mass %, More preferably, it is 5-30 mass %. The reaction initial stage can be performed at high concentration, and an organic solvent can be added after that.

In the polymerization reaction of a polyimide precursor, it is preferable that ratio of the total number of moles of a diamine component and the total number of moles of a tetracarboxylic-acid component is 0.8-1.2. As in a typical polycondensation reaction, the closer this molar ratio to 1.0, the greater the molecular weight of the polyimide precursor produced.

The polyimide of the present invention is a polyimide obtained by ring-closing the polyimide precursor described above, and in this polyimide, the ring-closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%, and is not necessarily 100%. It can be adjusted arbitrarily according to

As a method of imidating a polyimide precursor, the thermal imidation which heats the solution of a polyimide precursor as it is, or catalyst imidation which adds a catalyst to the solution of a polyimide precursor is mentioned.

The temperature in the case of thermal imidation of a polyimide precursor in a solution is 100 degreeC - 400 degreeC, Preferably it is 120 degreeC - 250 degreeC, It is preferable to carry out, removing the water produced|generated by the imidation reaction to the outside of a system.

Catalyst imidation of a polyimide precursor is -20-250 degreeC, adding a basic catalyst and an acid anhydride to the solution of a polyimide precursor, Preferably it can perform by stirring at 0-180 degreeC. The amount of the basic catalyst is 0.5 to 30 mole times of the amic acid group, preferably 2 to 20 mole times, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times of the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, or trioctylamine, and among them, pyridine is preferable because it has suitable basicity to advance the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferably used because purification after completion of the reaction becomes easy. The imidation rate by catalytic imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

When collect|recovering the produced|generated polyimide precursor or polyimide from the reaction solution of a polyimide precursor or a polyimide, what is necessary is just to inject|throw-in a reaction solution to a solvent and just to precipitate. 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, and water. The polymer precipitated by putting it in a solvent can be collected by filtration, and then dried under normal pressure or reduced pressure, at room temperature or by heating. Moreover, if the polymer which carried out precipitation collection|recovery is made to dissolve again in an organic solvent, and operation of reprecipitation collection|recovery is repeated 2-10 times, the impurity in a 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 solvents selected from these is preferable because the efficiency of purification further increases.

The molecular weight of the specific polyimide-type polymer of this invention is the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method, when the intensity|strength of the resin film or liquid crystal aligning film obtained there, workability|workability at the time of film formation, and coating film property are considered It is preferable to set it as 5,000-1,000,000, More preferably, it is 10,000-150,000.

<Composition, liquid crystal aligning agent>

The composition or liquid crystal aligning agent of the present invention is a coating solution for forming a resin film or liquid crystal aligning film (collectively referred to as a resin film), and a resin film containing a specific cellulose polymer, a specific polyimide polymer and a solvent to form a resin film application solution for

When the ratio of the specific cellulose polymer in the composition of this invention or a liquid-crystal aligning agent and a specific polyimide-type polymer makes the ratio of a specific polyimide-type polymer 1, the ratio of a specific cellulose polymer is 0.1-9. Especially preferable are 0.2-4.

As for all the polymer components in the composition or liquid-crystal aligning agent of this invention, the specific cellulose polymer of this invention and a specific polyimide type polymer may be sufficient as all, and other polymers other than that may be mixed. In that case, content of other polymers other than that is 0.5 mass % - 15 mass % of the specific polymer of this invention, Preferably they are 1 mass % - 10 mass %. As another polymer other than that, the polyimide-type polymer which does not use the diamine compound shown by the said Formula [2a-1] - a formula [2a-5], the diamine compound shown by a formula [2b], and a specific tetracarboxylic-acid component can be heard Furthermore, polymers other than a cellulosic polymer and a polyimide-type polymer, specifically, an acrylic polymer, a methacryl polymer, polystyrene, polyamide, or polysiloxane, etc. are mentioned.

It is preferable that content of the organic solvent in the composition of this invention or the organic solvent in a liquid-crystal aligning agent forms a uniform resin film by application|coating that content of an organic solvent is 70-99.9 mass %. This content can be suitably changed with the film thickness of the resin film made into the objective, or a liquid crystal aligning film.

The organic solvent used for the composition of this invention or a liquid-crystal aligning agent will not be specifically limited if it is an organic solvent (it is also mentioned a good solvent) in which a specific cellulose-type polymer and a specific polyimide-type polymer are dissolved. Although the specific example of a good solvent is given below, 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. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, or a solvent represented by the above formulas [D-1] to [D-3], etc. can be heard These may be used independently and may be mixed and used.

Among these, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone (above (also referred to as component (C)). Furthermore, when the solubility with respect to the solvent of a specific cellulosic polymer and a specific polyimide-type polymer is high, the solvent (it is mentioned above (D) component) shown by said formula [D-1] - a formula [D-3] It is preferable to use

It is preferable that the good solvent in the composition of this invention or a liquid-crystal aligning agent is 10-100 mass % of the whole solvent contained in a composition or a liquid-crystal aligning agent. Especially, 20-90 mass % is preferable. More preferably, it is 30-80 mass %.

As long as the composition or liquid-crystal aligning agent of this invention does not impair the effect of this invention, the organic solvent (also called a poor solvent) which improves the coating-film property and surface smoothness of the resin film or liquid-crystal aligning film when a composition or a liquid-crystal aligning agent is apply|coated do) 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, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoacetate Ethyl ether acetate, diethylene glycol monobutyl ether Le acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate , n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxymethylpropionate, 3-ethoxymethylethylethylpropionate, 3-methoxyethylpropionate, 3-ethoxypropionic acid, 3-methyl Toxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionate butyl, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester or the above formula [D] -1] - the solvent shown by a formula [D-3], etc. are mentioned.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether (also referred to as component (E) above), or the above It is preferable to use the solvent shown by one said formula [D-1] - a formula [D-3].

It is preferable that these poor solvents are 1-70 mass % of the whole organic solvent contained in a composition or a liquid-crystal aligning agent. Especially, 1-60 mass % is preferable. More preferably, it is 5-60 mass %.

In the composition or liquid-crystal aligning agent of this invention, unless the effect of this invention is impaired, the crosslinkable compound which has an epoxy group, an isocyanate group, an oxetane group, or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group A crosslinkable compound having at least one substituent selected from the group or a crosslinkable compound having a polymerizable unsaturated bond may be introduced. It is necessary to have two or more of these substituents and a polymerizable unsaturated bond in a crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminodiphenylene , tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyletherethane, triphenylglycidyletherethane, bisphenolhexafluoroacet Diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis( 2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, 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-epoxyprop and epoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol.

The crosslinkable compound which has an oxetane group is a crosslinkable compound which has at least two oxetane groups shown by following formula [4].

[Formula 53]

It is a crosslinking|crosslinked compound specifically, shown by a following formula [4-1] - a formula [4-11].

[Formula 54]

(in formula [4-1], n represents the integer of 1-3).

[Formula 55]

[Formula 56]

[Formula 57]

(in formula [4-7], n represents the integer of 1-3, in formula [4-8], n represents the integer of 1-3, and in formula [4-9], n is 1-100 represents an integer of ).

[Formula 58]

(in formula [4-11], n represents the integer of 1-10).

As a crosslinkable compound which has a cyclocarbonate group, it is a crosslinkable compound which has at least two cyclocarbonate groups shown by following formula [5].

[Formula 59]

It is a crosslinking|crosslinked compound specifically, shown by a following formula [5-1] - a formula [5-37].

[Formula 60]

[Formula 61]

[Formula 62]

[Formula 63]

[Formula 64]

[Formula 65]

[Formula 66]

[Formula 67]

[Formula 68]

[Formula 69]

[Formula 70]

[Formula 71]

(in formula [5-24], n shows the integer of 1-10, and in formula [5-25], n shows the integer of 1-10).

