TWI542632B - A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device - Google Patents

Description

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

The present invention relates to a composition for forming a resin film, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

A resin film composed of an organic material such as a polymer material has been widely used as an interlayer insulating film or a protective film in an electronic device, because of its ease of formation or insulating properties. Among them, a liquid crystal display element which is a well-known display device, and a resin film made of an organic material is used as a liquid crystal alignment film.

At present, a resin film used industrially uses a polyimide-based organic film excellent in durability. The polyimine-based organic film is formed of a composition of a polyamic acid or a polyimine containing a polyimide precursor. In other words, the polyimide film-based organic film is formed by applying a composition containing polyglycine or polyimine to a substrate and baking it. At this time, these compositions use a solvent having a high boiling point such as N-methyl-2-pyrrolidone (also referred to as NMP) or γ-butyrolactone (also referred to as γ-BL), and therefore must be used. It is baked at a high temperature of about 200 to 300 ° C (see, for example, Patent Document 1).

In recent years, a resin film formed of a composition containing a polyimine-based polymer (referred to as a polyimide precursor or a polyimide) and a polyoxyalkylene is used for an interlayer insulating film or a protective film and Liquid crystal alignment film. In particular, in order to improve the reliability of the long-term driving of the liquid crystal display device, a liquid crystal alignment treatment agent and a liquid crystal alignment film of a polymer of a polyfluorene-based polymer and a polyoxyalkylene are proposed (see, for example, Patent Document 2).

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 09-278724

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-097007

[Summary of the Invention]

When a liquid crystal alignment film is formed using a liquid crystal alignment treatment agent containing a polyimine-based polymer, the firing step is required to be high-temperature firing in the step of producing a liquid crystal display element for the above reasons. Therefore, even if it is a liquid crystal alignment treatment agent containing a polyimine-based polymer and a polyoxyalkylene, in order to dissolve a polyimide-based polymer, NMP or γ-BL is used as a solvent, so that high temperature is required. Burnt. However, the substrate of the liquid crystal display element is replaced by a normal glass substrate, and the use is thin and lightweight, but When a plastic substrate having low heat resistance is required, it is required to be fired at a lower temperature. Similarly, in order to suppress the deterioration of the color characteristics of the color filter of the liquid crystal display element accompanying the high-temperature firing, and to reduce the energy cost at the time of manufacturing the liquid crystal display element, it is necessary to perform low-temperature firing.

Further, the liquid crystal alignment treatment agent obtained by dissolving the polyamidene-based polymer in a solvent which is generally used, that is, a polymer solution of NMP or γ-BL and a polyoxyalkylene oxide, has a high polarity of NMP or γ-BL and hydrophobicity. The compatibility of the highly polyoxyalkylene oxide is deteriorated. Therefore, when this liquid crystal alignment treatment agent is applied to a substrate, pinholes are easily generated by repulsion on the liquid crystal alignment film. In other words, the conventional polyimide-based polymer and the liquid crystal alignment treatment agent with polysiloxane are likely to cause alignment defects in the pinholes.

Further, in the liquid crystal alignment film, a liquid crystal alignment treatment agent is applied to the substrate, and then the coating film is formed by firing. In this case, in order to improve the coating property (also referred to as coating property) of the liquid crystal alignment film, that is, to suppress the occurrence of pinholes due to repulsion, it is required to improve the wettability of the liquid crystal alignment agent for the substrate.

The resin film obtained from the composition containing the polyimine-based polymer and the polyoxyalkylene has a higher chemical stability than the resin film obtained from the composition containing no polyoxyalkylene, so that in addition to the liquid crystal The alignment film can also be used for an interlayer insulating film or a protective film in other electronic devices. In these films, it is also necessary to form a resin film by low-temperature firing or to improve the coatability of the resin film. By low-temperature firing, the energy cost at the time of manufacture can be reduced. Moreover, by improving the coatability, pinholes due to repulsion on the resin film can be suppressed.

Accordingly, it is an object of the present invention to provide a composition having the above characteristics. That is, an object of the present invention is to provide a composition in which a composition of a resin film can be formed by firing at a low temperature in a composition comprising a polyamidene-based polymer and a polyoxyalkylene. Further, an object of the present invention is to provide a composition which can suppress pinholes generated by repulsion when a resin film is formed.

Moreover, an object of the present invention is to provide a liquid crystal alignment treatment agent which is a liquid crystal alignment treatment agent which can form a liquid crystal alignment film by low-temperature baking in a liquid crystal alignment treatment agent using the above composition. Further, an object of the present invention is to provide a liquid crystal alignment treatment agent which can suppress pinholes accompanying repulsion when forming a liquid crystal alignment film.

It is an object of the present invention to provide a liquid crystal alignment film which corresponds to the above requirements. That is, a liquid crystal alignment film which can be formed by low-temperature firing and a liquid crystal alignment film which can suppress alignment defects accompanying pinholes.

Further, an object of the present invention is to provide a liquid crystal display element comprising a liquid crystal alignment film corresponding to the above requirements.

As a result of intensive studies, the present inventors have found a composition containing a "solvent" having a specific structure selected from the group consisting of reacting a diamine component containing a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component. The polymer of at least one of the quinone imine precursor or the polyimine, and the polyoxyalkylene of a specific structure are extremely effective for achieving the above object, and the present invention has been completed.

That is, the present invention is the one having the following points.

(1) A composition comprising the following components (A), (B) and (C).

(A) component: a solvent selected from at least one of the following formula [1a] or formula [1b].

(In the formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms).

(B) Component: a polymer selected from at least one of a polyimine precursor obtained by reacting a diamine component having a diamine compound having a carboxyl group and a tetracarboxylic dianhydride component, or a polyimine.

(C) component: a polyoxyalkylene obtained by polycondensing an alkoxy decane containing any one of the alkoxy decane represented by the following formula [A1], the formula [A2], or the formula [A3].

(A ² ) _m Si(A ² ) _n (OA ³ ) _p [A1]

(In the formula [A1], A ¹ represents an aliphatic hydrocarbon, a benzene ring, a cyclohexane ring, a heterocyclic ring or an organic group having a steroid structure of 8 to 35 carbon atoms, and A ² represents a hydrogen atom or a carbon number of 1 to 5, respectively. The alkyl group, A ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3. However, m+n+p is 4) .

(Chemical Formula 3) (B ¹ ) _m Si(B ² ) _n (OB ³ ) _p [A2]

(In the formula [A2], B ¹ represents a vinyl group, an epoxy group, an amine group, a decyl group, an isocyanate group, a methacryl fluorenyl group, an acryl fluorenyl group, a ureido group or an organic group having a cinnamyl group of 2 to 12 carbon atoms; Base, B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents 0. An integer of ~3, but m+n+p is 4).

(D ⁴ ) _n Si(OD ² ) _4-n [A3]

(In the formula [A3], D ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, D ² represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3).

(2) The composition according to the above (1), wherein the component (A) is 50 to 100% by mass of the entire solvent contained in the composition.

(3) The composition according to the above (1) or (2), wherein the diamine compound having a carboxyl group as the component (B) is a diamine compound having a structure represented by the following formula [2].

[Chemical 5]-(CH ₂ ) _a -COOH [2]

(In the formula [2], a represents an integer from 0 to 4).

(4) The composition according to (1) or (2) above, which The diamine compound having a carboxyl group as the component (B) is a diamine compound having a structure represented by the following formula [2a].

(In the formula [2a], a represents an integer from 0 to 4, and n represents an integer from 1 to 4).

(5) The composition according to the above (3) or (4), wherein the diamine compound having a carboxyl group is 20 mol% to 100 mol% of the total diamine used in the component (B).

The composition of any one of the above-mentioned (1), wherein the diamine component of the component (B) contains at least one selected from the structures represented by the following formula [2b]. Kind of diamine compound.

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

(In the formula [2b-1], a represents an integer of 0 to 4, and in the formula [2b-2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O -, -CH ₂ O-, -COO- or -OCO-, Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), and Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ⁴ represents a divalent ring selected from a benzene ring, a cyclohexane ring or a hetero ring a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or carbon a fluorine-containing alkyl group having 1 to 3, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ representing a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring; Any hydrogen atom on the cyclic group may have an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom, n represents an integer of 0 to 4, and Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or containing from 1 to 18 carbon atoms, fluoroalkoxy of the formula [2b-3] in, Y ⁷ represents an alkyl group having 8 to 22 carbon atoms, the formula [2b-4] in The Y ⁸ and Y ⁹ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, the formula [2b-5] in, Y ¹⁰ represent carbon atoms of an alkyl group having 1 to 8).

The composition of any one of the above (1), wherein the tetracarboxylic dianhydride component of the component (B) is the following formula: The compound shown in [3].

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

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

(A) The composition according to any one of the above (1), wherein the alkoxydecane represented by the formula [A2] of the component (C) is selected from allyltriethoxydecane. , allyl trimethoxy decane, diethoxymethyl vinyl decane, dimethoxymethyl vinyl decane, triethoxy vinyl decane, vinyl trimethoxy decane, vinyl ginseng (2- Methoxy Ethyloxy)decane, 3-(triethoxydecyl)propyl methacrylate, 3-(trimethoxydecyl)propyl acrylate or 3-(trimethoxydecyl)propyl At least one of the acrylates.

(9) The composition according to any one of the above (1), wherein the alkoxydecane represented by the formula [A2] of the component (C) is selected from the group consisting of 3-glycidyloxypropane (dimethoxy)methyl decane, 3-glycidoxy propyl (diethoxy) methyl decane, 3-glycidoxy propyl trimethoxy decane or 2- (3, 4 At least one of - epoxycyclohexyl)ethyltrimethoxydecane.

(10) The composition according to any one of the above (1), wherein the polyoxane of the component (C) is a compound of the formula [A1], the formula [A2] and the formula [A3] The polyoxyalkylene obtained by polycondensation of the alkoxydecane shown.

(11) The composition according to any one of the above (1), wherein the component (D) contains N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butane. a solvent of at least one of the esters.

The composition according to any one of the above (1), wherein the component (E) contains 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol. , propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl a solvent of at least one of the ethers.

(13) A resin film obtained by the composition according to any one of the above (1) to (12).

(14) A liquid crystal alignment treatment agent characterized by The composition according to any one of the above (1) to (12).

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

(16) A liquid crystal alignment film which is obtained by the inkjet method using the liquid crystal alignment treatment agent described in the above (14).

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

(18) The liquid crystal alignment film according to the above (15) or (16), which is used in a liquid crystal display device produced by the following steps, wherein the step is such that one of the electrodes has a liquid crystal layer between the substrates, A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes to polymerize the polymerizable compound.

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

(20) The liquid crystal alignment film according to the above (15) or (16), which is used in a liquid crystal display device produced by the following steps, wherein the step is such that one of the electrodes has a liquid crystal layer between the substrates, A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes to polymerize the polymerizable group.

(21) A liquid crystal display device comprising the liquid crystal alignment film according to (20) above.

The composition of the present invention contains a solvent having a specific structure, a polyimine precursor selected from a reaction of a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic dianhydride component, or a polyfluorene. A resin film can be formed by firing at a low temperature and at least one polymer of the amine and a polyoxyalkylene having a specific structure. Further, when the composition of the present invention is applied to a substrate, pinholes can be suppressed from being generated by repulsion on the resin film.

Further, the liquid crystal alignment treatment agent composed of the composition of the present invention can form a liquid crystal alignment film by firing at a low temperature. When the liquid crystal alignment treatment agent is applied to a substrate, pinholes can be suppressed from being generated by repulsion on the liquid crystal alignment film. Therefore, the liquid crystal display element having the liquid crystal alignment film thus obtained can be a liquid crystal display element having no alignment defects and high reliability.

[Best Mode for Carrying Out the Invention]

As a result of intensive studies by the present inventors, the following findings were obtained, and the present invention was completed.

The present invention relates to a composition comprising the following components (A), (B) and (C), a liquid crystal alignment treatment agent, a resin film obtained by using the composition, and a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, And a liquid crystal display element having the liquid crystal alignment film.

(A) component: a solvent (also referred to as a specific solvent) selected from at least one of the following formula [1a] or formula [1b].

(In the formula [1a], X ¹ represents an alkyl group having 1 to 4 carbon atoms, and in the formula [1b], X ² represents an alkyl group having 1 to 4 carbon atoms).

(B) component: a polymer selected from at least one of a polyimine precursor or a polyimine obtained by reacting a diamine component having a diamine compound having a carboxyl group with a tetracarboxylic dianhydride component (also Called a specific polymer).

(C) component: a polyoxyalkylene obtained by polycondensing an alkoxy decane containing any one of the alkoxy decane represented by the following formula [A1], the formula [A2], or the formula [A3] (also called For a specific polyoxane).

(A ¹ ) _m Si(A ² ) _n (OA ³ ) _p [A1]

(In the formula [A1], A ¹ represents an aliphatic hydrocarbon, a benzene ring, a cyclohexane ring, a heterocyclic ring or an organic group having a steroid structure of 8 to 35 carbon atoms, and A ² represents a hydrogen atom or a carbon number of 1 to 5, respectively. The alkyl group, A ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3, but m+n+p is 4) .

(Chemical Formula 13) (B ¹ ) _m Si(B ² ) _n (OB ³ ) _p [A2]

(In the formula [A2], B ¹ represents a vinyl group, an epoxy group, an amine group, a decyl group, an isocyanate group, a methacryl fluorenyl group, an acryl fluorenyl group, a ureido group or an organic group having a cinnamyl group of 2 to 12 carbon atoms; Base, B ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents 0. An integer of ~3, but m+n+p is 4).

(14) (D ¹ ) _n Si(OD ² ) _4-n [A3]

(In the formula [A3], D ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, D ² represents an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3).

The specific solvent of the present invention is generally lower in boiling point than the solvent NMP or γ-BL used in the composition containing the polyimine-based polymer, and can dissolve the specific polymer of the present invention. The specific polyoxyalkylene of the present invention can be dissolved not only in a solvent having a high boiling point such as NMP or γ-BL but also in a specific solvent of the present invention, a general alcohol solvent or a glycol solvent. Therefore, the composition of the present invention can be formed into a resin film by firing at a low temperature.

Further, the composition of the present invention is such that even if a polymer solution of a specific polyoxane or a specific polyoxane is mixed with a polymer solution in which a specific polymer is dissolved in a specific solvent, since the specific solvent is not like NMP or γ-BL The solvent is highly polar, so the compatibility of the solvent with the polymer solution of a specific polyoxane or a specific polyoxane becomes high. Therefore, when this composition is applied to a substrate, pinholes can be suppressed from being generated by repulsion on the resin film.

In addition, the specific solvent of the present invention is generally compared to having a poly When a solvent such as NMP or γ-BL used in the composition of the quinone imine polymer is used, the surface tension as a solvent is low. Therefore, the composition using a specific solvent has high wettability to the substrate. Therefore, it is possible to suppress the occurrence of pinholes due to repulsion on the resin film.

From the above viewpoints, the composition of the present invention can form a resin film by firing at a low temperature, and when it is further applied to a substrate, pinholes can be suppressed from being repelled on the resin film. Moreover, the liquid crystal alignment treatment agent obtained from the composition of the present invention can also obtain the above effects for the same reason.

Hereinafter, embodiments of the present invention will be described in more detail.

<specific solvent>

The specific solvent of the component (A) of the present invention is a solvent selected from at least one of the following formulas [1a] or [1b].

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

(In the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms).

Specifically, for example, there is a structure represented by the following formula [1a-1] to the formula [1a-4] and the formula [1b-1] to the formula [1b-4].

Among them, from the viewpoint of the boiling point of the solvent and the ease of availability, the formula [1a-1], the formula [1b-1], the formula [1b-2] or the formula [1b-3] is preferred.