[Formula 72]

[Formula 73]

[Formula 74]

[Formula 75]

[Formula 76]

(in formula [5-36], n represents the integer of 1-100, and in formula [5-37], n represents the integer of 1-10).

Moreover, the polysiloxane which has at least 1 sort(s) of structure shown to a following formula [5-38] - a formula [5-40] is also mentioned.

[Formula 77]

(In formula [5-38] - formula [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a structure represented by formula [5], a hydrogen atom, a hydroxyl group, and 1 to carbon atoms The alkyl group of 10, an alkoxyl group, an aliphatic ring, or an aromatic ring is shown, and at least 1 shows the structure shown by Formula [5]).

More specifically, the compounds of the following formulas [5-41] and [5-42] are mentioned.

[Formula 78]

(in formula [5-42], n represents the integer of 1-10).

Examples of the crosslinkable compound having at least one substituent 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, for example, a melamine resin, a urea resin, and guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin or ethyleneurea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. This melamine derivative or benzoguanamine derivative may exist as a dimer or a trimer. These preferably have 3 or more and 6 or less methylol groups or alkoxymethyl groups on average per triazine ring.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750, in which an average of 3.7 methoxymethyl groups are substituted per triazine ring, and MW in which an average of 5.8 methoxymethyl groups are substituted per triazine ring. -30 (above, manufactured by Sanwa Chemical) Ina Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 Methoxymethylated melamine, Cymel 235, 236, 238, 212, 253 Methoxymethylated butoxymethylated melamine such as , 254, butoxymethylated melamine such as Cymel 506 and 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, methoxymethylated ethoxymethylated such as Cymel 1123 Benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, methoxymethylated ethoxymethylated benzoguan containing carboxyl group such as Cymel 1125-80 Namine (above, the Mitsui cyanamide company make) is mentioned. Moreover, as an example of a glycoluril, a butoxymethylation glycoluril like Cymel 1170, a methylolation glycoluril like Cymel 1172, methoxymethylolation glycoluril like Powder Link 1174, etc. are mentioned.

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

More specifically, the crosslinking|crosslinked compound shown 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.

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 the molecule, such as acryloyloxyethoxytrimethylolpropane or glycerin polyglycidyl ether poly(meth)acrylate, and 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, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth)acrylic rate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as diglycidyl ester di(meth)acrylate or hydroxypivalate neopentyl glycol di(meth)acrylate, and 2-hydroxyethyl(meth)acryl Rate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy- 2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate or N-methylol (meth) The crosslinkable compound which has one polymerizable unsaturated group, such as acrylamide, in a molecule|numerator is mentioned.

Moreover, the compound shown by following formula [7] can also be used.

[Formula 79]

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

[Formula 80]

The compound is an example of a crosslinkable compound, but is not limited thereto. Moreover, the number of the crosslinking|crosslinked compounds used for the composition or liquid-crystal aligning agent of this invention may be one, and they may combine them two or more types.

It is preferable that content of the crosslinkable compound in the composition of this invention or a liquid-crystal aligning agent is 0.1-150 mass parts with respect to 100 mass parts of all the polymer components. In order for a crosslinking reaction to advance and to express the target effect, 0.1-100 mass parts is more preferable with respect to 100 mass parts of all polymer components, and 1-50 mass parts is the most preferable especially.

When it is set as a liquid crystal aligning film using the liquid-crystal aligning agent using the composition of this invention, the charge transfer in a liquid crystal aligning film is accelerated|stimulated, As a compound which accelerates|stimulates charge drop-off of the liquid crystal cell using this liquid crystal aligning film, International publication WO2011/132751 ( It is preferable to add the nitrogen-containing heterocyclic amine compound shown by Formula [M1] - Formula [M156] published on page 69 - page 73 of 2011.10.27 publication). Although you may add this amine compound directly to a composition, it is 0.1 mass % - 10 mass % with a suitable solvent, It is preferable to add after setting it as the solution of preferably 1 mass % - 7 mass %. It will not specifically limit, if it is an organic solvent in which the specific polyimide-type polymer mentioned above is dissolved as this solvent.

As long as the composition or liquid-crystal aligning agent of this invention does not impair the effect of this invention, the compound which improves the uniformity and surface smoothness of the film thickness of the resin film or liquid-crystal aligning film when a composition or a liquid-crystal aligning agent is apply|coated is used can Moreover, the compound etc. which improve the adhesiveness of a resin film or a liquid crystal aligning film, and a board|substrate can also be used.

As a compound which improves the uniformity of the film thickness of a resin film or a liquid crystal aligning film, and surface smoothness, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned.

More specifically, for example, eftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapac F171, F173, R-30 (above, manufactured by Dainippon Ink), Florad FC430, FC431 ( As mentioned above, the Sumitomo 3M company make), Asahi Guard AG710, Sufflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, the Asahi Glass company make) etc. are mentioned. To [ the usage ratio of these surfactant / 100 mass parts of all the polymer components contained in a composition or a liquid-crystal aligning agent ], Preferably it is 0.01-2 mass parts, More preferably, it is 0.01-1 mass part.

As a specific example of the compound which improves the adhesiveness of a resin film or a liquid crystal aligning film, and a board|substrate, the functional silane containing compound and epoxy group containing compound shown below are mentioned.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3 -Aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonylacetate, 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-tetraglycidyl ether Cydyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

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

In the composition or liquid-crystal aligning agent of this invention, other than the compound which makes said poor solvent, a crosslinkable compound, the compound which improves the uniformity and surface smoothness of the film thickness of a resin film or a liquid crystal aligning film, and a board|substrate, the compound made to adhere, the effect of this invention As long as it is a range in which is not inhibited, a dielectric or conductive substance for the purpose of changing electrical properties such as the dielectric constant or conductivity of the resin film or liquid crystal aligning film may be added.

<Resin film>

After apply|coating and baking the composition of this invention on a board|substrate, it can be used as a resin film. As a board|substrate used at this time, plastic substrates, such as a glass substrate, a silicon wafer, an acrylic board|substrate, a polycarbonate board|substrate, etc. can be used according to the target device. The coating method of the composition is not particularly limited, but industrially, a method performed by a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, a screen printing method, an offset printing method, a flexographic printing method, or an inkjet method is common. am. These can be appropriately selected according to the purpose.

After the composition is applied on the substrate, by heating means such as a hot plate, heat circulation type oven or IR (infrared) type oven, depending on the solvent used for the composition, 30 to 300°C, preferably 30 to 250 It can be made into a resin film by evaporating a solvent at the temperature of °C. The thickness of the resin film after baking can be adjusted in 0.01-100 micrometers according to the objective.

<Liquid crystal alignment film, liquid crystal display element>

After apply|coating and baking the liquid-crystal aligning agent using the composition of this invention on a board|substrate, it can orientate-process by a rubbing process, light irradiation, etc., and can be used as a liquid crystal aligning film. Moreover, in the case of a vertical alignment use, etc., it can use as a liquid crystal aligning film without an orientation process. It will not specifically limit as a board|substrate used at this time, if it is a board|substrate with high transparency, In addition to a glass substrate, plastic substrates, such as an acryl board|substrate and a polycarbonate board|substrate, etc. can be used. From a viewpoint of simplification of a process, it is preferable to use the board|substrate with which the ITO electrode etc. for liquid crystal drive were formed. In the reflective liquid crystal display device, an opaque substrate such as a silicon wafer can also be used as long as it is a one-sided substrate, and a material that reflects light such as aluminum can also be used as the electrode in this case.

Although the application method of a liquid-crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method, the spray method, etc., You may use these according to the objective.

After apply|coating a liquid-crystal aligning agent on a board|substrate, it is 30-300 degreeC according to the solvent used for a liquid-crystal aligning agent by heating means, such as a hot plate, heat circulation type oven, or IR (infrared) type|mold oven, Preferably can evaporate a solvent at the temperature of 30-250 degreeC, and can be set as a liquid crystal aligning film. When the thickness of the liquid crystal aligning film after baking is too thick, it becomes disadvantageous from the point of power consumption of a liquid crystal display element, and since the reliability of a liquid crystal display element may fall when too thin, Preferably it is 5-300 nm, More preferably, it is 10 ∼ 100 nm. When a liquid crystal is horizontally orientated or diagonally aligned, the liquid crystal aligning film after baking is processed by rubbing, 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 said method, a liquid crystal cell was manufactured by a well-known method, and it was set as the liquid crystal display element.

As a manufacturing method of a liquid crystal cell, a pair of board|substrates with a liquid crystal aligning film are prepared, a spacer is spread|dispersed on the liquid crystal aligning film of one board|substrate, a liquid crystal aligning film surface is made inside, and the other board|substrate is bonded together. ), the method of injecting and sealing a liquid crystal under reduced pressure, or the method of bonding a board|substrate together and sealing after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, etc. can be illustrated.

Moreover, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board|substrates provided with an electrode, The liquid crystal containing a polymeric compound which superposes|polymerizes by at least one of an active energy ray and a heat|fever between a pair of board|substrates. It is preferably used also for the liquid crystal display element manufactured through the process of superposing|polymerizing a polymeric compound by at least one of irradiation and heating of an active energy ray, arranging a composition and applying a voltage between electrodes. Here, as an active energy ray, an ultraviolet-ray is preferable. As an ultraviolet-ray, a wavelength is 300-400 nm, Preferably it is 310-360 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 irradiation of an ultraviolet-ray and heating simultaneously.

The liquid crystal display device is to control the pretilt of the liquid crystal molecules by the PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, a liquid crystal cell is assembled, and then ultraviolet rays are applied to the photopolymerizable compound in a state where a predetermined voltage is applied to the liquid crystal layer. and the like to control the pretilt of the liquid crystal molecules by the resulting polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is memorized even after 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, in the PSA system, since a rubbing process is not required, it is suitable for formation of the liquid-crystal layer of the vertically-aligned type in which it is difficult to control a pretilt by a rubbing process.

That is, after the liquid crystal display element of this invention obtains the board|substrate with a liquid crystal aligning film from the liquid-crystal aligning agent of this invention by said method, it manufactures a liquid crystal cell, and is polymerizable by at least one of irradiation of an ultraviolet-ray, and a heating. By polymerizing the compound, the alignment of the liquid crystal molecules can be controlled.

To give an example of liquid crystal cell production of the PSA system, a pair of substrates with a liquid crystal aligning film are prepared, a spacer is dispersed on the liquid crystal aligning film of one substrate, the liquid crystal aligning film surface is inside, and the other substrate is The method of bonding and sealing a liquid crystal by pressure_reduction|reduced_pressure injection|pouring and sealing, or the method of bonding a board|substrate, after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, etc. are mentioned.

A polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed with the liquid crystal. As a polymeric compound, the compound which has one or more polymerizable unsaturated groups, such as an acrylate group and a methacrylate group, in a molecule|numerator is mentioned. In that case, it is preferable that a polymeric compound is 0.01-10 mass parts with respect to 100 mass parts of a liquid crystal component, More preferably, it is 0.1-5 mass parts. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and alignment control of the liquid crystal becomes impossible, and when it exceeds 10 parts by mass, the unreacted polymeric compound increases and the exposure characteristics of the liquid crystal display element decrease. do.

After manufacturing a liquid crystal cell, a heating or an ultraviolet-ray is irradiated and a polymeric compound is superposed|polymerized, applying the voltage of alternating current or direct current to a liquid crystal cell. Thereby, the orientation of liquid crystal molecules can be controlled.

In addition, 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 a polymeric group which superposes|polymerizes by at least one of an active energy ray and heat between said pair of board|substrate It is used suitably also for the liquid crystal display element manufactured through the process of arrange|positioning a liquid crystal aligning film and applying a voltage between electrodes. Here, as an active energy ray, an ultraviolet-ray is preferable. As an ultraviolet-ray, a wavelength is 300-400 nm, Preferably it is 310-360 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 irradiation of an ultraviolet-ray and heating simultaneously.

In order to obtain the liquid crystal aligning film containing the polymeric group which superposes|polymerizes by at least one of an active energy ray and a heat|fever, the method of adding this polymeric group-containing compound in a liquid-crystal aligning agent, and the polymer component containing a polymeric group are used method can be found. Since the liquid-crystal aligning agent of this invention contains the specific compound which has a double bond site|part which reacts by irradiation of a heat|fever or ultraviolet-ray, the orientation of a liquid crystal molecule can be controlled by at least one of irradiation of an ultraviolet-ray and heating. there is.

To give an example of liquid crystal cell production, a pair of substrates with a liquid crystal aligning film are prepared, a spacer is dispersed on the liquid crystal aligning film of one substrate, the liquid crystal aligning film surface is inside, and the other substrate is bonded together, After dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the method of inject|pouring and sealing a liquid crystal under reduced pressure or the method of sealing by bonding a board|substrate, etc. are mentioned.

After manufacturing a liquid crystal cell, the orientation of a liquid crystal molecule can be controlled by irradiating a heating or an ultraviolet-ray, applying the voltage of alternating current or direct current to a liquid crystal cell.

As mentioned above, the liquid crystal display element manufactured using the liquid-crystal aligning agent of this invention becomes the thing excellent in reliability, and it can use suitably for a high-definition liquid crystal television etc. with a large screen.

Example

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

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

(Specific cellulose polymer which is component (A) of the present invention)

CE-1: hydroxyethyl cellulose (manufactured by WAKO)

CE-2: Hydroxypropylmethylcellulose phthalate (manufactured by ACROS)

(Diamine compound represented by Formula [2a] of this invention)

A1: 3,5-diaminobenzoic acid (diamine compound represented by the following formula [A1])

A2: 2,5-diaminobenzoic acid (diamine compound represented by the following formula [A2])

[Formula 81]

(Diamine compound represented by Formula [2b] of this invention)

B1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene (diamine compound represented by the following formula [B1])

B2: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene (diamine compound represented by the following formula [B2])

B3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene (diamine compound represented by the following formula [B3])

B4: a diamine compound represented by the following formula [B4]

B5: 1,3-diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [B5])

B6: a diamine compound represented by the following formula [B6]

[Formula 82]

[Formula 83]

[Formula 84]

(Other diamine compounds)

C1: p-phenylenediamine (diamine compound represented by the following formula [C1])

C2: m-phenylenediamine (diamine compound represented by the following formula [C2])

[Formula 85]

(Tetracarboxylic acid component)

D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [D1])

D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [D2])

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

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

[Formula 86]

(Solvent which is component (C) of the present invention)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

(Solvent which is component (D) of the present invention)

PGME: propylene glycol monomethyl ether (solvent represented by formula [D-1] of the present invention)

PCS: ethylene glycol monopropyl ether (solvent represented by formula [D-2] of the present invention)

DEEE: diethylene glycol monoethyl ether (solvent represented by formula [D-3] of the present invention)

[Formula 87]

(Solvent which is component (E) of the present invention)

BCS: Ethylene glycol monobutyl ether

PB: propylene glycol monobutyl ether

(Measurement of molecular weight of polyimide precursor and polyimide)

The molecular weight of the polyimide precursor and polyimide in the synthesis example was determined by a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., Ltd.), a column (KD-803, KD-805) (manufactured by Shodex Corporation). ) was used for measurement as follows.