In the specific solvent of the present invention, the resin film or the liquid crystal alignment film can be formed by firing at a low temperature, and the effect of improving the wettability of the substrate can be improved. Therefore, in the composition or the liquid crystal alignment treatment agent using the composition, The solvent contained in the whole is preferably 50 to 100% by mass. Among them, it is preferably 55 to 100% by mass. More preferably 55 to 95% by mass.

In the entire solvent of the composition or the liquid crystal alignment treatment agent using the composition, the larger the amount of the specific solvent of the present invention, the effect of the present invention, that is, the resin film or the liquid crystal alignment film can be formed by firing at a low temperature. The wettability of the cloth solution to the substrate becomes higher, and a resin film or a liquid crystal alignment film excellent in coatability can be obtained.

<specific polymer>

The specific polymer of the component (B) of the present invention is at least one selected from the group consisting of a polyamine imine precursor or a polyimine obtained by reacting a diamine component having a carboxyl group-containing diamine compound with a tetracarboxylic dianhydride component. Kind of polymer.

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

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

The diamine component is a diamine compound having two primary or secondary amine groups in the molecule, and the tetracarboxylic acid component is, for example, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dicarboxylic acid dihalide compound, or a dicarboxylic acid II. An alkyl ester compound or a dialkyl ester dihalide compound.

The specific polymer of the present invention can be obtained relatively simply by using a diamine compound having a carboxyl group represented by the following formula [B] and a tetracarboxylic dianhydride represented by the following formula [C] as a raw material. The reason is preferably a polylysine composed of a structural formula of a repeating unit represented by the following formula [D] or a polyimine which is ruthenium imidized with the polylysine.

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

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

Further, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and a formula [A] can be introduced into the polymer of the formula [D] obtained above by a usual synthesis method. The alkyl group or the ethylidene group having a carbon number of 1 to 5 of A ³ and A ⁴ is shown.

<Diamine compound having a carboxyl group>

The diamine compound having a carboxyl group of the present invention is a diamine compound having a structure represented by the following formula [2] in the molecule.

[Chem. 21]-(CH ₂ ) _a -COOH [2]

In the formula [2], a represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferred.

Specific examples of the diamine compound having a structure represented by the formula [2] include a structure represented by the following formula [2a].

In the formula [2a], a represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, it is preferably 0 or 1.

In the formula [2a], n represents an integer of 1 to 4. Among them, from the viewpoint of easiness of synthesis, it is preferably 1.

The method for producing the diamine compound represented by the formula [2a] of the present invention is not particularly limited, and preferred methods are, for example, those described below.

One example of the diamine compound represented by the formula [2a] is obtained by synthesizing a dinitro compound represented by the following formula [2a-A], followed by reduction of the nitro group and conversion into an amine group.

(In the formula [2a-A], a represents an integer of 0 to 4, and n represents an integer of 1 to 4).

The dinitro group of the dinitro compound represented by the formula [2a-A] is further The original method is not particularly limited, and is usually used in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent, and palladium-carbon, platinum oxide, nickel nickel, platinum black, lanthanum-alumina or A method in which platinum sulphide carbon or the like is used as a catalyst and reacted under hydrogen, hydrazine or hydrogen chloride.

Further, for example, the diamine compound having a carboxyl group of the present invention has a structure represented by the following formula [2a-1] to formula [2a-4].

In the formula [2a-1], A ¹ represents 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, from the viewpoint of easiness of synthesis, a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO- or -OCO-. More preferably, it is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH- or -N(CH ₃ )-.

In the formula [2a-1], m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4. Among them, m ¹ + m ^{2 is} preferably 1 or 2.

In the formula [2a-2], m ³ and m ⁴ each represent an integer of 1 to 5. Among them, from the viewpoint of easiness of synthesis, it is preferably 1 or 2.

In the formula [2a-3], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, a linear alkyl group having 1 to 3 carbon atoms is preferred.

In the formula [2a-3], m ⁵ represents an integer of 1 to 5. Of these, it is preferably 1 or 2.

In the formula [2a-4], A ³ represents 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-. Of these, a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _{2 is} preferred. -, -COO- or -OCO-. More preferably -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-.

In the formula [2a-4], m ⁶ represents an integer of 1 to 4. Among them, from the viewpoint of easiness of synthesis, it is preferably 1.

The diamine compound having a carboxyl group of the present invention is preferably 20 mol% to 100 mol%, more preferably 30 mol% to 100 mol% in the total diamine component.

The diamine compound having a carboxyl group may be blended with the solubility of the solvent or the coating property of the composition, the liquid crystal alignment property when forming the liquid crystal alignment film, the voltage retention ratio, the storage charge, etc., in combination with the specific polymer of the present invention. It is used in the type or in two or more types.

<2nd bisamine compound>

In the diamine component for producing the specific polymer of the present invention, a diamine compound (also referred to as a second diamine compound) represented by the following formula [2b] can be used as the second diamine compound.

(In the formula [2b], Y represents a structure of the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], and m represents An integer from 0 to 4.)

In the formula [2b-1], a represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials or ease of synthesis, an integer of 0 or 1 is preferred.

In the formula [2b-2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the viewpoint of availability of raw materials or ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO is preferred. -. More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), - O -, - CH 2 O- or -COO-.

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

In the formula [2b-2], Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, from the viewpoint of easiness of synthesis, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable. More preferably 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 the cyclic group may pass through an alkyl group having 1 to 3 carbon atoms. The group is substituted with an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Further, Y ⁴ may also be a divalent organic group selected from an organic group having a carbon number of 12 to 25 having a steroid skeleton. Among them, from the viewpoint of easiness of synthesis, a benzene ring, a cyclohexane ring or an organic group having a carbon number of 12 to 25 having a steroid skeleton is preferred.

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 atom on the cyclic group may pass through an alkyl group having 1 to 3 carbon atoms. The group is substituted with an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferred.

In the formula [2b-2], n represents an integer of 0 to 4. Among them, the raw materials are taken The viewpoint of the availability or the ease of synthesis is preferably 0 to 3. More preferably 0~2.

In the formula [2b-2], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are alkyl groups having 1 to 9 carbon atoms or alkoxy groups having 1 to 9 carbon atoms.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2b-2] of the substituent Y in the formula [2b], for example, are disclosed in the international publication. The same combination of (2-1) to (2-629) shown in Tables 6 to 47 of 13 to 34 of WO2011/132751 (2011.10.27). Further, in the tables of the International Publications, although Y ¹ to Y ⁶ of the present invention are represented by Y1 to Y6, Y1 to Y6 can also be interpreted as Y ¹ to Y ⁶ .

In the formula [2b-3], Y ⁷ represents an alkyl group having 8 to 22 carbon atoms.

In the formula [2b-4], Y ⁸ and Y ⁹ each independently represent a hydrocarbon group having 1 to 6 carbon atoms.

In the formula [2b-5], Y ¹⁰ represents an alkyl group having 1 to 8 carbon atoms.

The method for producing the diamine compound represented by the formula [2b] of the present invention is not particularly limited, and preferred methods are, for example, those described below.

One of the examples is a diamine compound represented by the formula [2b] which is obtained by synthesizing a dinitro compound represented by the following formula [2b-A], followed by reduction of the nitro group and conversion into an amine group.

(In the formula [2b-A], Y represents a compound selected from the above formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5]. A substituent of at least one structure, m represents an integer from 0 to 4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [2b-A] is not particularly limited, and is usually a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. A method in which palladium-carbon, platinum oxide, nickel stellate, platinum black, ruthenium-alumina or sulphide sulphide carbon is used as a catalyst, and is reacted under hydrogen, hydrazine or hydrogen chloride.

The specific structure of the second bisamine compound represented by the formula [2b] of the present invention is as follows, but is not limited thereto.

That is, the second diamine represented by the formula [2b], except m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-di In addition to aminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, for example, the following A diamine compound of the structure represented by the formula [2b-6] to [2b-46].

(In the formula [2b-6] to the formula [2b-9], A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(In the formula [2b-34]~Form [2b-36], R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² represents a carbon number of 1 ~22 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy).

(In the formula [2b-37]~Form [2b-39], R ³ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -, 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).

(In the formula [2b-40] and the formula [2b-41], R ⁵ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ - or -O-, R ⁶ represents a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group).

(In the formula [2b-42] and the formula [2b-43], R ⁷ represents an alkyl group having 3 to 12 carbon atoms. Further, the cis-trans isomerization of the 1,4-cyclohexylene group is each a counter Preferred isomers).

(In the formula [2b-44] and the formula [2b-45], R ⁸ represents an alkyl group having a carbon number of 3 to 12. Further, the cis-trans isomerization of the 1,4-cyclohexylene group is inversely Preferred isomers).

(In the formula [2b-46], B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, and B ² represents an oxygen group. Atom or -COO-* (but with a "*" bond and B ³ bond), B ¹ represents an oxygen atom or -COO-* (but with a "*" bond and (CH ₂ )a ² Bond))). Further, a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1.

In the second bisamine compound of the present invention, the composition of the diamine compound having the structure represented by the formula [2b-2] in the formula [2b] can be used to improve the hydrophobicity of the resin film. Further, when the liquid crystal alignment film is formed, the liquid crystal pretilt angle can be improved. In this case, for the purpose of improving the effects, two of the above diamine compounds are represented by the formula [2b-28] to the formula [2b-39] or the formula [2b-42] to the formula [2b-46]. Amine compounds are preferred. More preferably, it is a diamine compound represented by the formula [2b-24] to the formula [2b-39] or the formula [2b-42] to the formula [2b-46]. Moreover, in order to further enhance these effects, these diamine compounds are preferably 5 mol% or more and 80 mol% or less of the entire diamine component. The diamine compound is more preferably 5 mol% or more and 60 mol% or less of the entire diamine component from the viewpoints of the coating property of the composition and the liquid crystal alignment agent or the electrical properties of the liquid crystal alignment film. It is particularly preferably 10 mol% or more and 60 mol% or less of the entire diamine component.

The second bisamine compound of the present invention can be blended with a solvent or a coating property of a specific polymer of the present invention, a liquid crystal alignment property when forming a liquid crystal alignment film, a voltage retention ratio, a storage charge, and the like. It can be used in two types or more.

<Other diamine compounds>

In the specific polymer of the present invention, in addition to the effect of the present invention, in addition to the diamine compound having a carboxyl group in the molecule represented by the formula [2a], the formula [2a-1] to the formula [2a-4], Alternatively, other diamine compounds (also referred to as other diamine compounds) may be used as the diamine component in addition to the second diamine compound represented by the formula [2b].

Specific examples of the other diamine compounds are listed below, but are not limited thereto.

That is, other diamine compounds such as 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4 , 4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3, 3'-Difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3' -diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diamino Diphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-di Aminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diamino group Diphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)decane, bis(3-aminophenyl)decane, dimethyl Base-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4,4' -diaminodiphenylamine, 3,3'-diaminodiphenyl Amine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4' -diaminodiphenyl)amine, N-methyl (3,3'-diaminodiphenyl) Amine, N-methyl (3,4'-diaminodiphenyl)amine, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl (2,3'- Diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 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, double (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-double (4-Aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]diphenylamine, 4,4'-[1,3-phenylene bis(Asia Methyl)]diphenylamine, 3,4'-[1,4-phenylene bis (nara )]Diphenylamine, 3,4'-[1,3-phenylenebis(methylene)]diphenylamine, 3,3'-[1,4-phenylenebis(methylene)]diphenylamine , 3,3'-[1,3-phenylenebis(methylene)]diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-stretch Phenyl bis[(3-aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-amine) Phenyl phenyl) ketone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylphenyl bis(3-aminobenzoate), 1,3- Phenyl bis(4-aminobenzoate), 1,3-phenylene bis(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)m-xylyleneamine, N,N'-bis(3-amine Benzophenyl)m-xylamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2' - bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-double (4-Aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexa Fluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methyl Phenyl)propane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxyl) Butane, 1,4-bis(3-aminophenoxyl) Butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxyl) Hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-(3-aminophenoxyl) Heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminobenzene Oxy) decane, 1,9-bis(3-aminophenoxy)decane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxyl) Base) decane, 1,11-(4-aminophenoxy)undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxyl Dodecane, 1,12-(3-aminophenoxy Dodecyl, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutyl Alkane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminoguanidine Alkane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

Further, the other diamine compound may, for example, be an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in a side chain of a diamine, or a large cyclic substituent having such a structure. Specifically, for example, there are diamine compounds represented by the following formulas [DA1] to [DA13].

(In the formula [DA1]~Form [DA6], A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-; A ² It is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(In the formula [DA7], p represents an integer from 1 to 10).

The diamine compound represented by the following formula [DA8] to formula [DA13] can be used as the other diamine compound insofar as the effect of the present invention is not impaired.

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

Further, a diamine compound represented by the following formula [DA14] can also be used within a range not impairing the effects of the present invention.

(In the formula [DA14], A ¹ is selected from the group consisting of -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH) _a divalent organic group in ₃ )- or -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 selected From a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ ) CO- or -O(CH ₂ ) _m - (m is an integer of 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4).

Further, as the other diamine compound, a diamine compound represented by the following formula [DA15] and formula [DA16] can also be used.

The above-mentioned other diamine compound may have a solubility in a solvent or a coating property of a specific polymer of the present invention, and properties such as liquid crystal alignment property, voltage holding ratio, and storage charge when the liquid crystal alignment film is formed, may be one type. Or use 2 or more types.

<tetracarboxylic dianhydride component>

The tetracarboxylic dianhydride component for producing the specific polymer of the present invention is, for example, a tetracarboxylic dianhydride represented by the following formula [3] or a tetracarboxylic acid derivative (also referred to as a specific tetracarboxylic dianhydride component). ).

In the formula [3], Z ¹ is a group selected from at least one of the following formulas [3a] to [3j].

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and each may be the same or different.

In the structure represented by the formula [3] of the specific tetracarboxylic dianhydride component of the present invention, Z ^{1 is} preferably a formula [3a] from the viewpoint of easiness of synthesis or easiness of polymerization reactivity at the time of producing a polymer. The structure represented by the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula [3g]. More preferably, it is a structure represented by the formula [3a], the formula [3e], the formula [3f], or the formula [3g].

The specific tetracarboxylic dianhydride component of the present invention is preferably 1 mol% or more of the total tetracarboxylic acid component. More preferably, it is 5 mol% or more, and particularly preferably 10 mol% or more.

Further, when a specific tetracarboxylic dianhydride component having a structure of the formula [3e], the formula [3f] or the formula [3g] is used, the amount of the tetracarboxylic dianhydride component is set to be tetracarboxylic dianhydride. If the body is 20% or more, the desired effect can be obtained. It is preferably 30 mol% or more. Further, all of the tetracarboxylic dianhydride components may be a tetracarboxylic dianhydride component having the structure of the formula [3e], the formula [3f] or the formula [3g].

In the specific polymer of the present invention, other tetracarboxylic dianhydride components other than the specific tetracarboxylic dianhydride component can be used within a range that does not impair the effects of the present invention.

The other tetracarboxylic dianhydride component is, for example, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dicarboxylic acid dihalide compound, a dicarboxylic acid dialkyl ester compound or a dialkyl ester dihalide compound shown below.

That is, for example, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-decanetetracarboxylic acid, 1,2,5,6-nonanetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4- Biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)fluorene , 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)dimethyloxane, bis(3,4-dicarboxyphenyl)diphenylnonane, 2,3,4 , 5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10 - tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

The specific tetracarboxylic dianhydride component and the other tetracarboxylic acid component are compatible with the solubility of the specific polymer of the present invention, the coating property of the composition, the liquid crystal alignment property when the liquid crystal alignment film is formed, the voltage retention ratio, The characteristics of the stored charge and the like can be used in one type or in a mixture of two or more types.

<Method of Manufacturing Specific Polymer>

In the present invention, a method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component with a tetracarboxylic dianhydride component. In general, a tetracarboxylic dianhydride component selected from at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof is reacted with a diamine component formed from one or more kinds of diamine compounds. , get polyamic acid. Specifically, a method of polycondensing a tetracarboxylic dianhydride with a primary or secondary diamine compound to obtain a polyamic acid, and a tetracarboxylic acid and a primary or secondary diamine compound may be used. A method of obtaining a polyamic acid by dehydration polycondensation or a method of polycondensing a dicarboxylic acid dihalide with a primary or secondary diamine compound to obtain a polyamic acid.

In order to obtain a polyalkyl amide, the following method can be used: a method of polycondensing a tetracarboxylic acid which dialkylates a carboxylic acid group, a polycondensation with a primary or secondary diamine compound, and a carboxylic acid group. A method of polycondensation of a dialkyl esterified dicarboxylic acid dihalide, a primary or secondary diamine compound, or a method of converting a carboxyl group of a polylysine to an ester.

In order to obtain a polyimine, a method of forming a polyimine by ring-closing the polyamic acid or polyalkyl amide may be used.

The reaction of the diamine component with the tetracarboxylic acid component usually involves the diamine component and the tetracarboxylic acid component in an organic solvent. The organic solvent to be used in this case is not particularly limited as long as it dissolves the specific solvent of the component (A) of the present invention or the produced polyimide precursor.

The solvent other than the specific solvent of the present invention has, for example, the following Solvent.

Namely, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl hydrazine, γ- Butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

These can be used alone or in combination. Further, even a solvent which does not dissolve the polyimide precursor can be used in the above solvent as long as it does not precipitate in the precipitated polyimide precursor. Further, since the water in the organic solvent hinders the polymerization reaction and causes hydrolysis of the produced polyimide precursor, the organic solvent is preferably dried and dried.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, a solution in which a diamine component is dispersed or dissolved in an organic solvent is stirred to directly add a tetracarboxylic acid component or to disperse or dissolve a tetracarboxylic acid component. a method of adding to an 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 adding a tetracarboxylic acid component and a diamine component, etc. Use any of these methods. Further, when the diamine component or the tetracarboxylic acid component is reacted in a plurality of types, the reaction may be carried out in advance, or the reaction may be carried out in sequence, and the respective reactions may be low. The molecular weight body is mixed and reacted to become a polymer. The polymerization temperature at this time may be any temperature of from -20 ° C to 150 ° C, but is preferably in the range of from -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration, but when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution is high. It becomes too high and it is difficult to stir evenly. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent may be added.

In the polymerization reaction of the polyimine precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably from 0.8 to 1.2. As with the general polycondensation reaction, as the molar ratio approaches 1.0, the molecular weight of the resulting polyimine precursor becomes larger.

The polyimine of the present invention is a polyimine obtained by ring-closing the polyimine precursor. In the polyimine, the ring closure ratio of the guanamine group (also referred to as a ruthenium imidation ratio) is not Must be 100%, can be adjusted according to the purpose or purpose.

A method for subjecting a polyimine precursor to ruthenium imidization, for example, a hydrazine imidization in which a solution of a polyimide precursor is directly heated, or a solution in which a catalyst is added to a polyimide precursor The catalyst in the oxime is imidized.

The temperature at which the polyimine precursor is thermally imidated in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, preferably water produced by the imidization reaction. The reaction was carried out while excluding the outside of the system.

The catalyst oxime imidization of the polyimine precursor adds a basic catalyst and an acid anhydride to the solution of the polyimide precursor, and is at -20 to 250 ° C, preferably 0 to 180 ° C. Stir it down. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group; the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles. The basic catalyst is, for example, pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate basicity required for carrying out the reaction. The acid anhydride is, for example, acetic anhydride, trimellitic anhydride or pyromellitic anhydride. When acetic anhydride is used, purification after completion of the reaction is easy, which is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the resulting polyimine precursor or polyimine is recovered from the reaction solution of the polyimide precursor or the polyimide, the reaction solution is poured into a solvent to precipitate. The solvent used for the precipitation is, for example, methanol, ethanol, isopropanol, acetone, hexane, butyl sirolimus, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water or the like. After being introduced into a solvent and allowing the precipitated polymer to be recovered by filtration, it can be dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the precipitate-recovered polymer is redissolved in an organic solvent, and the reprecipitation recovery operation is repeated 2 to 10 times to reduce impurities in the polymer. In the solvent at the time, for example, an alcohol, a ketone, a hydrocarbon, or the like is used, and when a solvent selected from three or more types selected from the above is used, the purification efficiency can be further improved, which is preferable.

The molecular weight of the specific polymer of the present invention, in consideration of the strength of the resin film or the liquid crystal alignment film obtained by the above, and the workability and film coating property at the time of film formation, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method Preferably, it is 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<specific polyoxane>

The specific polyoxyalkylene of the component (C) of the present invention is subjected to polycondensation of an alkoxydecane containing any one of the alkoxysilanes represented by the above formula [A1], the formula [A2] or the formula [A3]. And the polyoxyalkylene obtained.

The alkoxydecane represented by the formula [A1] of the present invention is an alkoxydecane represented by the following formula [A1].

(A ¹ ) _m Si(A ² ) _n (OA ³ ) _p [A1]

In the formula [A1], A ¹ is an aliphatic hydrocarbon, a benzene ring, a cyclohexane ring, a heterocyclic ring or an organic group having a steroid structure of 8 to 35 carbon atoms.

In the formula [A1], A ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred.

In the formula [A1], A ³ is an alkyl group having 1 to 5 carbon atoms, respectively. Among them, from the viewpoint of the reactivity of the polycondensation, an alkyl group having 1 to 3 carbon atoms is preferable.

In the formula [A1], m is an integer of 1 or 2. Among them, from the viewpoint of synthesis, it is preferably 1.

In the formula [A1], n is an integer of 0 to 2.

In the formula [A1], p is an integer of 0 to 3. Among them, from the viewpoint of the reactivity of the polycondensation, an integer of 1 to 3 is preferable. More preferably 2 or 3.

In the formula [A1], m+n+p is 4.

Specific examples of the alkoxydecane represented by the formula [A1] include, for example, octyltrimethoxydecane, octyltriethoxydecane, decyltrimethoxydecane, dodecyltrimethoxydecane, and twelve. Alkyl triethoxy decane, hexadecyl trimethoxy decane, cetyl triethoxy decane, pentyl triethyl Oxydecane, heptadecyltrimethoxynonane, heptadecyltriethoxydecane,octadecyltrimethoxydecane,octadecyltriethoxydecane,dodecyltrimethoxydecane , nonadecyltriethoxydecane, isooctyltriethoxydecane, phenethyltriethoxydecane, pentafluorophenylpropyltrimethoxydecane, m-styrylethyltrimethoxy Decane, p-styrylethyltrimethoxydecane, 1-naphthyltriethoxydecane, 1-naphthyltrimethoxynonane, triethoxy-1H,1H,2H,2H-tridecafluoro- N-octyldecane, dimethoxydiphenyl decane, dimethoxymethylphenyl decane or triethoxyphenyl decane.

Further, an alkoxydecane represented by the following formula [A1-1] to formula [A1-32] can also be used.

(In the formula [A1-1] to the formula [A1-18], R ¹ each represents an alkyl group having 1 to 5 carbon atoms).

(In the formula [A1-19]~[A1-22], R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² represents -O-, -COO-, -OCO-, -CONH-, - NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, R ³ represents a carbon number of 1~ 12 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy).

(In the formula [A1-23] and the formula [A1-24], R ¹ represents an alkyl group having 1 to 5 carbon atoms, respectively, and R ² represents -O-, -COO-, -OCO-, -CONH-, - NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, R ³ represents a carbon number of 1~ 12 alkyl, alkoxy, fluoroalkyl, fluoroalkoxy, fluoro, cyano, trifluoromethyl, nitro, azo, decyl, ethenyl, ethoxylated Or hydroxy).

(In the formula [A1-25]~Form [A1-31], R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² represents -O-, -COO-, -OCO-, -CONH-, -, respectively. NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or -CH ₂ OCO-, R ³ represents a carbon number of 1~ 12 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy).

(In the formula [A1-32], R ¹ represents an alkyl group having 1 to 5 carbon atoms, B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, and B ³ represents a 1,4-stretched ring. Hexyl or 1,4-phenylene, B ² represents an oxygen atom or COO-* (however, the "*" linkage is bonded to B ³ ), and B ¹ represents an oxygen atom or COO-* (but, attached) *" The link key is bonded to (CH ₂ )a ² )). Further, a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1.

The alkoxydecane represented by the above formula [A1] is compatible with the strength of the resin film or the liquid crystal alignment film, the workability at the time of formation of the film, the liquid crystal alignment property, the voltage retention ratio, the storage charge, and the like when the liquid crystal alignment film is used. Characteristics, Use 1 type or mix 2 types or more.

The alkoxydecane represented by the formula [A2] of the present invention is an alkoxydecane represented by the following formula [A2].

(B ¹ ) _m Si(B ² ) _n (OB ³ ) _p [A2]

In the formula [A2], B ¹ is a vinyl group, an epoxy group, an amine group, a decyl group, an isocyanate group, a methacryl fluorenyl group, an acryl fluorenyl group, a ureido group or an organic group having a cinnamyl group having 2 to 12 carbon atoms. . Among them, a vinyl group, an epoxy group, an amine group, a methacryl fluorenyl group, an acryl fluorenyl group or a ureido group is preferred from the viewpoint of easiness. More preferably, it is a methacryl oxime group, an acryl oxime group or a urea group.

In the formula [A2], B ^{2 is} each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred.

In the formula [A2], B ³ represents an alkyl group having 1 to 5 carbon atoms, respectively. Among them, from the viewpoint of the reactivity of the polycondensation, an alkyl group having 1 to 3 carbon atoms is preferable.

In the formula [A2], m is an integer of 1 or 2. Among them, from the viewpoint of synthesis, it is preferably 1.

In the formula [A2], n is an integer of 0 to 2.

In the formula [A2], p is an integer of 0 to 3. Among them, from the viewpoint of the reactivity of the polycondensation, an integer of 1 to 3 is preferable. More preferably 2 or 3.

In the formula [A2], m+n+p is 4.

Specific examples of the alkoxydecane represented by the formula [A2] include, for example, allyltriethoxydecane, allyltrimethoxydecane, diethoxymethylvinylnonane, and dimethoxymethyl. Vinyl decane, triethoxy B Alkenyl decane, vinyl trimethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, m-styrylethyl triethoxy decane, p-styrylethyl triethoxy Decane, m-styrylmethyltriethoxydecane, p-styrylmethyltriethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyl Trimethoxy decane, diethoxy (3-glycidyloxypropyl) methyl decane, 3-glycidoxy propyl (dimethoxy) methyl decane, 3-glycidyloxy Propyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-(2-aminoethylamino)propyldimethoxymethyldecane, 3- (2-Aminoethylamino)propyltriethoxydecane, 3-(2-aminoethylamino)propyltrimethoxydecane, 3-aminopropyldiethoxymethyldecane , 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, trimethoxy[3-(phenylamino)propyl]decane, 3-mercaptopropyl (dimethoxy) Methyl decane, (3-mercaptopropyl) triethoxy decane, (3-mercaptopropyl) trimethoxy decane, 3-(triethoxy decyl) propyl Isocyanate, 3-(triethoxydecyl)propyl methacrylate, 3-(trimethoxydecyl)propyl methacrylate, 3-(triethoxydecyl)propyl acrylate , 3-(trimethoxydecyl)propyl acrylate, 3-(triethoxydecyl)ethyl methacrylate, 3-(trimethoxydecyl)ethyl methacrylate, 3- (triethoxydecyl)ethyl acrylate, 3-(trimethoxydecyl)ethyl acrylate, 3-(triethoxydecyl)methyl methacrylate, 3-(trimethoxy)矽alkyl)methyl methacrylate, 3-(triethoxydecyl)methacrylate, 3-(trimethoxydecyl)methacrylate, γ-ureidopropyltriethoxydecane Γ-urea Propyltrimethoxydecane, γ-ureidopropyltripropoxydecane, (R)-N-1-phenylethyl-N'-triethoxydecylpropylurea, (R)- N-1-phenylethyl-N'-trimethoxydecyl propyl urea, bis[3-(trimethoxydecyl)propyl]urea, bis[3-(tripropoxydecyl)propyl Urea, 1-[3-(trimethoxydecyl)propyl]urea, and the like.

The alkoxydecane represented by the above formula [A2] is compatible with the strength of the resin film or the liquid crystal alignment film, the workability at the time of formation of the film, and the liquid crystal alignment property, voltage retention ratio, and storage charge when the liquid crystal alignment film is used. The characteristics can be used in one type or in two or more types.

The alkoxydecane represented by the formula [A3] of the present invention is an alkoxydecane represented by the following formula [A].

(D ¹ ) _n Si(OD ² ) _4-n [A3]

In the formula [A3], D ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, but these may be substituted by a halogen atom, a nitrogen atom, an oxygen atom or a sulfur atom. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred.

In the formula [A3], D ² represents an alkyl group having 1 to 5 carbon atoms, respectively. Among them, from the viewpoint of the reactivity of the polycondensation, an alkyl group having 1 to 3 carbon atoms is preferable.

In the formula [A3], n is an integer of 0 to 3.

Specific examples of the alkoxydecane represented by the formula [A3] include, for example, tetramethoxynonane, tetraethoxydecane, tetrapropoxydecane, tetrabutoxydecane, methyltrimethoxydecane, and A. Triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl trimethoxy decane, C Triethoxy decane, methyl tripropoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, diethoxy diethyl decane, dibutoxy dimethyl decane , (chloromethyl)triethoxydecane, 3-chloropropyldimethoxymethylnonane, 3-chloropropyltriethoxydecane, 2-cyanoethyltriethoxydecane, trimethoxy A group of (3,3,3-trifluoropropyl)decane, hexyltrimethoxydecane or 3-trimethoxydecylpropyl chloride.

In the above formula [A3], the alkoxydecane wherein n is 0 may, for example, be tetramethoxydecane, tetraethoxydecane, tetrapropoxydecane or tetrabutoxydecane.

The alkoxydecane represented by the above formula [A3] is compatible with the strength of the resin film or the liquid crystal alignment film, the workability at the time of formation of the film, the liquid crystal alignment property, the voltage retention ratio, the storage charge, and the like when the liquid crystal alignment film is used. The characteristics can be used in one type or in a mixture of two or more types.

The specific polyoxyalkylene of the present invention is obtained by polycondensation of an alkoxysilane containing any one of the alkoxysilanes represented by the above formula [A1], the formula [A2] or the formula [A3]. The alkane is preferably a polyoxyalkylene obtained by subjecting alkoxydecane containing a plurality of kinds of such alkoxydecanes to polycondensation. That is, for example, there are two types of alkoxydecane including the above formula [A1] and formula [A2], the above formula [A1] and formula [A3], or the above formula [A2] and formula [A3]; [A1], a polyoxyalkylene obtained by polycondensation of three types of alkoxydecane of the formula [A2] and the formula [A3]. In particular, it is preferable to include two types of alkoxydecanes of the above formula [A1] and formula [A2], the above formula [A1] and formula [A3]; or the above formula [A1], formula [A2] and formula 3 kinds of alkoxydecane of [A3].

The alkoxydecane represented by the above formula [A1], the formula [A2] or the formula [A3] is used to obtain the specific polyoxyalkylene of the present invention.