Column temperature: 50℃

Eluent: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr·H ₂ O) is 30 mmol/L (liter), phosphoric acid and anhydrous crystals (o-phosphoric acid) are 30 mmol/L , tetrahydrofuran (THF) is 10 ㎖ / ℓ)

Flow rate: 1.0 ml/min

Standard samples for calibration curve preparation: 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 Laboratories) .

(Measurement of imidization rate of polyimide)

The imidation ratio of the polyimide in a synthesis example was measured as follows. 20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) was mixed. product) (0.53 ml) was added, and ultrasonic wave was applied to dissolve it completely. Proton NMR of 500 MHz was measured for this solution with the NMR measuring instrument (JNW-ECA500) (made by Nippon Electronics Datum). The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the integrated peak value of this proton and the proton peak derived from the NH group of the amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It calculated|required by the following formula using the value.

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

In the above formula, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated peak of the reference proton, and α is the NH of the amic acid in the case of polyamic acid (imidization rate is 0%) It is the ratio of the number of reference protons to one group proton.

"Synthesis of the specific polyimide-type polymer which is component (B) of this invention"

<Synthesis Example 1>

D1 (9.00 g, 45.9 mmol) and A1 (6.98 g, 45.9 mmol) are mixed in NMP (48.0 g), reacted at 40°C for 8 hours, and a polyamic acid solution having a resin solid content concentration of 25% by mass (1 ) was obtained. The number average molecular weight of this polyamic acid was 26,900, and the weight average molecular weight was 78,100.

<Synthesis Example 2>

D2 (8.17 g, 32.7 mmol) and A2 (6.21 g, 40.8 mmol) were mixed in NMP (26.4 g), and after reacting at 80° C. for 5 hours, D1 (1.60 g, 8.16 mmol) and NMP ( 21.6 g) was 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 (40.0g) and diluting to 6 mass %, acetic anhydride (4.85g) and pyridine (3.70g) 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 (800 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (2). The imidation ratio of this polyimide was 54 %, the number average molecular weight was 19,800, and the weight average molecular weight was 44,300.

<Synthesis Example 3>

D2 (6.25 g, 25.0 mmol), B1 (6.79 g, 17.8 mmol) and A1 (2.72 g, 17.9 mmol) were mixed in NMP (29.5 g), and after reacting at 80 ° C. for 5 hours, D1 ( 2.10 g, 10.7 mmol) and NMP (24.1 g) were added, and it was made to react at 40 degreeC for 8 hours, and the polyamic-acid solution (3) whose resin solid content concentration is 25 mass % was obtained. The number average molecular weight of this polyamic acid was 23,500, and the weight average molecular weight was 65,600.

<Synthesis Example 4>

After adding NMP to the polyamic acid solution (3) (30.0 g) obtained in Synthesis Example 3 and diluting to 6 mass %, acetic anhydride (6.75 g) and pyridine (4.90 g) are added as an imidation catalyst, It was made to react at 90 degreeC for 3 hours. This reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (4). The imidation ratio of this polyimide was 82 %, the number average molecular weight was 17,500, and the weight average molecular weight was 40,100.

<Synthesis Example 5>

D2 (6.63 g, 26.5 mmol), B1 (5.05 g, 13.3 mmol), A1 (2.52 g, 16.6 mmol) and C1 (0.36 g, 3.33 mmol) are mixed in NMP (26.2 g), 80 After making it react at °C for 5 hours, D1 (1.30 g, 6.63 mmol) and NMP (21.4 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 and diluting to 6 mass % to the obtained polyamic-acid solution (40.0g), acetic anhydride (4.78g) and pyridine (3.73g) 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 (800 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (5). The imidation ratio of this polyimide was 55 %, the number average molecular weight was 17,200, and the weight average molecular weight was 41,600.

<Synthesis Example 6>

D2 (5.17 g, 20.7 mmol), B2 (4.07 g, 10.3 mmol), A1 (2.09 g, 13.7 mmol) and B6 (2.10 g, 10.3 mmol) were mixed in NMP (26.6 g), 80 After making it react at °C for 5 hours, D1 (2.70 g, 13.8 mmol) and NMP (21.8 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 (40.0g) and diluting to 6 mass %, acetic anhydride (4.80g) and pyridine (3.75g) 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 (800 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (6). The imidation ratio of this polyimide was 52 %, the number average molecular weight was 17,600, and the weight average molecular weight was 41,300.

<Synthesis Example 7>

D2 (4.34 g, 17.3 mmol), B3 (4.50 g, 10.4 mmol), A2 (3.17 g, 20.8 mmol) and C2 (0.37 g, 3.42 mmol) were mixed in NMP (26.0 g), 80 After making it react at °C for 5 hours, D1 (3.40 g, 17.3 mmol) and NMP (21.3 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 (30.0g) and diluting to 6 mass %, acetic anhydride (6.74g) and pyridine (4.90g) were added as an imidation catalyst, and it was made to react at 90 degreeC for 3 hours. . This reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (7). The imidation ratio of this polyimide was 78 %, the number average molecular weight was 18,500, and the weight average molecular weight was 42,100.

<Synthesis Example 8>

D2 (6.12 g, 24.5 mmol), B4 (2.26 g, 4.59 mmol) and A2 (3.96 g, 26.0 mmol) were mixed in NMP (22.3 g) and reacted at 80° C. for 6 hours, followed by D1 ( 1.20 g, 6.12 mmol) and NMP (18.3 g) 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 and diluting to 6 mass % to the obtained polyamic-acid solution (40.0g), acetic anhydride (4.82g) and pyridine (3.75g) 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 (800 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (8). The imidation ratio of this polyimide was 50 %, the number average molecular weight was 16,200, and the weight average molecular weight was 38,100.

<Synthesis Example 9>

D3 (7.70 g, 34.3 mmol), B1 (3.92 g, 10.3 mmol) and A1 (3.66 g, 24.1 mmol) were mixed in NMP (45.8 g) and reacted at 40°C for 5 hours, resin solid content concentration A polyamic acid solution having a value of 25% by mass was obtained.

After adding NMP to the obtained polyamic-acid solution (40.0g) and diluting to 6 mass %, acetic anhydride (4.70g) and pyridine (3.60g) 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 (800 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (9). The imidation ratio of this polyimide was 54 %, the number average molecular weight was 17,300, and the weight average molecular weight was 41,000.

<Synthesis Example 10>

D3 (7.50 g, 33.5 mmol), B5 (3.78 g, 10.0 mmol), B6 (1.36 g, 6.69 mmol) and A1 (2.55 g, 16.8 mmol) were mixed in NMP (45.6 g), 40 It was made to react at °C for 5 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 (40.0g) and diluting to 6 mass %, acetic anhydride (4.80g) and pyridine (3.75g) 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 (800 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (10). The imidation ratio of this polyimide was 55 %, the number average molecular weight was 18,100, and the weight average molecular weight was 39,900.

<Synthesis Example 11>

D4 (5.51 g, 18.4 mmol), B2 (3.62 g, 9.17 mmol), C2 (0.66 g, 6.10 mmol) and A1 (2.33 g, 15.3 mmol) were mixed in NMP (24.0 g), 80 After making it react at degreeC for 5 hours, D1 (2.40g, 12.2 mmol) and NMP (19.6g) were added, it was made to react at 40 degreeC for 5 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 (40.0g) and diluting to 6 mass %, acetic anhydride (4.80g) and pyridine (3.70g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 4.5 hours. . This reaction solution was poured into methanol (800 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (11). The imidation ratio of this polyimide was 60 %, the number average molecular weight was 16,800, and the weight average molecular weight was 37,500.