The alkoxydecane represented by the formula [A1] is preferably from 1 to 40 mol%, more preferably from 1 to 30 mol%, based on the total alkoxydecane. Further, the alkoxydecane represented by the formula [A2] is preferably from 1 to 70 mol%, more preferably from 1 to 60 mol%, based on the total alkoxydecane. Further, the alkoxydecane represented by the formula [A3] is preferably from 1 to 99 mol%, more preferably from 1 to 80 mol%, based on the total alkoxydecane.

The method for obtaining the specific polyoxyalkylene used in the present invention is not particularly limited. The specific polyoxyalkylene in the present invention contains an alkoxydecane of any one of the alkoxydecanes represented by the above formula [A1], formula [A2] or formula [A3], and is condensed in an organic solvent. Further, a plurality of types of alkoxydecane in the alkoxydecane represented by the above formula [A1], formula [A2] or formula [A3] are obtained by polycondensation in an organic solvent. Further, the specific polyoxyalkylene of the present invention is obtained by polycondensing an alkoxydecane and then uniformly dissolving the solution in an organic solvent.

The method of polycondensing the specific polyoxyalkylene of the present invention is not particularly limited. Among them, for example, a method in which alkoxydecane is subjected to a hydrolysis ‧ polycondensation reaction in a specific solvent, an alcohol solvent or an ethylene glycol solvent of the present invention is carried out. At this time, the hydrolysis ‧ polycondensation reaction can partially hydrolyze or completely hydrolyze. In the case of complete hydrolysis, it is theoretically possible to add water in an amount of 0.5 times the molar amount of all alkoxy groups in the alkoxysilane, but it is preferred to add more water than 0.5 times the molar amount. In order to obtain the specific polyoxyalkylene of the present invention, the amount of water used in the above hydrolysis and polycondensation reaction can be matched. Suitably, it is preferably 0.5 to 2.5 times the molar amount of all alkoxy groups in the alkoxydecane.

Further, for the purpose of promoting hydrolysis ‧ polycondensation reaction, an acidic compound such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid; ammonia, methylamine, ethylamine, ethanolamine or triethylamine may be used; A basic compound such as an amine; or a catalyst such as a metal salt such as hydrochloric acid, nitric acid or nitric acid. Further, by heating the solution in which the alkoxydecane is dissolved, the hydrolysis and the polycondensation reaction can be promoted. At this time, the heating temperature and the heating time can be appropriately selected in accordance with the purpose. For example, the mixture is heated and stirred at 50 ° C for 24 hours, and then heated under reflux for 1 hour.

Further, another method of performing polycondensation, for example, a method of heating a mixture of alkoxysilane, an organic solvent, and oxalic acid to carry out a polycondensation reaction. Specifically, a method in which oxalic acid is added to a specific solvent or an alcohol solvent of the present invention to obtain a solution of oxalic acid, and then the solution is heated, and alkoxysilane is mixed. In this case, the amount of oxalic acid used in the above reaction is preferably 1 to 2.0 moles per 1 mole of all alkoxy groups in the alkoxydecane. Further, the reaction can be carried out at a temperature of from 50 to 180 ° C in the solution, but evaporation or volatilization of the solvent is avoided, and it is preferably carried out under reflux for several tens of minutes to several tens of hours.

In the polycondensation reaction of the specific polyoxane of the present invention, when a plurality of types of alkoxysilanes represented by the above formula [A1], formula [A2] and formula [A3] are used, a plurality of types may be used in advance. The mixture of the alkoxydecanes may be reacted, and the reaction may be carried out while adding a plurality of kinds of alkoxydecanes in this order.

The solvent to be used in the polycondensation reaction of the alkoxydecane is not particularly limited as long as it is dissolved in the alkoxysilane. Further, the solvent in which the alkoxysilane is not dissolved may be dissolved as the polycondensation reaction of the alkoxydecane proceeds. The solvent used in the polycondensation reaction generally uses an alcohol solvent, an ethylene glycol solvent, a glycol ether solvent, or a good compatibility with an alcohol because the alcohol is produced by the polycondensation reaction of the alkoxydecane. Organic solvent. Specific examples of the solvent used in the polycondensation reaction include alcohol solvents such as methanol, ethanol, propanol, butanol or diacetone alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and hexanediol. , 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3 - a glycol system such as pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol or 1,6-hexanediol Solvent; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, B Diol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol II Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether Or a glycol ether solvent such as propylene glycol dibutyl ether; N-methyl-2-pyrrolidone, N-ethyl -2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, tetramethylurea, hexamethylphosphonium An organic solvent such as hexamethylphosphotriamide or m-cresol which has good phase properties with an alcohol.

Among them, from the preparation of the composition of the present invention or the liquid crystal alignment treatment agent using the composition, it is preferred to use the specific solvent of the present invention. Further, in the present invention, in the case of the polycondensation reaction, the solvent may be used in one type or in a mixture of two or more types.

In the polymerization solution of the specific polyoxane obtained by the above method, the argon atom contained in the peralkoxy decane to be charged as a raw material is preferably 20 mass in terms of the SiO ₂ concentration (also referred to as SiO ₂ conversion concentration). %the following. Among them, it is preferably 5 to 15% by mass. In this concentration range, by selecting an arbitrary concentration, gelation in the solution can be suppressed, and a uniform polycondensation solution of a specific polyoxane can be obtained.

In the present invention, the polycondensation solution of the specific polyoxyalkylene obtained by the above method can be directly used as a solution of the specific polyoxane of the component (C) of the present invention, and if necessary, the specific method obtained by the above method can be obtained. The polycondensation solution of polyoxyalkylene is concentrated, or diluted with a solvent, or substituted with another solvent, as a solution of the specific polyoxyalkylene of the component (C).

The solvent (also referred to as an additive solvent) used in the dilution of the above solvent may be a solvent used in the polycondensation reaction, a specific solvent of the present invention, and other solvents. The solvent to be added is not particularly limited as long as it is uniformly dissolved in a specific polyoxane, and one type or two types or more can be used arbitrarily. The solvent to be added is, in addition to the solvent used in the above polycondensation reaction, for example, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, methyl acetate, ethyl acetate or ethyl lactate. Ester solvent, etc.

In the present invention, the specific polyoxane of the component (C) is Before the specific polymer of the component (B) is mixed, it is preferred to distill off the alcohol produced by the polycondensation reaction of the specific polyoxyalkylene under normal pressure or reduced pressure.

<Composition ‧ Liquid crystal alignment treatment agent>

A coating solution for forming a composition of the present invention or a liquid crystal alignment agent-based resin film or a liquid crystal alignment film (also collectively referred to as a resin film) using the composition, which is formed to contain a specific solvent, a specific polymer, and a specific polyfluorene A coating solution for a resin film of oxyalkylene. Among them, the composition of the present invention or the polymer of the present invention in the liquid crystal alignment treatment agent using the composition means a specific polymer and a specific polyoxyalkylene.

In the composition of the present invention or the liquid crystal alignment treatment agent using the composition, the content of the specific polyoxyalkylene is preferably 0.1 to 90 parts by mass based on 100 parts by mass of the specific polymer component. In particular, the viewpoint of the stability of the composition or the liquid crystal alignment treatment agent is preferably from 1 to 70 parts by mass based on 100 parts by mass of the specific polymer. Particularly preferred is 5 to 60 parts by mass.

In the composition of the present invention or the liquid crystal alignment treatment agent using the composition, all of the polymer components may be the polymer of the present invention, and other polymers other than the polymer may be mixed in the polymer of the present invention. In this case, the content of the polymer other than the polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass based on the polymer of the present invention. Examples of the polymer other than the polymer include the above-described diamine compound having a carboxyl group, and a polyimine precursor or a polyimine which does not use a second diamine compound or a specific tetracarboxylic acid component. Further, a polyimine precursor and a polymer other than polyimine, specifically, for example, an acrylic polymer, a methyl group Acrylic polymer, polystyrene or polyamine.

The organic solvent in the liquid crystal alignment treatment agent of the composition of the present invention or the liquid crystal alignment treatment agent using the composition is preferably from 70 to 99.9% by mass from the viewpoint of coating a uniform resin film. This content can be appropriately changed depending on the film thickness of the intended resin film or liquid crystal alignment film.

All of the organic solvents in the organic solvent used in the composition of the present invention or the liquid crystal alignment treatment agent using the composition may be the specific solvent of the present invention, and the organic solvent may be mixed in the organic solvent of the present invention. Other organic solvents than others. In this case, the specific solvent of the present invention is preferably 50 to 100% by mass based on the total amount of the solvent contained in the composition or the liquid crystal alignment treatment agent. Among them, it is preferably 55 to 100% by mass. More preferably 55 to 95% by mass.

The organic solvent other than the organic solvent is not particularly limited as long as it is an organic solvent that dissolves a specific polymer and a specific polyoxyalkylene oxide. This specific example is as follows.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl hydrazine, γ-butyl Lactone, 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 or γ-butyrolactone (hereinafter also referred to as component (D)) is preferably used.

The component (D) is preferably from 1 to 50% by mass based on the total amount of the organic solvent contained in the liquid crystal alignment treatment agent of the composition or the composition. Among them, it is preferably from 1 to 40% by mass. More preferably 1 to 30% by mass, More preferably 5 to 30% by mass.

The composition of the present invention or the liquid crystal alignment treatment agent using the composition can be used to lift the resin film or liquid crystal when the coating composition or the liquid crystal alignment treatment agent using the composition is used within a range that does not impair the effects of the present invention. An organic solvent which is a film-coating property or a surface smoothness of an alignment film, that is, a weak solvent.

Specific examples of the weak solvent for improving the coating property or surface smoothness of the resin film or the liquid crystal alignment film are as follows.

For example, there are ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butene Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1 -methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol , 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-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-butyl Oxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl 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) Ethyl alcohol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, decyl alcohol, diethylene glycol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether, diethylene glycol monobutyl ether, 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 Alcohol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2- Ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, acetic acid Methyl ester, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropane Acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or An organic solvent having a low surface tension of a solvent such as isoamyl lactate.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and two are preferably used. Ethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether (also referred to as (E) component).

The component (E) is preferably from 1 to 50% by mass based on the total amount of the organic solvent contained in the composition or the liquid crystal alignment treatment agent using the composition. Among them, it is preferably from 1 to 45% by mass. More preferably 5 to 45% by mass, More preferably 5 to 40% by mass.

In the composition of the present invention or the liquid crystal alignment treatment agent using the composition, an epoxy group, an isocyanate group, an oxetane group or a ring may be introduced within a range not impairing the effects of the present invention. a crosslinkable compound of a carbonate group; having a crosslinkable compound selected from at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxy alkyl group; or having no polymerizability A cross-linking compound that saturates. These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.

A crosslinkable compound having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylamino group Diphenylene, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl Glycidyl etherethane, bisphenol hexafluoroacetic acid diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2 -trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octanefluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine (meta-xylenediamine), 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-epoxypropoxy)phenyl)-1-(4-(1-() 4-(2,3-Epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol.

a crosslinkable compound having an oxetane group has There are two less crosslinkable compounds of the oxetanyl group represented by the following formula [4].

Specifically, it is a crosslinkable compound represented by the following formula [4-1] - formula [4-11].

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

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

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

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

Specifically, as shown in the following formula [5-1] to formula [5-37] A combination compound.

(In the formula [5-24], n represents an integer of 1 to 10; in the formula [5-25], n represents an integer of 1 to 10).

(In the formula [5-36], n represents an integer from 1 to 100; in the formula [5-37], n represents an integer from 1 to 10).

Further, a polyoxyalkylene having at least one structure represented by the following formula [5-38] to formula [5-40] can also be exemplified.

(In the formula [5-38] to the formula [5-40], R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, and a carbon number. An alkyl group, an alkoxy group, an aliphatic ring or an aromatic ring of 1 to 10, and at least one represents a structure represented by the formula [5].

More specifically, for example, the following formula [5-41] and formula [5-42] Compound.

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

a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group, for example, an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or a guanamine resin , Glycoluril-formaldehyde resin, Succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both may be used. The melamine derivative or the benzoguanamine derivative may be present in the form of a dimer or a trimer. Among these, one triazine ring is preferred to have an average of three or more and six or less hydroxymethyl groups or alkoxymethyl groups.

Examples of such a melamine derivative or a benzoguanamine derivative, for example, a triazine ring of a commercial product, MX-750 substituted by an average of 3.7 methoxymethyl groups, and a triazine ring, an average of 5.8. Methoxymethylated melamine substituted by methoxymethyl substituted MW-30 (above manufactured by Sanwa-Chemical Co., Ltd.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. , Cymel 235, 236, 238, Methoxymethylated butoxymethylated melamine of 212, 253, 254, etc., butoxymethylated melamine of Cymel 506, 508, etc., carboxymethylated butyl methacrylate such as Cymel 1141 Oxymethylated melamine, methoxymethylated ethoxymethyl benzoguanamine such as Cymel 1123, methoxymethylated butoxymethyl benzoguanamine such as Cymel 1123-10, such as Butyloxymethylated benzoguanamine of Cymel 1128, a carboxyl group-containing methoxymethylated ethoxymethyl benzoguanamine such as Cymel 1125-80 (manufactured by Mitsui Cyanamid Co., Ltd.). Further, examples of the glycoluril include, for example, butoxymethylated glycoluril of Cymel 1170, methylolated glycoluril of Cymel 1172, and methoxymethylolated glycoluril of Powderlink 1174.

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

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

A crosslinkable compound having a polymerizable unsaturated bond, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tris(methyl) a propylene methoxy ethoxy trimethylolpropane or a glycerol polyglycidyl ether poly(meth) acrylate equivalent to a crosslinkable compound having three polymerizable unsaturated groups in the molecule; further, for example, ethylene glycol (Meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol di(methyl) Acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol ( Neopentyl glycol) di(meth)acrylate, ethylene oxide bisphenol A di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di Methyl) acrylate, glycerol di(meth) acrylate, pentaerythritol di(meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di (a) Acrylate, bis-glycidyl phthalate di(meth)acrylate or hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate is equivalent to crosslinking of two polymerizable unsaturated groups in the molecule a compound; further, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2 -Hydroxypropyl (meth) acrylate, 2-(methyl) propylene oxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono ( methyl) Acrylate, 2- (meth) Bing Xixi oxyethyl phosphate or N- methylol (meth) acrylamide having in the molecule is equal to a polymerizable unsaturated group is crosslinked compound.

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

(In the formula [7], E ₁ represents 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, an anthracene ring, an anthracene ring or a phenanthrene ring. The group, E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

The above compound is an example of a crosslinkable compound, but is not limited thereto. Moreover, the crosslinkable compound used for the composition of the present invention or the liquid crystal alignment treatment agent using the composition may be one type or a combination of two or more types.

In the composition of the present invention or the liquid crystal alignment treatment agent using the composition, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass based on 100 parts by mass of the total polymer component. In order to carry out the crosslinking reaction, it is more preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass, based on 100 parts by mass of the total polymer component.

When a liquid crystal alignment film is produced by using a liquid crystal alignment treatment agent (liquid crystal alignment treatment agent using the composition of the present invention), the charge movement in the liquid crystal alignment film is promoted, and a compound which releases a charge of a liquid crystal cell using the liquid crystal alignment film is promoted. The nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156] contained in pages 69 to 73 of International Publication WO2011/132751 (2011.10.27 publication) is preferably added. The amine compound may be directly added to the composition, but after a solution having a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass, in a suitable solvent Add it as better. The solvent is not particularly limited as long as it is an organic solvent capable of dissolving the above polymer.

The composition of the present invention or the liquid crystal alignment treatment agent using the composition can be used to lift the resin film or the coating composition or the liquid crystal alignment treatment agent using the composition, without damaging the effects of the present invention. A compound having a film thickness uniformity or surface smoothness of a liquid crystal alignment film. Further, a compound which lifts the adhesion between the resin film or the liquid crystal alignment film and the substrate can also be used.