<Synthesis Example 12>

D4 (5.66 g, 18.9 mmol), B1 (4.31 g, 11.3 mmol), B6 (2.30 g, 11.3 mmol) and A1 (2.30 g, 15.1 mmol) were mixed in NMP (30.2 g), 80 After making it react at °C for 5 hours, D1 (3.70 g, 18.9 mmol) and NMP (24.7 g) are added, and it is made to react at 40 degreeC for 5 hours, The polyamic acid solution (12) whose resin solid content concentration is 25 mass % got The number average molecular weight of this polyamic acid was 23,500, and the weight average molecular weight was 66,900.

<Synthesis Example 13>

After adding NMP to the polyamic acid solution (12) (30.0 g) obtained in Synthesis Example 12 and diluting to 6 mass %, acetic anhydride (6.70 g) and pyridine (4.80 g) are added as an imidation catalyst, It was made to react at 90 degreeC for 3.5 hours. This reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (13). The imidation ratio of this polyimide was 81 %, the number average molecular weight was 15,800, and the weight average molecular weight was 37,500.

Table 1 shows specific polyimide polymers of the present invention.

"Production of the composition and liquid-crystal aligning agent of this invention"

Examples 1 to 19 and Comparative Examples 1 to 5 below describe preparation examples of the composition. Moreover, these compositions are used also for evaluation of a liquid-crystal aligning agent.

The composition and liquid-crystal aligning agent of this invention are shown to Tables 2 - Table 4.

Using the composition or liquid-crystal aligning agent obtained in the Example and comparative example of this invention, "evaluation of transparency of a resin film", "evaluation of inkjet applicability of a liquid crystal aligning agent", "production of liquid crystal cell and evaluation of liquid crystal orientation (usually cell)", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (PSA cell)", and "evaluation of voltage retention in an insulating film-coated substrate" were performed. The conditions are as follows.

"Evaluation of transparency of resin film"

The composition obtained by the Example and the comparative example of this invention was pressure-filtered with the membrane filter of 1 micrometer of pore diameter, and the transparency of the resin film was evaluated. This solution was spin-coated on a 40 x 50 mm quartz substrate and heat-treated on a hot plate at 100°C for 5 minutes to obtain a quartz substrate with a polyimide resin coating having a film thickness of 100 nm.

Using the obtained quartz substrate with a resin film, the ultraviolet-visible absorption spectrum of the wavelength of 300-750 nm was measured with the ultraviolet-visible spectrophotometer (UV-2550) (made by Shimadzu Corporation). Among these, the thing with the higher transmittance|permeability of the wavelength of 310 nm and 340 nm was set as the thing excellent in transparency of the resin film.

The result of transparency of the resin film obtained by Table 5 - Table 7 by the Example and the comparative example is shown.

"Evaluation of the inkjet applicability|paintability of a liquid crystal aligning agent"

The liquid-crystal aligning agent (7) obtained in Example 7 of this invention, and the liquid-crystal aligning agent (13) obtained in Example 13 were filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and inkjet applicability|paintability was evaluated. HIS-200 (manufactured by Hitachi Plant Technology) was used for the inkjet applicator. Application was performed on an ITO (indium tin oxide) vapor deposition substrate cleaned with pure water and IPA (isopropyl alcohol), the application area was 70 × 70 mm, the nozzle pitch was 0.423 mm, the scan pitch was 0.5 mm, and the application rate was 40 mm/sec, time from application to temporary drying was 60 seconds, and temporary drying was performed on a hot plate at 70°C for 5 minutes.

"Preparation of liquid crystal cell and evaluation of liquid crystal orientation (normal cell)"

The liquid-crystal aligning agent obtained by the Example and the comparative example of this invention was filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and the liquid crystal cell was manufactured. This solution was spin-coated on the ITO side of a 30 x 40 mm ITO electrode-attached substrate (40 mm long x 30 mm wide, 0.7 mm thick) washed with pure water and IPA, and heated on a hot plate at 100°C for 5 minutes. It processed and obtained the ITO board|substrate with a polyimide liquid crystal aligning film whose film thickness is 100 nm. The coating film surface of this ITO substrate was rubbed with a rubbing device having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll advancing speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two ITO board|substrates with the obtained liquid crystal aligning film were prepared, the liquid crystal aligning film surface was turned inside, a 6 micrometers spacer was pinched|interposed, and it combined, and the sealing compound (XN-1500T) (made by Mitsui Chemicals) was printed. Then, after bonding the other board|substrate and liquid crystal aligning film surface so that it faced and bonded together, it hardened|cured by heat-processing a sealing compound at 120 degreeC for 90 minute(s) in heat-circulation type clean oven, and the empty cell was manufactured. The liquid crystal was injected into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal cell (normal cell) was obtained.

Furthermore, the liquid-crystal aligning agent (1) and liquid-crystal aligning agent (2) obtained in Example 1 and Example 2, the liquid-crystal aligning agent (20) and liquid-crystal aligning agent (21) obtained by the comparative example 1 and the comparative example 2, and the comparative example Nematic liquid crystal (MLC-2003) (made by Merck Japan) was used for the liquid crystal cell using the liquid-crystal aligning agent (24) obtained by 5 for a liquid crystal.

Moreover, the liquid-crystal aligning agent (3) - liquid-crystal aligning agent (6) obtained by Examples 3-6, the liquid-crystal aligning agent (8) obtained by Examples 8-12 - liquid-crystal aligning agent (12), the Example In the liquid crystal cell using the liquid-crystal aligning agent (14) - liquid-crystal aligning agent (19) obtained in 14 - Example 19, and the liquid-crystal aligning agent (22) obtained by the comparative example 3 and the comparative example 4, and the liquid-crystal aligning agent (23), liquid crystal An enematic liquid crystal (MLC-6608) (manufactured by Merck Japan) was used.

The liquid-crystal orientation was evaluated using the liquid crystal cell obtained above. The liquid-crystal orientation observed the liquid crystal cell with the polarizing microscope (ECLIPSE E600WPOL) (made by Nikon Corporation), and confirmed the presence or absence of an orientation defect. It was made into the thing which was specifically, excellent in this evaluation that an orientation defect was not seen (it showed as favorable in Tables 8-10).

The result of the liquid-crystal orientation obtained by Table 8 - Table 10 by the Example and the comparative example is shown.

"Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)"

The liquid-crystal aligning agent (6) obtained in Example 6, the liquid-crystal aligning agent (9) obtained in Example 9, and the liquid-crystal aligning agent (16) obtained in Example 16 were filtered under pressure with the membrane filter of 1 micrometer of pore diameter, -15 Preparation of a liquid crystal cell and evaluation of the liquid-crystal orientation were performed using the solution stored at degreeC for 48 hours. This solution was washed with pure water and IPA, and a substrate (40 mm long × 30 mm wide, 0.7 mm thick) with an ITO electrode having a pattern spacing of 10 × 10 mm at the center and an ITO of 10 × 40 mm at the center was applied. It spin-coated on the ITO surface of the board|substrate with an electrode (40 mm long x 30 mm wide, 0.7 mm thick), it heat-processed at 100 degreeC for 5 minute(s) on a hotplate, and the film thickness of 100 nm polyimide coating film was obtained. After wash|cleaning a coating-film surface with pure water, it heat-processed at 100 degreeC for 15 minute(s) in thermal circulation type clean oven, and obtained the board|substrate with a liquid crystal aligning film.

The liquid crystal aligning film surface was turned inside, this board|substrate with a liquid crystal aligning film was combined, the 6 micrometers spacer was pinched|interposed, and the periphery was adhere|attached with a sealing compound, and the empty cell was manufactured. 100 mass % of a nematic liquid crystal (MLC-6608) polymeric compound (1) represented by the following formula to a nematic liquid crystal (MLC-6608) (made by Merck Japan) to this empty cell by the reduced pressure injection method The liquid crystal which mixed 0.3 mass % of polymeric compound (1) was injected with respect to this, the injection port was sealed, and the liquid crystal cell was obtained.