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

More specifically, for example, EFTOP EF301, EF303, EF352 (above, TOHKEM PRODUCTS), MEGAFAC F171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), FLUORAD FC430, FC431 (above Sumitomo 3M) ASAHI GUARD AG710, SURFLONS-382, SC101, SC102, SC103, SC104, SC105, SC106 (above is manufactured by Asahi Glass Co., Ltd.). The use ratio of the surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total of the polymer components contained in the composition or the liquid crystal alignment treatment agent.

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

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane , N-(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N -ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriene Amine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxydecyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4, 7-Triazadecane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate , N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-amine Propyl triethoxy decane, ethylene glycol diminution Glycerol ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol condensed water Glycerol ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N ',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane or N,N,N',N' , -tetraglycidyl-4, 4'-diaminodiphenylmethane, and the like.

When such a compound which is adhered to the substrate is used, the total amount of the polymer contained in the liquid crystal alignment treatment agent with respect to the composition or the composition is used. The compound component is preferably 100 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. When the amount is less than 0.1 part by mass, the effect of improving the adhesion is not expected, and when it is more than 30 parts by mass, the storage stability of the composition or the liquid crystal alignment treatment agent using the composition may be deteriorated.

In the composition of the present invention or the liquid crystal alignment treatment agent using the composition, in addition to the above-mentioned weak solvent, crosslinkable compound, lifted resin film or liquid crystal alignment film, the film thickness uniformity or surface smoothness of the compound and the substrate are adhered to In addition to the compound, a dielectric or a conductive material for the purpose of changing the electrical properties such as the dielectric constant or the conductivity of the resin film or the liquid crystal alignment film may be added as long as the effect of the present invention is not impaired.

<Resin film>

The composition of the present invention is applied onto a substrate and, after firing, can be used as a resin film. The substrate used at this time can be used in conjunction with the intended device, and a plastic substrate such as a glass substrate, a germanium wafer, an acrylic substrate, or a polycarbonate substrate can be used. The coating method of the composition is not particularly limited, but industrially, the dipping method, the roll coating method, the slit coating method, the spin coating method, the spray method, the screen printing, the lithography, the letterpress printing, or the inkjet method are generally used. Etc. These methods can also use this for the purpose.

After the composition is applied onto the substrate, it can be heated at 50 to 250 ° C, preferably 80 to 200 ° C, more preferably 80 by a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven. The solvent was evaporated at ~150 ° C to form a resin film. The thickness of the resin film after firing can be adjusted to 0.01 to 100 μm in accordance with the purpose.

<Liquid alignment film ‧ Liquid crystal display element>

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

The coating method of the liquid crystal alignment treatment agent is not particularly limited, but is generally carried out industrially by screen printing, lithography, letterpress printing, or inkjet method. Other coating methods include, for example, a dipping method, a roll coating method, a slit coating method, a spin coating method, or a spray method, and the like can be used depending on the purpose.

After the liquid crystal alignment agent is applied onto the substrate, it is preferably heated at 50 to 250 ° C, preferably 80 to 200 ° C by a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven. The solvent is evaporated at 80 to 150 ° C to form a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element. When the thickness is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 5 to 300 nm. More preferably, it is 10 to 100 nm. Align or tilt the LCD horizontally In the oblique alignment, the liquid crystal alignment film after firing is treated by rubbing or polarized ultraviolet irradiation or the like.

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

In the method for producing a liquid crystal cell, for example, a pair of substrates on which a liquid crystal alignment film is to be formed is formed, and a spacer is spread on a liquid crystal alignment film of a single-sided substrate, so that the liquid crystal alignment film surface is inside, and the other single side is bonded. The substrate is sealed by injecting liquid crystal into a reduced pressure, or a method in which a liquid crystal is dropped onto a liquid crystal alignment film surface on which a spacer is dispersed, and a substrate is bonded and sealed.

Further, the liquid crystal alignment treatment agent of the present invention is preferably a liquid crystal display element produced by the step of providing a liquid crystal layer between one of the electrodes and the pair of substrates. a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat, wherein a voltage is applied between the electrodes, and at least one of irradiation and heating of the active energy ray is used to polymerize the polymerizable compound . Among them, the active energy ray is preferably ultraviolet ray. The ultraviolet light has, for example, a wavelength of 300 to 400 nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, the irradiation and heating of the ultraviolet rays can be simultaneously performed.

The above liquid crystal display element controls a pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of light is mixed in the liquid crystal material. In the state in which a liquid crystal cell is assembled, a photopolymerizable compound is irradiated with ultraviolet rays or the like in a state where a predetermined voltage is applied to the liquid crystal layer, and the polymer is controlled by the generated polymer. pour. Since the alignment state of the liquid crystal molecules at the time of polymer formation is memorized even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer or the like. Further, in the PSA method, since the rubbing treatment is not required, it is possible to form a liquid crystal layer of a vertical alignment type which is difficult to control the pretilt by the rubbing treatment.

In other words, in the liquid crystal display device of the present invention, the liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention, and a liquid crystal cell is produced, and at least one of ultraviolet light irradiation and heating is used to polymerize. Polymerization of the compound controls the alignment of the liquid crystal molecules.

In the case of the production of a PSA liquid crystal cell, for example, a substrate on which a liquid crystal alignment film is formed is prepared, and a spacer is spread on the liquid crystal alignment film of the single-sided substrate to form a liquid crystal alignment film surface. A method in which another single-sided substrate is bonded to a liquid crystal, and a liquid crystal is dropped by a sealing method or a liquid crystal alignment film surface on which a spacer is dispersed, and then the substrate is bonded and sealed.

A polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays is mixed in the liquid crystal. The polymerizable compound is, for example, a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not aggregate When the amount of the liquid crystal is too large, the unreacted polymerizable compound is increased, and the image sticking property of the liquid crystal display element is lowered.

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

Further, the liquid crystal alignment treatment agent of the present invention may preferably be a liquid crystal display element produced by the step of forming a liquid crystal layer between one of the electrodes and between the pair of substrates. A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat, and a step of applying a voltage between the electrodes. Here, the active energy ray is preferably ultraviolet ray. The ultraviolet light has, for example, a wavelength of 300 to 400 nm, preferably 310 to 360 nm. When the polymerization is carried out by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Further, the irradiation and heating of the ultraviolet rays can be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group which is polymerized by at least one of an active energy ray and heat, for example, a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or using a polymerizable group is used. The method of polymer composition. Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bond site which is reacted by heat or ultraviolet irradiation, the alignment of the liquid crystal molecules can be controlled by at least one of ultraviolet irradiation and heating.

When an example of the production of a liquid crystal cell is used, for example, a pair of substrates of a liquid crystal alignment film are prepared to be formed on a liquid crystal alignment film of a single-sided substrate. Dispersing the spacer so that the liquid crystal alignment film surface becomes the inner side, bonding the other single-sided substrate, injecting the liquid crystal under reduced pressure, sealing, or laminating the liquid crystal on the liquid crystal alignment film surface on which the spacer is dispersed A method of sealing a substrate or the like.

After the liquid crystal cell is produced, heat or ultraviolet rays are applied to the liquid crystal cell by applying an alternating current or a direct current voltage, whereby the alignment of the liquid crystal molecules can be controlled.

As described above, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and is suitable for use in a large-screen, high-definition liquid crystal television or the like.

[Examples]

Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is not limited thereto.

The abbreviations used in the synthesis examples, examples, and comparative examples are as follows.

(diamine compound having a carboxyl group)

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])

(second bisamine compound)

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 (hereinafter, the formula [B3] Diamine compound

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]

(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])

(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]

(alkoxydecane monomer)

MPMS: 3-methacryloxypropyltrimethoxydecane (alkoxydecane monomer represented by the formula [A2] of the present invention)

UPS: 3-ureidopropyltriethoxydecane (alkoxydecane monomer represented by the formula [A2] of the present invention)

TEOS: tetraethoxy decane (alkoxydecane monomer represented by the formula [A3] of the present invention)

(Component (A) of the present invention (specific solvent))

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

MCS: ethylene glycol monomethyl ether (solvent represented by the formula [1b-1] of the present invention)

ECS: ethylene glycol monoethyl ether (solvent represented by the formula [1b-2] of the present invention)

PCS: ethylene glycol monopropyl ether (dissolved as shown in the formula [1b-3] of the present invention] Agent)

(Component (D) of the present invention (other organic solvent))

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

(Component (E) of the present invention (other organic solvent))

BCS: ethylene glycol monobutyl ether

(Measurement of molecular weight of polyimine precursors and polyimine)

The molecular weight of the polyimine precursor and the polyimine in the synthesis example is a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., Ltd.), and a column (KD-803, KD). -805) (manufactured by Shodex Co., Ltd.) was measured in the following manner.

Column temperature: 50 ° C

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

Flow rate: 1.0ml/min

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

(Determination of the imidization rate of polyfluorene imine)

The ruthenium imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, 5 (manufactured by Kusano Scientific Co., Ltd.) was added with hydrogenated dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane) mixed product) (0.53 ml), and ultrasonic waves were applied to completely dissolve. This solution was measured for proton NMR at 500 MHz by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL DATUM Co., Ltd.). The sulfhydrylation rate is determined by using protons from a structure that does not change before and after imidization as a reference proton, and the peak value of the proton is used and the NH group derived from proline which is present in the vicinity of 9.5 ppm to 10.0 ppm. The cumulative value of the proton peak is obtained by the following formula.

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

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

"Synthesis of a specific polymer (polyimine precursor and polyimine) of the component (B) of the present invention" <Synthesis Example 1>

D1 (3.12 g, 15.9 mmol) and A1 (2.42 g, 15.9 mmol) were mixed in PGME (49.9 g), and reacted at 40 ° C for 8 hours to obtain a polyglycine solution having a resin solid content concentration of 10.0% by mass (1) ). The polyamine has a number average molecular weight of 10,100 and a weight average molecular weight of 23,500.

<Synthesis Example 2>

D2 (8.42 g, 33.7 mmol) and A2 (6.40 g, 42.1 mmol) were mixed in NMP (27.2 g), and reacted at 80 ° C for 5 hours, then D1 (1.65 g, 8.41 mmol) and NMP (22.2 g) were added. The reaction was carried out at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

After adding NMP to the obtained poly-proline solution (40.0 g) and diluting it to 6 mass %, Acetic anhydride (6.52g) and pyridine (5.05g) as a ruthenium-imidation catalyst were added, and 90. The reaction was carried out at ° C for 4 hours. This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (2). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 12,200, and a weight average molecular weight of 33,000.

<Synthesis Example 3>

D2 (1.82 g, 7.27 mmol), B1 (2.30 g, 6.04 mmol), A1 (0.92 g, 6.05 mmol) were mixed in PGME (29.7 g), and reacted at 80 ° C for 5 hours, then D1 (0.95 g, 4.84 mmol) and PGME (24.3 g) were reacted at 40 ° C for 8 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 10.0% by mass. The polyamine has a number average molecular weight of 12,500 and a weight average molecular weight of 34,100.

<Synthesis Example 4>

D2 (3.83 g, 15.3 mmol), B1 (4.86 g, 12.8 mmol), and A1 (1.94 g, 12.8 mmol) were mixed in NMP (20.8 g), and reacted at 80 ° C for 5 hours, then D1 (2.00 g, 10.2 mmol) and NMP (17.0 g) were reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid content concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6% by mass, acetic anhydride (5.16 g) and pyridine (4.00 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 80 ° C for 2 hours. . This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (4). The polyimine had a hydrazine imidation ratio of 61%, a number average molecular weight of 15,200, and a weight average molecular weight of 38,300.

<Synthesis Example 5>

D2 (6.12 g, 24.5 mmol), B1 (4.66 g, 12.2 mmol), A1 (2.33 g, 15.3 mmol), C1 (0.33 g, 3.05 mmol) were mixed in NMP (24.2 g), and reacted at 80 ° C After the hour, D1 (1.20 g, 6.12 mmol) and NMP (19.8 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6% by mass, acetic anhydride (5.33 g) and pyridine (4.13 g) as a ruthenium amide catalyst were added and reacted at 80 ° C for 2 hours. . This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (5). The polyimine had a hydrazine imidation ratio of 58%, a number average molecular weight of 16,100, and a weight average molecular weight of 39,100.

<Synthesis Example 6>

D2 (4.91 g, 19.6 mmol), B2 (3.32 g, 8.41 mmol), A1 (2.13 g, 14.0 mmol), B6 (1.14 g, 5.61 mmol) were mixed in NMP (21.7 g), and reacted at 80 ° C After the hour, D1 (1.65 g, 8.41 mmol) and NMP (17.8 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained poly-proline solution (40.0 g) and diluting it to 6 mass%, acetic anhydride as a ruthenium catalyst was added. (5.50 g), pyridine (4.25 g), and reacted at 80 ° C for 3 hours. This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (6). The polyimine had a hydrazine imidation ratio of 51%, a number average molecular weight of 17,900, and a weight average molecular weight of 41,200.

<Synthesis Example 7>

D2 (5.06 g, 20.2 mmol), B3 (3.75 g, 8.67 mmol), A2 (2.63 g, 17.3 mmol), C2 (0.31 g, 2.87 mmol) were mixed in NMP (22.2 g), and reacted at 80 ° C After the hour, D1 (1.70 g, 8.67 mmol) and NMP (18.2 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6 mass%, acetic anhydride (5.64 g) and pyridine (4.38 g) which are a ruthenium-imidation catalyst were added, and it reacted at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (7). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 18,900, and a weight average molecular weight of 42,900.

<Synthesis Example 8>

D2 (6.28 g, 25.1 mmol), B4 (2.32 g, 4.71 mmol), A1 (4.06 g, 26.7 mmol) were mixed in NMP (22.9 g) After reacting at 80 ° C for 6 hours, D1 (1.23 g, 6.27 mmol) and NMP (18.7 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6 mass%, acetic anhydride (5.77 g) and pyridine (4.47 g) which are a ruthenium-imidation catalyst were added, and it reacted at 80 degreeC for 3.5 hours. . This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (8). The polyimine had a ruthenium iodide ratio of 45%, a number average molecular weight of 15,100, and a weight average molecular weight of 36,500.

<Synthesis Example 9>

D3 (6.51 g, 29.0 mmol), B1 (3.32 g, 8.72 mmol), A1 (3.09 g, 20.3 mmol) were mixed in NMP (38.8 g), and reacted at 40 ° C for 5 hours to obtain a resin solid concentration of 25.0. Mass% polyamine solution.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6% by mass, acetic anhydride (5.74 g) and pyridine (4.45 g) as a ruthenium amide catalyst were added and reacted at 80 ° C for 3 hours. . This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (9). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 13,100, and a weight average molecular weight of 36,200.

<Synthesis Example 10>

D3 (6.54 g, 29.2 mmol), B5 (3.30 g, 8.76 mmol), B6 (1.19 g, 5.85 mmol), A2 (2.22 g, 14.6 mmol) were mixed in NMP (39.7 g), and reacted at 40 ° C. A polyamic acid solution having a resin solid content concentration of 25.0% by mass was obtained in an hour.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6% by mass, acetic anhydride (5.62 g) and pyridine (4.36 g) as a ruthenium amide catalyst were added and reacted at 80 ° C for 3 hours. . This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (10). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 12,100, and a weight average molecular weight of 32,900.