[Formula 88]

A wavelength of 350 nm or less is cut using a metal halide lamp with an illuminance of 60 mW, applying a voltage of AC 5V to the obtained liquid crystal cell, and ultraviolet irradiation of 20 J/cm 2 is performed in conversion of 365 nm, liquid crystal The liquid crystal cell (PSA cell) by which the orientation direction of was controlled was obtained. The temperature in the irradiation apparatus at the time of irradiating an ultraviolet-ray to a liquid crystal cell was 50 degreeC.

The response speed of the liquid crystal before ultraviolet irradiation of this liquid crystal cell and after ultraviolet irradiation was measured. The response speed measured T90 -> T10 from 90% of transmittance|permeability to 10% of transmittance|permeability.

Compared with the liquid crystal cell before ultraviolet irradiation, the PSA cell obtained in the Example confirmed that the orientation direction of a liquid crystal was controlled by the point with which the response speed of the liquid crystal cell after ultraviolet irradiation became quick. Moreover, any liquid crystal cell confirmed that the liquid crystal was orientating uniformly by observation with a polarization microscope (ECLIPSE E600WPOL) (made by Nikon Corporation).

"Evaluation of voltage retention in insulating film-coated substrates"

(Adjustment of composition for insulating film)

A propylene glycol monomethyl ether acetate solution of acrylic resin ((meth)acrylic acid/hydroxyethyl(meth)acrylate/methyl(meth)acrylate = 9/25.5/65.5 solid content concentration: 22.0 wt. %, weight average molecular weight 6000 (in terms of polystyrene) (7.07 g), propylene glycol monomethyl ether acetate (25.1 g), KAYARADDPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) (3.30 g), I-369 (manufactured by Chiba Specialty Chemicals) ) (0.30 g), ITX (manufactured by Fast Chemical Corporation), and Megapac R-30 (0.015 g) were added, followed by stirring at 25°C for 3 hours to obtain a composition for an insulating film. Insoluble matter was not seen in this composition for insulating films, and a uniform solution was obtained.

(Manufacture of an insulating film-coated substrate)

The composition for insulating films obtained above was filtered using a 0.2-micrometer filter. Thereafter, the composition was washed with pure water and IPA, and a substrate with an ITO electrode having a pattern interval of 20 μm with a pattern spacing of 10 × 10 mm in the center (40 mm in length × 30 mm in width, 0.7 mm in thickness) and 10 × 40 mm in the center It spin-coated on the ITO surface of the board|substrate with ITO electrode (length 40mm x width 30mm, thickness 0.7mm), and heat-processed at 110 degreeC for 5 minute(s) on a hotplate. This coating film was irradiated with an ultraviolet-ray whose irradiation amount in 365 nm is 500 mJ/cm<2> with the ultraviolet irradiation apparatus PLA-501(F) (made by Canon), and it heat-processed at 120 degreeC for 1 minute on a hotplate. . Then, it heat-processed at 200 degreeC for 60 minute(s) on a hotplate further, and obtained the board|substrate with which the insulating film with a film thickness of 1.12 micrometers was apply|coated.

(Production of liquid crystal cell)

The liquid-crystal cell was manufactured using the solution which pressure-filtered the liquid-crystal aligning agent obtained by the Example and the comparative example of this invention with the membrane filter of 1 micrometer of pore diameters, and stored at -15 degreeC for 48 hours. This solution was spin-coated on the insulating film-coated surface of the insulating film-coated substrate obtained above, and heat-treated on a hot plate at 100°C for 5 minutes to obtain an ITO substrate with a polyimide liquid crystal aligning film having a film thickness of 100 nm. The coating film surface of this ITO substrate was rubbed with a rubbing device having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll advancing speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two ITO board|substrates with the obtained liquid crystal aligning film were prepared, the liquid crystal aligning film surface was turned inside, a 6 micrometers spacer was pinched|interposed, and it combined, and the sealing compound (XN-1500T) (made by Mitsui Chemicals) was printed. Then, after bonding the other board|substrate and liquid crystal aligning film surface so that it faced and bonded together, it hardened|cured by heat-processing a sealing compound at 120 degreeC for 90 minute(s) in heat-circulation type clean oven, and the empty cell was manufactured. The liquid crystal was injected into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal cell was obtained.

(Evaluation of voltage retention)

60 microseconds of voltage of 1V is applied to the liquid crystal cell obtained above under the temperature of 70 degreeC, the voltage 16.67 ms after and 50 ms after is measured, and how much the voltage is maintained is as voltage retention (also referred to as VHR). Calculated. In addition, the measurement was performed using the voltage retention measuring apparatus (VHR-1) (made by Toyo Technica) by setting of Voltage:±1V, Pulse Width: 60 microseconds, Flame Period: 16.67 ms or 50 ms.

After irradiating a 10 J/cm<2> ultraviolet-ray to the liquid crystal cell which the measurement of voltage retention was complete|finished in conversion of 365 nm, VHR was measured on the same conditions. In addition, ultraviolet irradiation was performed using the tabletop UV curing apparatus (HCT3B28HEX-1) (made by SEN LIGHT CORPORATION).

The evaluation result of the voltage retention in the insulating film-coated board|substrate obtained by Tables 8-10 by the Example and the comparative example is shown.

<Example 1>

NMP (27.0 g) and BCS (26.2 g) were added to the polyamic acid solution (1) (11.5 g) and CE-2 (0.72 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 1, and stirred at 50°C for 6 hours to obtain a composition (1). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (1) was used for evaluation also as a liquid-crystal aligning agent (1).

Using the obtained composition (1) and liquid-crystal aligning agent (1), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate" on the conditions mentioned above evaluation of the voltage retention in ' was performed.

<Example 2>

To the polyimide powder (2) (2.33 g) and CE-1 (1.00 g) obtained by the synthesis method of Synthesis Example 2, NEP (32.7 g), PCS (5.70 g) and BCS (21.2 g) were added, 70 It stirred at degreeC for 24 hours, and obtained the composition (2). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (2) was used for evaluation also as a liquid-crystal aligning agent (2).

Using the obtained composition (2) and liquid-crystal aligning agent (2), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Example 3>

To the polyamic acid solution (3) (12.6 g) and CE-1 having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 3, NMP (15.7 g), BCS (15.9 g) and PB (19.1 g) It added and stirred at 50 degreeC for 6 hours, and obtained the composition (3). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (3) was used for evaluation also as a liquid-crystal aligning agent (3).

Using the obtained composition (3) and the liquid-crystal aligning agent (3), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Example 4>

To the polyamic acid solution (3) (7.80 g) and CE-2 having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 3, NMP (26.7 g), PCS (5.61 g) and BCS (17.7 g) were added It added and stirred at 50 degreeC for 6 hours, and obtained the composition (4). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (4) was used for evaluation also as a liquid-crystal aligning agent (4).

Using the obtained composition (4) and the liquid-crystal aligning agent (4), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate on the conditions mentioned above" evaluation of voltage retention in ' was performed.

<Example 5>

NMP (9.27 g), NEP (24.7 g) and PB (28.6 g) were added to polyimide powder (4) (2.45 g) and CE-2 (1.05 g) obtained by the synthesis method of Synthesis Example 4, 70 The composition (5) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (5) was used for evaluation also as a liquid-crystal aligning agent (5).

Using the obtained composition (5) and the liquid-crystal aligning agent (5), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Example 6>

NMP (11.6 g), NEP (17.3 g) and PB (30.2 g) were added to polyimide powder (5) (2.00 g) and CE-2 (1.33 g) obtained by the synthesis method of Synthesis Example 5, 70 The composition (6) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (6) was used for evaluation also as a liquid-crystal aligning agent (6).

Using the obtained composition (6) and liquid-crystal aligning agent (6), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" on the conditions mentioned above, "of a liquid crystal cell Manufacture and evaluation of liquid-crystal orientation (PSA cell)" and "evaluation of the voltage retention in an insulating-film-coated board|substrate" were performed.

<Example 7>

NMP (11.7 g), NEP (17.6 g) and PB (30.0 g) were added to polyimide powder (5) (1.08 g) and CE-2 (0.72 g) obtained by the synthesis method of Synthesis Example 5, 70 The composition (7) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (7) was used for evaluation also as a liquid-crystal aligning agent (7).

"Evaluation of the inkjet applicability|paintability of a liquid-crystal aligning agent" was performed on the conditions mentioned above using the obtained liquid-crystal aligning agent (7).

<Example 8>

To the polyimide powder (5) (2.15 g) and CE-2 (0.92 g) obtained by the synthesis method of Synthesis Example 5, γ-BL (24.2 g), DEEE (11.7 g) and BCS (24.5 g) were added, and stirred at 70°C for 24 hours to obtain a composition (8). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (8) was used for evaluation also as a liquid-crystal aligning agent (8).

Using the obtained composition (8) and the liquid-crystal aligning agent (8), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate on the conditions mentioned above" evaluation of voltage retention in ' was performed.

<Example 9>

NEP (35.9 g) and BCS (24.2 g) were added to polyimide powder (6) (2.83 g) and CE-1 (0.50 g) obtained by the synthesis method of Synthesis Example 6, and stirred at 70°C for 24 hours, A composition (9) was obtained. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (9) was used for evaluation also as a liquid-crystal aligning agent (9).

Using the obtained composition (9) and liquid-crystal aligning agent (9), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" on the conditions mentioned above, "of a liquid crystal cell Manufacture and evaluation of liquid-crystal orientation (PSA cell)" and "evaluation of the voltage retention in an insulating-film-coated board|substrate" were performed.

<Example 10>

To the polyimide powder (7) (1.89 g) and CE-2 (1.55 g) obtained by the synthesis method of Synthesis Example 7, NEP (26.6 g), BCS (12.5 g) and PB (21.9 g) were added, 70 The composition (10) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (10) was used for evaluation also as a liquid-crystal aligning agent (10).

Using the obtained composition (10) and the liquid-crystal aligning agent (10), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Example 11>

To the polyimide powder (8) (1.53 g) and CE-2 (1.87 g) obtained by the synthesis method of Synthesis Example 8, NMP (14.5 g), NEP (14.5 g) and PB (30.9 g) were added, 70 The composition (11) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (11) was used for evaluation also as a liquid-crystal aligning agent (11).

Using the obtained composition (11) and the liquid-crystal aligning agent (11), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate on the conditions mentioned above" evaluation of voltage retention in ' was performed.

<Example 12>

To the polyimide powder (8) (1.88 g) and CE-2 (1.25 g) obtained by the synthesis method of Synthesis Example 8, γ-BL (24.7 g), PGME (17.8 g) and PB (18.8 g) were added, , and stirred at 70°C for 24 hours to obtain a composition (12). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (12) was used for evaluation also as a liquid-crystal aligning agent (12).

Using the obtained composition (12) and the liquid-crystal aligning agent (12), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Example 13>

To the polyimide powder (8) (1.08 g) and CE-2 (0.75 g) obtained by the synthesis method of Synthesis Example 8, γ-BL (22.3 g) and PGME (39.4 g) were added, and at 70°C for 24 hours. It stirred to obtain a composition (13). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (13) was used for evaluation also as a liquid-crystal aligning agent (13).

"Evaluation of the inkjet applicability|paintability of a liquid-crystal aligning agent" was performed on the conditions mentioned above using the obtained liquid-crystal aligning agent (13).

<Example 14>

To the polyimide powder (9) (2.80 g) and CE-1 (0.70 g) obtained by the synthesis method of Synthesis Example 9, NMP (35.0 g), DEEE (12.0 g) and BCS (15.9 g) were added, 70 The composition (14) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (14) was used for evaluation also as a liquid-crystal aligning agent (14).

Using the obtained composition (14) and the liquid-crystal aligning agent (14), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Example 15>

NEP (26.8 g), BCS (24.7 g) and PB (9.27 g) were added to polyimide powder (10) (2.38 g) and CE-2 (1.02 g) obtained by the synthesis method of Synthesis Example 10, 70 The composition (15) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (15) was used for evaluation also as a liquid-crystal aligning agent (15).

Using the obtained composition (15) and liquid-crystal aligning agent (15), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Example 16>

NEP (37.5 g), DEEE (6.02 g) and BCS (19.1 g) were added to the polyimide powder (11) (2.45 g) and CE-2 (1.05 g) obtained by the synthesis method of Synthesis Example 11, 70 The composition (16) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (16) was used for evaluation also as a liquid-crystal aligning agent (16).

Using the obtained composition (16) and the liquid-crystal aligning agent (16), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" on the conditions mentioned above, "of a liquid crystal cell Manufacture and evaluation of liquid-crystal orientation (PSA cell)" and "evaluation of the voltage retention in an insulating-film-coated board|substrate" were performed.

<Example 17>

To the polyamic acid solution (12) (11.2 g) and CE-2 having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 12, NMP (26.3 g), BCS (12.8 g) and PB (12.8 g) were added It added and stirred at 50 degreeC for 6 hours, and obtained the composition (17). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (17) was used for evaluation also as a liquid-crystal aligning agent (17).

Using the obtained composition (17) and the liquid-crystal aligning agent (17), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Example 18>

To the polyimide powder (13) (2.23 g) and CE-2 (1.20 g) obtained by the synthesis method of Synthesis Example 13, NMP (30.8 g), PCS (14.7 g) and BCS (15.6 g) were added, 70 The composition (18) was obtained by stirring at °C for 24 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (18) was used for evaluation also as a liquid-crystal aligning agent (18).

Using the obtained composition (18) and liquid-crystal aligning agent (18), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate under the conditions mentioned above" evaluation of voltage retention in ' was performed.

<Example 19>

To the polyimide powder (13) (1.89 g) and CE-2 (1.26 g) obtained by the synthesis method of Synthesis Example 13, γ-BL (24.9 g), PCS (18.0 g) and PB (18.9 g) were added, , and stirred at 70°C for 24 hours to obtain a composition (19). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (19) was used for evaluation also as a liquid-crystal aligning agent (19).

Using the obtained composition (19) and the liquid-crystal aligning agent (19), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Comparative Example 1>

NMP (21.6g) and BCS (22.7g) were added to the polyamic acid solution (1) (12.5g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 1, and stirred at 25°C for 3 hours, A composition (20) was obtained. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (20) was used for evaluation also as a liquid-crystal aligning agent (20).

Using the obtained composition (20) and the liquid-crystal aligning agent (20), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Comparative Example 2>

To the polyimide powder (2) (3.12 g) obtained by the synthesis method of Synthesis Example 2, NEP (31.5 g), PCS (5.41 g) and BCS (19.9 g) were added, stirred at 70° C. for 24 hours, and the composition ( 21) was obtained. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (21) was used for evaluation also as a liquid-crystal aligning agent (21).

Using the obtained composition (21) and the liquid-crystal aligning agent (21), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Comparative Example 3>

NMP (12.5 g), BCS (13.6 g) and PB (16.4 g) were added to the polyamic acid solution (3) (12.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 3, 25 The composition (22) was obtained by stirring at °C for 3 hours. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (22) was used for evaluation also as a liquid-crystal aligning agent (22).