<Synthesis Example 11>

D4 (5.17g, 17.2mmol), B2 (3.40g, 8.62mmol), C2 (0.47g, 4.35mmol), A2 (2.40g, 15.8mmol) were mixed in NMP (22.6g) and reacted at 80 °C5 After the hour, D1 (2.25 g, 11.5 mmol) and NMP (18.5 g) were added, and the mixture was reacted at 40 ° C for 5.5 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6% by mass, acetic anhydride (6.45 g) and pyridine (3.35 g) as a ruthenium amide catalyst were added and reacted at 40 ° C for 1.5 hours. . The reaction solution was poured into methanol (650 ml), and the resulting precipitate was filtered. Got it. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (11). The polyimine had a hydrazine imidation ratio of 59%, a number average molecular weight of 19,100, and a weight average molecular weight of 40,600.

<Synthesis Example 12>

D4 (4.06 g, 13.5 mmol), B1 (3.09 g, 8.12 mmol), B6 (1.65 g, 8.12 mmol), A1 (1.64 g, 10.8 mmol) were mixed in NMP (21.6 g), and reacted at 80 ° C After the hour, D1 (2.65 g, 13.5 mmol) and NMP (17.7 g) were added, and the mixture was reacted at 40 ° C for 5.5 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6 mass%, acetic anhydride (6.33g) and pyridine (3.27g) which are a ruthenium-imidation catalyst were added, and it reacted at 40 degreeC for 1.5 hours. . This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (12). The polyimine had a hydrazine imidation ratio of 55%, a number average molecular weight of 17,800, and a weight average molecular weight of 39,100.

<Synthesis Example 13>

D1 (2.85 g, 14.5 mmol) and A1 (2.21 g, 14.5 mmol) were mixed in NMP (15.2 g), and reacted at 40 ° C for 8 hours to obtain a polyamine acid solution having a resin solid content of 25.0% by mass. ). The polyamine has a number average molecular weight of 18,100 and a weight average molecular weight of 35,200.

<Synthesis Example 14>

D2 (4.11 g, 16.4 mmol), B1 (5.22 g, 13.7 mmol), A1 (2.09 g, 13.7 mmol) were mixed in NMP (22.4 g), and reacted at 80 ° C for 5 hours, then D1 (2.15 g, 11.0 mmol) and NMP (18.3 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (14) having a resin solid content concentration of 25.0% by mass. The polyamine has a number average molecular weight of 19,100 and a weight average molecular weight of 45,800.

<Synthesis Example 15>

D2 (4.02 g, 16.1 mmol), B1 (5.09 g, 13.4 mmol), C1 (1.45 g, 13.4 mmol) were mixed in NMP (20.9 g), and reacted at 80 ° C for 5 hours, then D1 (2.10 g, 10.7 mmol) and NMP (17.1 g) were reacted at 40 ° C for 5.5 hours to obtain a polyaminic acid solution having a resin solid concentration of 25.0% by mass.

After adding NMP to the obtained polyamic acid solution (40.0 g) and diluting it to 6% by mass, acetic anhydride (5.40 g) and pyridine (4.18 g) as a ruthenium amide catalyst were added and reacted at 80 ° C for 3 hours. . This reaction solution was poured into methanol (650 ml), and the obtained precipitate was obtained by filtration. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (15). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 16,000, and a weight average molecular weight of 39,200.

Specific polymers of the invention (polyimine precursors and poly 醯imine) is shown in Table 1.

"Synthesis of alkoxydecane monomer represented by formula [A1] of the present invention" <Synthesis Example 16>

Compound (1) (30.0 g) and potassium carbonate were placed in a 500 ml Four Neck flask equipped with a magnetic stirrer. (25.2 g), DMF (120 g), and an allyl bromide (22.1 g) was added dropwise at 25 °C. Then, it was stirred at 50 ° C for 11 hours. The reaction solution was diluted with ethyl acetate (500 g), and the organic phase was washed three times with purified water (200 g). The organic phase was dried over sodium sulfate, and after filtration, the filtrate was concentrated and dried to give compound (2) (yield: 34.8 g, yield: 100%).

¹ H-NMR (400 MHz, CDCl ₃ , δ ppm): 0.90 (3H, t, J = 7.2 Hz, 3H), 0.99-1.09 (2H, m) 1.18-1.46 (11H, m), 1.84-1.89 (4H , m), 2.37-2.44 (1H, m), 4.51 (2H, dt, J = 5.4 Hz, 1.6 Hz), 5.26 (1H, dq, J = 10.6 Hz, 1.6 Hz), 5.40 (1H, dq, J =17.2 Hz, 1.6 Hz), 6.07 (1H, ddd, J = 17.2 Hz, 10.6 Hz, 5.4 Hz), 6.83 (2H, dd, J = 8.8 Hz, 2.9 Hz), 7.10 (2H, dd, J = 8.8) Hz, 2.9 Hz).

Compound (2) (20.0 g) and toluene (120 g) were placed in a 300 mL four-necked flask equipped with a magnetic stirrer, and stirred at 25 °C. Next, after adding a Karstedt catalyst (0.1 mol/L xylene solution of platinum (0)-1,1,3,3-tetramethyldioxane complex) (700 μl), trimethoxy group was added dropwise. Decane (12.4 ml). After stirring at 25 ° C for 29 hours, the reaction liquid was concentrated to dryness to give a crude product. This was distilled under reduced pressure, and the mixture was distilled off under the conditions of an external temperature: 245 ° C / pressure: 0.8 torr to obtain an alkoxydecane monomer (A) of the formula [A1] of the present invention (amount: 12.2 g, Yield: 43%).

^{1 H-NMR (400MHz, CDCl} 3, δ ppm): 0.76-0.82 (2H, m), 0.89 (3H, t, J = 7.2Hz), 0.98-1.08 (2H, m), 1.18-1.45 (11H, m), 1.84-1.93 (6H, m), 2.36-2.43 (1H, m), 3.58 (9H, s), 3.91 (2H, t, J = 6.8 Hz), 6.81 (2H, d, J = 8.8 Hz) ), 7.08 (2H, d, J = 8.8 Hz).

"Synthesis of a specific polyoxyalkylene of the component (C) of the present invention" <Synthesis Example 17>

PGME (28.3 g), TEOS (32.5 g), and alkoxydecane monomer (A) (4.10 g) obtained in Synthesis Example 16 were mixed with a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, and MPMS ( After 7.45 g), a solution of the alkoxydecane monomer was prepared. A solution prepared by mixing PGME (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise to the alkoxydecane monomer solution at 25 ° C for 30 minutes, and then 25 Stir at °C for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a previously prepared mixed solution of a methanol solution (1.20 g) and PGME (0.90 g) having a UPS content of 92% by mass was added. After refluxing for further 30 minutes, the mixture was cooled to obtain a polyoxyalkylene solution (1) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 18>

MCS (28.3 g), TEOS (32.5 g), the alkoxydecane monomer (A) (4.10 g) obtained in Synthesis Example 16, and MPMS were mixed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. After 7.45 g), a solution of the alkoxydecane monomer was prepared. A solution prepared by mixing MCS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise to the alkoxydecane monomer solution at 25 ° C for 30 minutes, and then 25 Stir at °C for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a mixed solution of a methanol solution (1.20 g) and MCS (0.90 g) having a pre-modulated UPS content of 92% by mass was added. After refluxing for further 30 minutes, the mixture was cooled to obtain a polyoxysilane solution (2) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 19>

In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, ECS (28.3 g), TEOS (32.5 g), alkoxydecane monomer (A) (4.10 g) obtained in Synthesis Example 16, and MPMS ( After 7.45 g), a solution of the alkoxydecane monomer was prepared. A solution prepared by mixing ECS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was added dropwise to the above alkoxydecane monomer solution at 25 ° C for 30 minutes, and then 25 Stir at °C for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a mixed solution of a methanol solution (1.20 g) and ECS (0.90 g) having a pre-modulated UPS content of 92% by mass was added. Further, the mixture was refluxed for 30 minutes, and then allowed to stand to cool to obtain a polyoxane solution (3) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 20>

In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, PCS (28.3 g), TEOS (32.5 g), alkoxydecane monomer (A) (4.10 g) obtained in Synthesis Example 16 and MPMS (MPMS) were mixed. 7.45 g) A solution of the alkoxydecane monomer. A solution prepared by premixing PCS (14.2 g), water (10.8 g), and oxalic acid (0.70 g) as a catalyst was dropped into the alkoxydecane monomer solution at 25 ° C for 30 minutes, and then Stir at 25 ° C for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a premixed solution of a methanol solution (1.20 g) having a UPS content of 92% by mass and PCS (0.90 g) was added. After refluxing for further 30 minutes, the mixture was cooled to obtain a polyoxoxane solution (4) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 21>

In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, PGME (25.4 g), TEOS (20.0 g), alkoxydecane monomer (A) (8.20 g) obtained in Synthesis Example 16 and MPMS (MPMS) were mixed. 19.9 g) A solution of an alkoxydecane monomer. A solution prepared by mixing PGME (12.7 g), water (10.8 g), and oxalic acid (1.10 g) as a catalyst was added dropwise to the alkoxydecane monomer solution at 25 ° C for 30 minutes, and then Stir at 25 ° C for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a mixed solution of a methanol solution (1.20 g) and PGME (0.90 g) having a pre-modulated UPS content of 92% by mass was added. After refluxing for further 30 minutes, the mixture was cooled to obtain a polyoxoxane solution (5) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 22>

In a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube, PGME (29.2 g), TEOS (38.8 g), and alkoxydecane monomer (A) (4.10 g) obtained in Synthesis Example 16 were mixed to prepare an alkoxylate. A solution of a decylene monomer. A solution prepared by mixing PGME (14.6 g), water (10.8 g), and oxalic acid (0.50 g) as a catalyst was added dropwise to the alkoxydecane monomer solution at 25 ° C for 30 minutes, and then Stir at 25 ° C for 30 minutes. Then, after heating using an oil bath and refluxing for 30 minutes, a mixed solution of a methanol solution (1.20 g) and PGME (0.90 g) having a pre-modulated UPS content of 92% by mass was added. After refluxing for further 30 minutes, the mixture was cooled to obtain a polyoxysilane solution (6) having a SiO ₂ conversion concentration of 12% by mass.

<Synthesis Example 23>

A solution of silane (31.6 g) and TEOS (41.7 g) in a four-neck reaction flask equipped with a thermometer and a reflux tube was mixed with an alkoxydecane monomer. A solution prepared by mixing PGME (15.8 g), water (10.8 g), and oxalic acid (0.20 g) as a catalyst was added dropwise to the alkoxydecane monomer solution at 25 ° C for 30 minutes, and then Stir at 25 ° C for 30 minutes. Then, the mixture was heated in an oil bath and refluxed for 60 minutes, and then left to stand to obtain a polyoxoxane solution (7) having a SiO ₂ conversion concentration of 12% by mass.

The specific polyoxyalkylene (polyoxane solution) of the present invention is as Table 2 shows.

"Manufacture of the composition of the present invention and liquid crystal alignment treatment agent"

The production examples of the composition are described in the following Examples 1 to 27 and Comparative Examples 1 to 7. Moreover, these compositions are also used to evaluate liquid crystal alignment treatment agents.

The composition of the present invention and the liquid crystal alignment treatment agent are shown in Tables 3 to 5.

The evaluation of the applicability of the composition and the liquid crystal alignment treatment agent and the evaluation of the inkjet coating property of the liquid crystal alignment treatment agent were carried out using the composition obtained by the examples and the comparative examples of the present invention or the liquid crystal alignment treatment agent. "Production of Liquid Crystal Cell (General Cell)", "Evaluation of Liquid Crystal Alignment (General Cell)" and "Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)" and "Voltage Hold" Rate assessment". The conditions are as follows.

"Evaluation of the coating properties of the composition and the liquid crystal alignment agent"

The coating property was evaluated using a solution obtained by subjecting the composition obtained in the examples and the comparative examples of the present invention to pressure filtration using a membrane filter having a pore diameter of 1 μm. For the coating system, a spin coater (1H-D7) (manufactured by Mikasa Co., Ltd.) was used. The coating system was spin-coated on an ITO surface of a substrate (length 40 mm × width 30 mm, thickness 0.7 mm) with a 30×40 mm ITO electrode after washing with pure water and IPA (isopropyl alcohol), and applied to the ITO surface. The time until drying was 30 seconds, and the temporary drying was carried out on a hot plate, and it was carried out at 80 ° C for 5 minutes.

The obtained resin film was subjected to pinhole evaluation. The pinhole evaluation of the resin film was carried out by visual observation of the resin film under a sodium lamp. Specifically, the number of pinholes confirmed on the resin film was calculated, and the smaller the number of pinholes, the more excellent the evaluation.

Further, the compositions obtained in the examples and comparative examples of the present invention can be used for a liquid crystal alignment treatment agent. Therefore, as a result of the coatability of the resin film obtained in the present examples and the comparative examples, the printability of the liquid crystal alignment film was also obtained.

Tables 6 to 8 show the number of pinholes of the resin film (liquid crystal alignment film) obtained in the examples and the comparative examples.

"Evaluation of inkjet coating properties of liquid crystal alignment agents"

The liquid crystal alignment treatment agent (9) obtained in Example 9 of the present invention and the liquid crystal alignment treatment agent (16) obtained in Example 16 were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and sprayed. ink Coating evaluation. The inkjet coater used HIS-200 (manufactured by Hitachi PLANT-TECHNOLOGIES Co., Ltd.). The coating was applied to an ITO (Indium Tin Oxide) vapor-deposited substrate washed with pure water and IPA (isopropyl alcohol), and the coated area was 70×70 mm, the nozzle pitch was 0.423 mm, and the scanning pitch was 0.5 mm. The cloth speed was 40 mm/sec, the time from application to temporary drying was 60 seconds, and the temporary drying was carried out on a hot plate at 70 ° C for 5 minutes.

The evaluation of the pinholes of the obtained liquid crystal alignment film was carried out under the same conditions as the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent.

Tables 6 and 7 show the number of pinholes of the liquid crystal alignment film obtained in the examples.

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

Using a liquid crystal alignment treatment agent obtained in Examples and Comparative Examples of the present invention, a solution obtained by pressure filtration using a membrane filter having a pore diameter of 1 μm was spin-coated and washed with pure water and IPA (isopropyl alcohol). The ITO surface of the substrate (length 40 mm × width 30 mm, thickness 0.7 mm) with a 30×40 mm ITO electrode was heat-treated on a hot plate at 100° C. for 5 minutes to obtain a film thickness of 100 nm. An ITO substrate of an amine liquid crystal alignment film. The coating film surface of this ITO substrate was rubbed by a rubbing apparatus having a roll diameter of 120 mm, and the rubbing was performed under the conditions of a roll rotation number of 1000 rpm, a roll travel speed of 50 mm/sec, and a press-in amount of 0.1 mm.

Two pieces of the obtained ITO substrate with the liquid crystal alignment film were prepared, and the liquid crystal alignment film surface was inside, and the 6 μm spacer was sandwiched and combined. After that, a sealant (XN-1500T) (manufactured by Mitsui Chemicals, Inc.) was printed. Next, after the other substrate and the liquid crystal alignment film surface were bonded to each other, the sealing agent was heat-treated at 120 ° C for 90 minutes in a heat cycle type clean oven, and was hardened to prepare an empty cell. In this empty cell, a liquid crystal cell (general unit cell) is obtained by injecting a liquid crystal and sealing the injection port by a vacuum injection method.

Further, the liquid crystal alignment treatment agent (1) to liquid crystal alignment treatment agent (3) obtained in each of Examples 1 to 3, and the liquid crystal alignment treatment agent (28) obtained in Comparative Example 1 to Comparative Example 3 were used for liquid crystal alignment treatment. In the liquid crystal cell of the agent (30), a nematic liquid crystal (MLC-2003) (manufactured by Merck Japan Co., Ltd.) was used for the liquid crystal.