Using the obtained composition (22) and the liquid-crystal aligning agent (22), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

<Comparative Example 4>

To the polyimide powder (5) (3.20 g) obtained by the synthesis method of Synthesis Example 5, NMP (11.6 g), NEP (17.5 g) and PB (29.1 g) were added, stirred at 70° C. for 24 hours, and the composition ( 23) was obtained. Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (23) was used for evaluation also as a liquid-crystal aligning agent (23).

Using the obtained composition (23) and the liquid-crystal aligning agent (23), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film-coated substrate on the conditions mentioned above" evaluation of voltage retention in ' was performed.

<Comparative Example 5>

To CE-2 (2.02 g), NMP (9.28 g), NEP (13.9 g) and PB (25.3 g) were added, followed by stirring at 70°C for 24 hours to obtain a composition (24). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (24) was used for evaluation also as a liquid-crystal aligning agent (24).

Using the obtained composition (24) and the liquid-crystal aligning agent (24), "evaluation of transparency of a resin film", "evaluation of manufacture of a liquid crystal cell and liquid-crystal orientation (normal cell)" and "insulation film coated substrate" on the conditions mentioned above evaluation of voltage retention in ' was performed.

As can be seen from the above results, the composition of the example of the present invention obtained a resin film with high transparency compared with the composition of the comparative example. Specifically, using the same specific polyimide polymer as component (B) of the present invention, a composition using the specific cellulosic polymer as component (A) of the present invention, and a composition using no specific cellulosic polymer Comparison of compositions, ie, comparison of Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, and Example 6 and Comparative Example 4.

Moreover, evaluation of the voltage retention in an insulating film application board|substrate WHEREIN: The liquid-crystal aligning agent obtained from the composition of this invention is compared with the liquid-crystal aligning agent obtained from the composition of a comparative example, In the state with the insulating film which consists of an organic member under the liquid-crystal aligning film Even when irradiated with light, a result excellent in voltage retention was obtained (from evaluation of voltage retention in the insulating film-coated substrates in Examples and Comparative Examples). Specifically, using the same specific polyimide polymer as component (B) of the present invention, a composition using the specific cellulosic polymer as component (A) of the present invention, and a composition using no specific cellulosic polymer Comparison of compositions, ie, comparison of Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3, and Example 6 and Comparative Example 4. Moreover, also about the comparative example 5 which does not contain a specific polyimide-type polymer, the result excellent in the said voltage retention was obtained.

Industrial Applicability

The composition of this invention has high transparency of a resin film, and can suppress decomposition|disassembly of the resin film by light, such as an ultraviolet-ray.

Moreover, even if the liquid-crystal aligning agent of this invention irradiates light in the state with the insulating film which consists of an organic member under a liquid crystal aligning film, it turns into a liquid crystal aligning film excellent in voltage retention.

Therefore, the liquid crystal display element which has a liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention becomes the thing excellent in reliability, and it can use suitably for a large screen and high-definition liquid crystal television etc., TN element, STN element, TFT liquid crystal element, especially vertical It is useful for an alignment type liquid crystal display element.

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

Claims (18)

A composition containing the following component (A) and component (B).
(A) Component: The polymer which has a structure shown by following formula [1].
[Formula 1]

(In formula [1], X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a group having a structure selected from the following formulas [1a] to [1m], and n is 100 to represents an integer of 1000000).
[Formula 2]

(In formulas [1c] to [1m], X ⁷ and X ⁸ each independently represent a phenyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a butyl group, and X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ and X ¹⁴ each independently represent a phenylene group, a methylene group, an ethylene group, an n-propylene group, an isopropylene group or a butylene group, in formula [1h], n represents an integer of 0 to 3; In formula [1i], m represents the integer of 0-3).
(B) Component: The at least 1 sort(s) of polymer chosen from the polyimide precursor obtained by making the diamine component containing the diamine compound which has a structure shown by following formula [2a], and a tetracarboxylic-acid component react, and a polyimide.
[Formula 3]

(in formula [2a], a represents the integer of 0-4). The method of claim 1,
The composition characterized in that the diamine compound having a structure represented by the formula [2a] is a diamine compound having a structure represented by the following formula [2a-1].
[Formula 4]

(in formula [2a-1], a represents the integer of 0-4, n represents the integer of 1-4). The method of claim 1,
The diamine component in the polymer of the said (B) component contains at least 1 sort(s) chosen from the diamine compound of the structure shown by following formula [2b], The composition characterized by the above-mentioned.
[Formula 5]

(In formula [2b], Y is a substituent having a structure selected from the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4], or formula [2b-5] , and m represents an integer of 1 to 4).
[Formula 6]

(in formula [2b-1], a represents an integer of 0 to 4, in formula [2b-2], Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15) , -O-, -CH ₂ O-, -COO- or -OCO-, Y ² is a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15), Y ³ is represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ is a benzene ring or a cyclohexane ring or a divalent cyclic group selected from a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, wherein any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms; It may be substituted with a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, or a heterocyclic ring, and these rings Any hydrogen atom on the type group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is 0 an integer of to 4, Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, formula [2b- In 3], Y ⁷ represents -O-, -CH ₂ O-, -COO-, -OCO-, -CONH- or -NHCO-, Y ⁸ represents an alkyl group having 8 to 22 carbon atoms, formula [2b In -4], Y ⁹ and Y ¹⁰ each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and in formula [2b-5], Y ¹¹ represents an alkyl group having 1 to 5 carbon atoms). The method of claim 1,
The tetracarboxylic-acid component in the polymer of the said (B) component contains at least 1 sort(s) chosen from the compound shown by following formula [3], The composition characterized by the above-mentioned.
[Formula 7]

(In formula [3], Z<^1> is group of a structure chosen from following formula [3a] - a formula [3j]).
[Formula 8]

(In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, respectively, and in the formula [3g], Z ⁶ and Z ⁷ are a hydrogen atom or a methyl group may be the same or different from each other). The method of claim 1,
(C) A composition containing, as a component, at least one solvent selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. The method of claim 1,
(D) The composition containing the at least 1 sort(s) of solvent chosen from the solvent shown by a following formula [D-1] - a formula [D-3] as a component.
[Formula 9]

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ³ represents a C1-C4 alkyl group). The method of claim 1,
(E) contains at least one solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether as component composition to do. The resin film obtained from the composition in any one of Claims 1-7. The liquid-crystal aligning agent obtained from the composition of Claim 1. The liquid crystal aligning film obtained using the liquid-crystal aligning agent of Claim 9. The liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent of Claim 9. The liquid crystal display element which has the liquid crystal aligning film of Claim 10. 11. The method of claim 10,
A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with an electrode and comprising a polymerizable compound that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates, the electrode A liquid crystal aligning film, characterized in that it is used in a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage therebetween. 12. The method of claim 11,
A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with an electrode and comprising a polymerizable compound that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates, the electrode A liquid crystal aligning film, characterized in that it is used in a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage therebetween. It has the liquid crystal aligning film of Claim 13 or 14, The liquid crystal display element characterized by the above-mentioned. 11. The method of claim 10,
A liquid crystal aligning film comprising a liquid crystal layer between a pair of substrates provided with an electrode and containing a polymerizable group that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates, between the electrodes A liquid crystal aligning film, characterized in that it is used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage to the . 12. The method of claim 11,
A liquid crystal aligning film comprising a liquid crystal layer between a pair of substrates provided with an electrode and containing a polymerizable group that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates, between the electrodes A liquid crystal aligning film, characterized in that it is used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage to the . It has the liquid crystal aligning film of Claim 16 or 17, The liquid crystal display element characterized by the above-mentioned.