Further, the liquid crystal alignment treatment agent (4) to liquid crystal alignment treatment agent (8) obtained in Examples 4 to 8 and the liquid crystal alignment treatment agent (10) to liquid crystal alignment treatment obtained in Examples 10 to 15 were used. Liquid crystal alignment treatment agent (17) to liquid crystal alignment treatment agent (27) obtained in Examples 17 to 27, and liquid crystal alignment treatment agent (31) to liquid crystal obtained in Comparative Example 4 to Comparative Example 7 In the liquid crystal cell of the alignment treatment agent (34), nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.) was used as the liquid crystal.

"Evaluation of Liquid Crystal Alignment (General Cell)"

The liquid crystal cell obtained by the above-mentioned "production of liquid crystal cell (general cell)" was used, and evaluation of liquid crystal alignment was performed. A liquid crystal alignment system uses a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Co., Ltd.). Observe the liquid crystal cell and confirm the presence or absence of the alignment defect. Specifically, in the case where no alignment defect was found, the evaluation was excellent (good in Tables 6 to 8).

Tables 6 to 8 show the results of liquid crystal alignment obtained in the examples and comparative examples.

"Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)"

The liquid crystal alignment treatment agent (7) obtained in Example 7, the liquid crystal alignment treatment agent (12) obtained in Example 12, the liquid crystal alignment treatment agent (14) obtained in Example 14, and the obtained Example 26 were used. The liquid crystal alignment treatment agent (26) was subjected to pressure filtration of a membrane filter having a pore diameter of 1 μm, and then washed with pure water and IPA (isopropyl alcohol), and spin-coated at the center with a map of 10 × 10 mm. A substrate of an ITO electrode having a spacing of 20 μm (40 mm in length × 30 mm in width, 0.7 mm in thickness) and an ITO surface of a substrate (40 mm in length × 30 mm in width and 0.7 mm in thickness) with an ITO electrode of 10 × 40 mm in the center, on a heating plate The film was heat-treated at 100 ° C for 5 minutes to obtain a polyimide film having a film thickness of 100 nm. The surface of the coating film was washed with pure water, and then heat-treated at 100 ° C for 15 minutes in a heat cycle type clean oven to obtain a substrate with a liquid crystal alignment film.

The substrate on which the liquid crystal alignment film was attached was placed on the inner side of the liquid crystal alignment film surface, and a spacer of 6 μm was sandwiched and bonded, and an empty cell was formed by adhesion around the sealant. In the empty cell, a liquid crystal obtained by mixing a polymerizable compound represented by the following formula in a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.) was injected by a vacuum injection method. (1) A liquid crystal of the polymerizable compound (1) in an amount of 0.3% by mass based on 100% by mass of the nematic liquid crystal (MLC-6608), and then the liquid crystal cell is obtained by sealing the injection port.

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

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

In the PSA unit cell obtained in the examples, the liquid crystal cell after the ultraviolet irradiation had a faster response speed of the liquid crystal cell after the ultraviolet irradiation, and it was confirmed that the liquid crystal alignment direction was controlled. Further, any liquid crystal cell can be confirmed by a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Co., Ltd.) to confirm that the liquid crystal is uniformly aligned.

"Evaluation of Voltage Retention Rate"

For the above "production of liquid crystal cell (general cell)" The liquid crystal cell was subjected to a voltage of 1 V for 60 μs at a temperature of 80 ° C, and the voltage after 16.67 ms and after 50 ms was measured, and how much the voltage can be maintained is calculated by a voltage holding ratio (also referred to as VHR). The measurement was carried out using a voltage holding ratio measuring device (VHR-1) (manufactured by Toyo Kagyo Co., Ltd.) with a setting of Voltage: ±1 V, Pulse Width: 60 μs, Flame Period: 16.67 ms, or 50 ms.

Table 9 shows the results of the voltage holding ratios obtained in the examples and comparative examples.

<Example 1>

PGME (10.5 g) was added to a polyglycine solution (1) (12.0 g) having a resin solid content concentration of 10.0% by mass obtained by the synthesis method of Synthesis Example 1, and stirred at 25 ° C for 1 hour. To the solution, a polyoxoxane solution (7) (2.50 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 23 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (1). It was confirmed that no abnormality such as turbidity or precipitate formation was observed in the composition, and it was a uniform solution. Further, this composition (1) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (1).

Using the obtained composition (1) and the liquid crystal alignment treatment agent (1), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 2>

PGME (10.5 g) and γ-BL (1.27 g) were added to a polyamic acid solution (1) (10.5 g) having a solid content concentration of 10.0% by mass of the resin obtained by the synthesis method of Synthesis Example 1. Stir at ° C for 1 hour. To the solution, a polyoxoxane solution (7) (4.71 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 23 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (2). . It was confirmed that no abnormality such as turbidity or precipitate formation was observed in the composition, and it was a uniform solution. Further, this composition (2) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (2).

Using the obtained composition (2) and the liquid crystal alignment treatment agent (2), "evaluation of the applicability of the composition and the liquid crystal alignment treatment agent", "production of a liquid crystal cell (general unit cell)", and "Evaluation of liquid crystal alignment (general unit cell)".

<Example 3>

PGME (28.0 g) and NMP (4.20 g) were added to the polyimine powder (2) (1.34 g) obtained by the synthesis method of Synthesis Example 2, and stirred at 70 ° C for 24 hours to dissolve. To the solution, a polyoxoxane solution (7) (11.2 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 23 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (3). ). It was confirmed that no abnormality such as turbidity or precipitate formation was observed in the composition, and it was a uniform solution. Further, this composition (3) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (3).

Using the obtained composition (3) and liquid crystal alignment treatment agent (3), Under the above conditions, "evaluation of the coating properties of the composition and the liquid crystal alignment treatment agent", "production of a liquid crystal cell (general unit cell)", and "evaluation of liquid crystal alignment (general cell)" were carried out.

<Example 4>

PGME (11.8 g) was added to a polyamic acid solution (3) (13.5 g) having a resin solid content concentration of 10.0% by mass obtained by the synthesis method of Synthesis Example 3, and stirred at 25 ° C for 1 hour. To the solution, a polyoxoxane solution (5) (2.81 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 21 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (4). ). It was confirmed that no abnormality such as turbidity or precipitate formation was observed in the composition, and it was a uniform solution. Further, this composition (4) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (4).

Using the obtained composition (4) and the liquid crystal alignment treatment agent (4), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)" and "Evaluation of Voltage Retention Rate".

<Example 5>

PGME (10.1 g) and γ-BL (2.66 g) were added to a polyamic acid solution (3) (8.50 g) having a solid content of 10.0% by mass of the resin obtained by the synthesis method of Synthesis Example 3 at 25 ° C. Stir for 1 hour. To the solution, a polyoxoxane solution (1) (7.08 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 17 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (5). ). It was confirmed that no abnormality such as turbidity or precipitate formation was observed in the composition, and it was a uniform solution. Further, this composition (5) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (5).

Using the obtained composition (5) and the liquid crystal alignment treatment agent (5), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 6>

PGME (3.56 g), γ-BL (2.61 g), and BCS (5.22 g) were added to a polyglycine solution (3) (15.0 g) having a solid content of 10.0% by mass of the resin obtained by the synthesis method of Synthesis Example 3. ), stirring at 25 ° C for 1 hour. To the solution, a polyoxoxane solution (5) (1.39 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 21 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (6). . It was confirmed that no abnormality such as turbidity or precipitate formation was observed in the composition, and it was a uniform solution. Further, this composition (6) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (6).

Using the obtained composition (6) and the liquid crystal alignment treatment agent (6), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 7>

PGME (35.0 g) was added to the polyimine powder (4) (1.65 g) obtained by the synthesis method of Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, a polyoxoxane solution (1) (9.17 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 17 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (7). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (7) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (7).

Using the obtained composition (7) and the liquid crystal alignment treatment agent (7), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. , "Evaluation of Liquid Crystal Alignment (General Cell)" and "Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)" and "Evaluation of Voltage Retention Rate".

<Example 8>

PCS (23.6 g) and γ-BL (8.33 g) were added to the polyimine powder (4) (1.33 g) obtained by the synthesis method of Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To the solution, a polyoxoxane solution (4) (11.1 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 20 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (8). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (8) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (8).

Using the obtained composition (8) and the liquid crystal alignment treatment agent (8), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 9>

PCS (36.8 g) and γ-BL (11.0 g) were added to the polyimine powder (4) (1.00 g) obtained by the synthesis method of Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To the solution, a polyoxoxane solution (4) (8.33 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 20 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (9). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (9) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (9).

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

<Example 10>

PCS (14.7 g), γ-BL (4.28 g), and BCS (12.9 g) were added to the polyimine powder (4) (1.23 g) obtained by the synthesis method of Synthesis Example 4, and stirred at 70 ° C. Allow to dissolve in hours. To the solution, a polyoxoxane solution (4) (12.5 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 20 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (10). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (10) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (10).

Using the obtained composition (10) and the liquid crystal alignment treatment agent (10), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 11>

MCS (20.8 g), NEP (6.17 g), and BCS (10.3 g) were added to the polyimine powder (5) (2.10 g) obtained by the synthesis method of Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours. Dissolved. To the solution, a polyoxoxane solution (2) (4.38 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 18 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (11). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (11) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (11).

Using the obtained composition (11) and the liquid crystal alignment treatment agent (11), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 12>

PGME (24.6 g), γ-BL (13.3 g), and BCS (4.44 g) were added to the polyimine powder (5) (2.55 g) obtained by the synthesis method of Synthesis Example 5, and stirred at 70 ° C. Allow to dissolve in hours. To the solution, a polyoxoxane solution (6) (2.36 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 22 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (12). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (12) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (12).

Using the obtained composition (12) and the liquid crystal alignment treatment agent (12), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. "Evaluation of Liquid Crystal Alignment (General Cell)" and "Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)".

<Example 13>

PGME (32.4 g) was added to the polyimine powder (6) (1.35 g) obtained by the synthesis method of Synthesis Example 6, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, a polyoxoxane solution (5) (11.3 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 21 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (13). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (13) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (13).

Using the obtained composition (13) and the liquid crystal alignment treatment agent (13), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 14>

In the polyimine powder (6) (2.10 g) obtained by the synthesis method of Synthesis Example 6, PGME (33.2 g) and γ-BL (4.11 g) were added, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To the solution, a polyoxoxane solution (7) (4.38 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 23 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (14). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (14) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (14).

Using the obtained composition (14) and the liquid crystal alignment treatment agent (14), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. "Evaluation of Liquid Crystal Alignment (General Cell)" and "Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)".

<Example 15>

PCS (21.9 g), NEP (7.83 g), BCS (3.92 g) were added to the polyimine powder (6) (1.75 g) obtained by the synthesis method of Synthesis Example 6, and stirred at 70 ° C for 24 hours. Dissolved. To the solution, a polyoxoxane solution (4) (6.25 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 20 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (15). . It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (15) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (15).

Using the obtained composition (15) and the liquid crystal alignment treatment agent (15), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 16>

In the polyimine powder (6) (1.05 g) obtained by the synthesis method of Synthesis Example 6, PCS (25.7 g), NEP (8.27 g), BCS (4.14 g) were added, and stirred at 70 ° C for 24 hours. Soluble. To the solution, a polyoxoxane solution (4) (3.75 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 20 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (16). . It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (16) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (16).

Using the obtained liquid crystal alignment treatment agent (16), "evaluation of inkjet coating property of liquid crystal alignment treatment agent" was carried out under the above conditions.

<Example 17>

In the polyimine powder (7) (2.11 g) obtained by the synthesis method of Synthesis Example 7, ECS (20.9 g), NMP (8.26 g), BCS (8.26 g) were added, and the mixture was stirred at 70 ° C for 24 hours. Soluble. To the solution, a polyoxoxane solution (3) (4.40 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 19 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (17). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (17) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (17).

Using the obtained composition (17) and the liquid crystal alignment treatment agent (17), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 18>

PGME (37.9 g) and γ-BL (4.44 g) were added to the polyimine powder (8) (2.55 g) obtained by the synthesis method of Synthesis Example 8, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To the solution, a polyoxoxane solution (6) (2.36 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 22 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (18). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (18) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (18).

Using the obtained composition (18) and the liquid crystal alignment treatment agent (18), the coating properties of the composition and the liquid crystal alignment treatment agent are carried out under the above conditions. Evaluation", "Production of liquid crystal cell (general cell)" and "Evaluation of liquid crystal alignment (general cell)".

<Example 19>

MCS (27.8 g), γ-BL (1.96 g), BCS (3.92 g) were added to the polyimine powder (8) (1.75 g) obtained by the synthesis method of Synthesis Example 8, and stirred at 70 ° C. Allow to dissolve in hours. To the solution, a polyoxoxane solution (2) (6.25 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 18 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (19). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (19) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (19).

Using the obtained composition (19) and the liquid crystal alignment treatment agent (19), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 20>

PGME (26.5 g) and γ-BL (3.85 g) were added to the polyimine powder (9) (1.35 g) obtained by the synthesis method of Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, a polyoxoxane solution (5) (9.20 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 21 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (20). . It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (20) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (20).

Using the obtained composition (20) and the liquid crystal alignment treatment agent (20), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 21>

PCS (22.2 g), γ-BL (7.92 g), BCS (3.96 g) were added to the polyimine powder (9) (1.77 g) obtained by the synthesis method of Synthesis Example 9, and stirred at 70 ° C. Allow to dissolve in hours. To the solution, a polyaluminoxane solution (4) (6.32 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 20 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (21). . It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (21) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (21).

Using the obtained composition (21) and the liquid crystal alignment treatment agent (21), "evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "production of a liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 22>

PCS (23.3 g) and NMP (9.94 g) were added to the polyimine powder (10) (1.65 g) obtained by the synthesis method of Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, a polyoxoxane solution (4) (7.40 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 20 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (22). . It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (22) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (22).

Using the obtained composition (22) and the liquid crystal alignment treatment agent (22), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 23>

PGME (30.8 g) and γ-BL (3.82 g) were added to the polyimine powder (11) (1.95 g) obtained by the synthesis method of Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To the solution, a polyoxoxane solution (1) (4.06 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 17 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (23). . It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (23) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (23).

Using the obtained composition (23) and the liquid crystal alignment treatment agent (23), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "liquid crystal alignment" Assessment of sexuality (general unit cell).

<Example 24>

PGME (32.3 g) and γ-BL (4.25 g) were added to the polyimine powder (11) (1.90 g) obtained by the synthesis method of Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. To the solution, a polyoxoxane solution (6) (6.79 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 22 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (24). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (24) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (24).

Using the obtained composition (24) and the liquid crystal alignment treatment agent (24), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 25>

PCS (25.4 g), γ-BL (3.88 g), BCS (7.76 g) were added to the polyimine powder (11) (2.23 g) obtained by the synthesis method of Synthesis Example 11, and stirred at 70 ° C. Allow to dissolve in hours. To the solution, a polyoxoxane solution (4) (2.06 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 20 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (25). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (25) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (25).

Using the obtained composition (25) and the liquid crystal alignment treatment agent (25), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Example 26>

PGME (25.5 g) and γ-BL (3.82 g) were added to the polyimine powder (12) (1.22 g) obtained by the synthesis method of Synthesis Example 12, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, a polyoxoxane solution (5) (10.2 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 21 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (26). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (26) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (26).

Using the obtained composition (26) and the liquid crystal alignment treatment agent (26), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. "Evaluation of Liquid Crystal Alignment (General Cell)" and "Production of Liquid Crystal Cell and Evaluation of Liquid Crystal Alignment (PSA Cell)".

<Example 27>

MCS (28.4 g), γ-BL (2.18 g), and BCS (10.9 g) were added to the polyimine powder (12) (2.50 g) obtained by the synthesis method of Synthesis Example 12, and stirred at 70 ° C. Allow to dissolve in hours. To the solution, a polyoxoxane solution (2) (2.31 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 18 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (27). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (27) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (27).

Using the obtained composition (27) and the liquid crystal alignment treatment agent (27), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Comparative Example 1>

NMP (28.4 g) was added to a polyamic acid solution (13) (7.70 g) having a resin solid concentration of 25.0% by mass obtained by the synthesis method of Synthesis Example 13, and stirred at 25 ° C for 1 hour. To the solution, a polyoxoxane solution (7) (4.01 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 23 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (28). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (28) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (28).

Using the obtained composition (28) and the liquid crystal alignment treatment agent (28), the coating properties of the composition and the liquid crystal alignment treatment agent are carried out under the above conditions. Evaluation", "Production of liquid crystal cell (general cell)" and "Evaluation of liquid crystal alignment (general cell)".

<Comparative Example 2>

γ-BL (28.6 g) was added to a polyamic acid solution (13) (7.75 g) having a resin solid concentration of 25.0% by mass obtained by the synthesis method of Synthesis Example 13, and stirred at 25 ° C for 1 hour. To the solution, a polyoxoxane solution (7) (4.04 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 23 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (29). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (29) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (29).

Using the obtained composition (29) and the liquid crystal alignment treatment agent (29), "evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "production of a liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Comparative Example 3>

NMP (17.6 g) and BCS (6.36 g) were added to a polyamic acid solution (13) (6.50 g) having a resin solid content concentration of 25.0% by mass obtained by the synthesis method of Synthesis Example 13, and stirred at 25 ° C. hour. To the solution, a polyoxoxane solution (7) (3.39 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 23 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (30). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (30) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (30).

Using the obtained composition (30) and the liquid crystal alignment treatment agent (30), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Comparative Example 4>

NMP (29.9 g) was added to a polyamic acid solution (14) (8.12 g) having a resin solid content concentration of 25.0% by mass obtained by the synthesis method of Synthesis Example 14, and stirred at 25 ° C for 1 hour. To the solution, a polyoxoxane solution (5) (4.23 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 21 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (31). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (31) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (31).

Using the obtained composition (31) and the liquid crystal alignment treatment agent (31), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)" and "Evaluation of Voltage Retention Rate".

<Comparative Example 5>

NMP (21.9 g) and BCS (7.93 g) were added to a polyamic acid solution (14) (8.10 g) having a solid content concentration of 25.0% by mass of the resin obtained by the synthesis method of Synthesis Example 14, and stirred at 25 ° C. hour. In this solution, a polyoxoxane solution (5) (4.22 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 21 was stirred, and stirred at 25 ° C for 2 hours to obtain a composition (32). . It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (32) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (32).

Using the obtained composition (32) and the liquid crystal alignment treatment agent (32), "the evaluation of the applicability of the composition and the liquid crystal alignment treatment agent" and "the production of the liquid crystal cell (general unit cell)" were carried out under the above conditions. And "Evaluation of Liquid Crystal Alignment (General Cell)".

<Comparative Example 6>

NMP (35.0 g) was added to the polyimine powder (4) (1.65 g) obtained by the synthesis method of Synthesis Example 4, and the mixture was stirred at 70 ° C for 24 hours to dissolve. To the solution, a polyoxoxane solution (1) (9.17 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthesis method of Synthesis Example 17 was added, and the mixture was stirred at 25 ° C for 2 hours to obtain a composition (33). ). It was confirmed that no abnormality such as turbidity or precipitation occurred in the composition, and it was a uniform solution. Further, this composition (33) can also be used for evaluation in the form of a liquid crystal alignment treatment agent (33).

Using the obtained composition (33) and the liquid crystal alignment treatment agent (33), the coating properties of the composition and the liquid crystal alignment treatment agent are carried out under the above conditions. "Evaluation", "Production of Liquid Crystal Cell (General Cell)" and "Evaluation of Liquid Crystal Alignment (General Cell)" and "Evaluation of Voltage Retention Rate".

<Comparative Example 7>

PGME (32.9 g) was added to (15) (1.55 g) of the polyimine powder obtained by the synthesis method of Synthesis Example 15, and stirred at 70 ° C for 24 hours. Since the dissolution of the polyimine powder was found in the solution, the polyimine powder was not completely dissolved even after stirring at 70 ° C for 12 hours.

Therefore, the composition (34) and the liquid crystal alignment treatment agent (34) cannot be produced.

As is apparent from the above results, when the composition of the example of the present invention was applied to a substrate as compared with the composition of the comparative example, it was shown that uniform coating property with pinholes due to repulsion did not occur. Specifically, in use Comparison of composition of the same polyimine precursor or solvent-soluble polyimine, ie, comparison of Example 1 with Comparative Example 1, Comparative Example 2 or Comparative Example 3; Example 4 and Comparative Example 4 or Comparison of Comparative Example 5; and Comparison of Example 7 with Comparative Example 6.

Further, the same results were obtained from the liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent of the composition of the present invention. Specifically, a comparison of a liquid crystal alignment treatment agent using the same polyimide intermediate or a solvent-soluble polyimide, that is, a comparison between Example 1 and Comparative Example 1, Comparative Example 2, or Comparative Example 3; Example 4 is compared with Comparative Example 4 or Comparative Example 5; and Example 7 is compared with Comparative Example 6. In particular, even if a liquid crystal alignment treatment agent using a polyimine precursor obtained by using a diamine compound having a side chain and a solvent-soluble polyimine is used, the display does not occur as described above. Uniform coating properties of pinholes.

Further, in the evaluation of the liquid crystal alignment of the liquid crystal cell, the liquid crystal crystal obtained by using the liquid crystal alignment treatment agent of the composition of the present invention is compared with the liquid crystal cell obtained by using the liquid crystal alignment treatment agent of the composition of the comparative example. The cell has no misalignment due to pinholes, and uniform liquid crystal alignment is obtained. Specifically, a comparison of a liquid crystal alignment treatment agent using the same polyimide intermediate or a solvent-soluble polyimide, that is, a comparison of Example 1 with Comparative Example 1, Comparative Example 2, or Comparative Example 3; Comparison of Example 4 with Comparative Example 4 or Comparative Example 5; and Comparison of Example 7 with Comparative Example 6.

In addition, in the evaluation of the voltage holding ratio, compared with the liquid crystal cell obtained by using the liquid crystal alignment treatment agent of the composition of the comparative example, The liquid crystal cell obtained by the liquid crystal alignment treatment agent of the composition of the present invention shows a high value. Specifically, a comparison of a liquid crystal alignment treatment agent using the same polyimide intermediate or a solvent-soluble polyimide, that is, a comparison between Example 4 and Comparative Example 4 and Examples 7 and 6 Comparison.

[Industrial availability]

When the composition of the present invention is applied to a substrate, a resin film which exhibits uniform coating properties without causing pinholes accompanying repulsion can be obtained. Further, the same results were obtained by using the liquid crystal alignment treatment agent of the composition of the present invention.

Further, the liquid crystal alignment agent of the present invention can obtain a liquid crystal cell which does not cause an alignment defect caused by pinholes accompanying repulsion. In particular, the same result can be obtained even if a liquid crystal alignment treatment agent using a polyamine imine precursor obtained by using a diamine compound having a side chain or a solvent-soluble polyimine is used.

Further, the liquid crystal alignment treatment agent of the present invention can be used for a liquid crystal display element which is switched between a liquid crystal transmission state (also referred to as a transparent state) and a scattering state, that is, a polymer dispersed liquid crystal (PDLC) (Polymer Dispersed Liquid Crystal) Or a liquid crystal display element of a polymer network liquid crystal (PNLC) is also suitable.

It is especially suitable for reverse-type components that are transparent when no voltage is applied and that are scattered when voltage is applied. This reverse type component can be used for glass substrates or PET (polyethylene terephthalate) or acrylic A liquid crystal display for the purpose of display of a plastic substrate such as a board, a dimming window for controlling light transmission and interruption, a light shutter element, a dimming window of a vehicle such as an automobile, and a back panel of a transparent display.

Further, the liquid crystal alignment treatment agent of the present invention has a high voltage holding ratio even when fired at a low temperature.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and is applicable to a large screen, a high-definition liquid crystal television, etc., and can also be used for a TN element, an STN element, or the like. A TFT liquid crystal element, particularly a vertical alignment type liquid crystal display element.

Further, when the liquid crystal display element is produced from the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention, it can be used for a liquid crystal display element which is required to be irradiated with ultraviolet rays. In other words, it can be used to form a liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat between the pair of substrates via a liquid crystal layer provided between one of the electrodes; a liquid crystal display element produced by a step of applying a voltage between the electrodes to polymerize the polymerizable compound, and a liquid crystal layer formed between a pair of substrates including electrodes, and disposed between the pair of substrates A liquid crystal alignment film produced by the step of polymerizing the polymerizable group by applying a voltage between the electrodes, and a polymerizable group-based liquid crystal alignment film in which at least one of an active energy ray and a heat is polymerized.

Claims (26)

A composition comprising the following components (A), (B) and (C), and the following component (A) is 55 to 100% by mass of the solvent contained in the composition, (A) Component: a solvent selected from at least one of the following formula [1a] or formula [1b], (In the formula [1a], X ¹ represents an alkyl group having 1 to 3 carbon atoms, in the formula [1b], X ² represents an alkyl group having 1 to 3 carbon atoms), and the component (B) is selected from the group consisting of a carboxyl group. a polymer of at least one of a polyimine precursor obtained by reacting a diamine component of a diamine compound with a tetracarboxylic dianhydride component or a polyimine, (C) component: comprising the following formula [A1] a polyoxyalkylene obtained by polycondensation of an alkoxydecane of any one of the alkoxydecanes represented by the formula [A2] or the formula [A3], [Chemical Formula 2] (A ¹ ) _m Si(A ² ) _n (OA ³ ) _p [A1] (In the formula [A1], A ¹ represents an aliphatic hydrocarbon, a benzene ring, a cyclohexane ring, a heterocyclic ring or an organic group having a steroid structure of 8 to 35 carbon atoms, and A ² respectively Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3, However, m+n+p is 4), ( Chemical Formula ³ ) (B ¹ ) _m Si(B ² ) _n (OB ³ ) _p [A2] (In the formula [A2], B ¹ represents a vinyl group, an epoxy group, An amine group, a fluorenyl group, an isocyanate group, a methacryl fluorenyl group, an acryl fluorenyl group, a ureido group or an organic group having a cinnamyl group having 2 to 12 carbon atoms, and B ² represents a hydrogen atom or a carbon number, respectively. ~5 alkyl, B ³ represents an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, and p represents an integer of 0 to 3, but m+n+p is 4), [Chemical 4] (D ¹ ) _n Si(OD ² ) _4-n [A3] (In the formula [A3], D ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and D ² represents carbon. An alkyl group of 1 to 5, and n represents an integer of 0 to 3). The composition of claim 1, wherein the diamine compound having a carboxyl group of the component (B) is a diamine compound having a structure represented by the following formula [2], [Chem. 5] -(CH ₂ ) _a -COOH [2] (in the formula [2], a represents an integer from 0 to 4). The composition of claim 2, wherein the diamine compound having a carboxyl group of the component (B) is a diamine compound having a structure represented by the following formula [2a], (In the formula [2a], a represents an integer from 0 to 4, and n represents an integer from 1 to 4). The composition of claim 2, wherein the aforementioned dimethylation of a carboxyl group The compound is 20 mol% to 100 mol% of the total diamine used in the above component (B). The composition of claim 3, wherein the diamine compound having a carboxyl group is 20 mol% to 100 mol% of the total diamine used in the component (B). The composition of claim 1, wherein the diamine component of the component (B) contains at least one diamine compound selected from the group consisting of the structures represented by the following formula [2b], (In the formula [2b], Y represents a structure of the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5], and m represents An integer from 1 to 4), (In the formula [2b-1], a represents an integer of 0 to 4, and in the formula [2b-2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O -, -CH ₂ O-, -COO- or -OCO-, Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), and Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, and Y ⁴ represents a divalent ring selected from a benzene ring, a cyclohexane ring or a hetero ring a divalent organic group having a carbon number of 12 to 25 having a steroid skeleton, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or carbon a fluorine-containing alkyl group having 1 to 3, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and Y ⁵ representing a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring; Any hydrogen atom on the cyclic group may have an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine atom having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom, n represents an integer of 0 to 4, and Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms; in the formula [2b-3], Y ⁷ represents an alkyl group having 8 to 22 carbon atoms, and in the formula [2b-4], Y ⁸ and Y ⁹ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and in the formula [2b-5], Y ¹⁰ represents an alkyl group having 1 to 8 carbon atoms). The composition of claim 1, wherein the tetracarboxylic dianhydride component of the component (B) is a compound represented by the following formula [3], (In the formula [3], Z ¹ is a group selected from at least one of the following formulas [3a] to [3j]), (In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group. Each can be the same or different). The composition of claim 1, wherein the alkoxydecane represented by the formula [A2] of the above component (C) is selected from the group consisting of allyltriethoxydecane, allyltrimethoxydecane, and diethoxy. Methyl vinyl decane, dimethoxymethyl vinyl decane, triethoxy vinyl decane, vinyl trimethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, 3- (three At least one of ethoxylated alkyl)propyl methacrylate, 3-(trimethoxydecyl)propyl acrylate or 3-(trimethoxydecyl)propyl methacrylate. The composition of claim 1, wherein the alkoxydecane represented by the formula [A2] of the above component (C) is selected from the group consisting of 3-glycidyloxypropyl (dimethoxy)methyl decane, 3- Glycidyloxypropyl (diethoxy)methyl decane, 3-glycidoxy propyl trimethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane At least one of them. The composition of claim 1, wherein the polyoxane of the component (C) is a polyoxane obtained by polycondensing the alkoxydecane represented by the above formula [A1], the formula [A2] and the formula [A3]. alkyl. The composition of claim 1, further comprising (D) a component comprising at least N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone 1 solvent. The composition of claim 1, further comprising (E) a component comprising 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutylate At least one of ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether or diethylene glycol monobutyl ether 1 solvent. A resin film obtained by the composition of any one of claims 1 to 12. A liquid crystal alignment treatment agent obtained by the composition of any one of claims 1 to 12. A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent of claim 14. A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of claim 14 and obtained by an inkjet method. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 15. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 16. The liquid crystal alignment film of claim 15, which is used for the following In the liquid crystal display device produced in the step, the liquid crystal layer is formed between one of the electrodes, and the polymerizable compound which is polymerized by at least one of the active energy ray and the heat is disposed between the pair of substrates. The liquid crystal composition is a step of applying a voltage between the electrodes to polymerize the polymerizable compound. The liquid crystal alignment film of claim 16, which is used in a liquid crystal display device manufactured by the following steps, wherein the step of providing a liquid crystal layer between the substrates is performed on one of the electrodes, and the substrate is disposed between the pair of substrates. A liquid crystal composition of a polymerizable compound which is polymerized by at least one of an active energy ray and heat, and a step of applying a voltage between the electrodes to polymerize the polymerizable compound. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 19. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 20. The liquid crystal alignment film of claim 15, which is used in a liquid crystal display device manufactured by the following steps, wherein the step of providing a liquid crystal layer between the substrates is performed on one of the electrodes, and the substrate is disposed between the pair of substrates. A liquid crystal alignment film of a polymerizable group which is polymerized by at least one of an active energy ray and heat, and a step of applying a voltage between the electrodes to polymerize the polymerizable group. The liquid crystal alignment film of claim 16, which is used in a liquid crystal display device manufactured by the following steps, wherein the step of providing a liquid crystal layer between the substrates is performed on one of the electrodes, and the substrate is disposed between the pair of substrates. A liquid crystal alignment film of a polymerizable group which is polymerized by at least one of an active energy ray and heat, and a step of applying a voltage between the electrodes to polymerize the polymerizable group. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 23. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 24.