TW201833180A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The invention relates to a liquid crystal alignment agent and a method for manufacturing the liquid crystal alignment agent. The liquid crystal alignment agent includes a polymer (A), a polysiloxane (B) containing a photo-reactive group and a solvent (C). The polymer (A) is selected from a polyamide acid polymer, a polyimide polymer, a polyimide-based block copolymer or a combination thereof. The liquid crystal alignment agent of the invention has the advantages of low liquid crystal contact angle and high impedance. Furthermore, the invention also provides a liquid crystal alignment film made by the aforementioned liquid crystal alignment agent, a method for forming the liquid crystal alignment film, and a liquid crystal display element including the liquid crystal alignment film.

Description

Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

The invention relates to a liquid crystal alignment agent and a method for manufacturing the same, a liquid crystal alignment film and a method for manufacturing the same, and a liquid crystal display element, in particular to a liquid crystal alignment agent with a low liquid crystal contact angle and a high bulk impedance, a method for manufacturing the same, and the liquid crystal alignment Liquid crystal alignment film formed by an agent, a method for manufacturing the same, and a liquid crystal display element having the liquid crystal alignment film.

Generally, in liquid crystal display elements, various driving methods have been developed according to the structure of the electrodes or the physical properties of the liquid crystal molecules used. Currently known driving methods of liquid crystal display elements are, for example, TN type or STN type, VA type, lateral electric field effect display technology type (IPS type), and the like. The liquid crystal display element includes a liquid crystal alignment film for aligning liquid crystal molecules. The material of the liquid crystal alignment film may be, for example, known materials such as polyamic acid, polyimide, polyester, polyorganosiloxane, and the like.

In recent years, in order to control the alignment of liquid crystal molecules of liquid crystal display elements, new technologies such as Polymer Sustained Alignment (PSA) have been proposed, for example, Japanese Publication No. JP 2003-149647, and the polymer stable alignment technology described therein The photopolymerizable component is added to the liquid crystal layer of the liquid crystal cell, and the liquid crystal molecules are tilted under a voltage applied state, and then the liquid crystal cell is irradiated with light, thereby polymerizing the photopolymerizable component, thereby controlling the alignment of the liquid crystal molecules. .

However, when using polymer stabilized alignment technology to control the alignment of liquid crystal molecules, a relatively high light exposure is required, which causes defects such as decomposition of liquid crystal molecules and deterioration of the properties of the liquid crystal alignment film, thereby causing display unevenness of the liquid crystal display element. And panel durability is degraded. On the other hand, if the amount of light irradiation is reduced, the reaction rate of liquid crystal molecules in the formed liquid crystal display element to a voltage change becomes slow. In order to make the liquid crystal alignment agent for forming a coating film, a predetermined pretilt angle characteristic can be achieved with a small amount of light irradiation as much as possible, and the liquid crystal molecules in the formed liquid crystal display element have a fast response rate to voltage, Japanese Patent No. The technology of Patent No. 2011-118358 discloses a liquid crystal alignment agent using a polyorganosiloxane containing, for example, a (meth) acrylfluorenyl group, and a photopolymerizable component of polyimide acid or polyimide, in A liquid crystal alignment film is formed on the substrate. Next, the substrate is formed into a liquid crystal cell, and when a voltage is applied between the substrates, the liquid crystal cell is irradiated with light to produce a liquid crystal display element.

However, in the above method, because the liquid crystal contact angle of the liquid crystal alignment agent is too high, the liquid crystal cannot be uniformly covered on the liquid crystal alignment film. In addition, the bulk impedance of the above-mentioned liquid crystal alignment agent is still low, which cannot meet industrial requirements. Therefore, there is an urgent need to propose a liquid crystal alignment agent, which can improve the shortcomings of too high a liquid crystal contact angle and a low bulk impedance.

In the present invention, liquid crystal alignment agents are obtained by using components such as a special polymer and a polysiloxane containing a photoreactive group, and the liquid crystal alignment film and the liquid crystal display element formed by the liquid crystal alignment agent have a low liquid crystal contact angle and a compact body. The advantage of high impedance.

Therefore, the present invention relates to a liquid crystal alignment agent, which comprises: a polymer (A), which is selected from the group consisting of a polyimide polymer, a polyimide polymer, a polyimide block copolymer, or the above. Any combination of polymers; a photoreactive group-containing polysiloxane (B); and a solvent (C); wherein the polymer (A) comprises a unit represented by formula (Ia): Formula (Ia) In Formula (Ia), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or a straight or branched chain of C ₁ to C ₁₀ Alkyl; R _e is a single bond, or a linear or branched alkyl group of C ₁ to C ₁₀ ; R _a is a single bond, or _a linear or branched alkyl group of C ₁ to C ₁₀ ; Ht is a nitrogen-containing heterocyclic ring; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c each other Can be combined to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; when Y is -COO-, -CONR _d -or -R _e -NR _{When d-} , a1 is 1; and * is a bond; the photoreactive group-containing polysiloxane (B) includes a structure represented by formula (IIa): Formula (IIa) In Formula (IIa), R ₁ is a methylene group, a linear or branched alkylene group, a phenylene group, or a cyclohexyl group from C ₂ to C ₁₀ , and a part of the hydrogen atom of the R ₁ functional group is Substituted or unsubstituted; R ₂ is a methylene group, or a linear or branched alkylene group of C ₂ to C ₁₀ , and a part of hydrogen atoms of the R ₂ functional group is substituted or unsubstituted; R ₃ is a single bond , Methylene, or C ₂ to C ₁₀ linear or branched alkylene, a part of the hydrogen atom of the R ₃ functional group is substituted or unsubstituted; R ₄ is a hydrogen atom or a methyl group; L is -OCO -, -O- or -S-; a is an integer from 0 to 10; b is an integer from 0 to 1; when b is 0, a is not 0; when a is plural, a plurality of R ₂ and L are each Are the same or different; and * is the bond.

The present invention further provides a liquid crystal alignment film, which is formed by the aforementioned liquid crystal alignment agent.

The present invention also provides a liquid crystal display device including the aforementioned liquid crystal alignment film.

The present invention also provides a method for manufacturing a liquid crystal alignment agent, which comprises a mixed polymer (A), a polysiloxane containing a photoreactive group (B), and a solvent (C).

The invention further provides a method for manufacturing a liquid crystal alignment film, which comprises forming the liquid crystal alignment film from a liquid crystal alignment agent, wherein the liquid crystal alignment agent is formed by the aforementioned method for manufacturing a liquid crystal alignment agent.

The present invention also provides a method for manufacturing a liquid crystal display element. The liquid crystal display element includes a liquid crystal alignment film. The manufacturing method includes forming the liquid crystal alignment film from a liquid crystal alignment agent. The liquid crystal alignment agent is made of the aforementioned liquid crystal alignment agent. Formed by manufacturing methods.

The present invention provides a liquid crystal alignment agent, which comprises: a polymer (A), which is selected from the group consisting of a polyimide polymer, a polyimide polymer, a polyimide block copolymer, or the polymer described above. Any combination; a photoreactive group-containing polysiloxane (B); and a solvent (C); wherein the polymer (A) comprises a unit represented by formula (Ia): Formula (Ia) In Formula (Ia), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or a straight or branched chain of C ₁ to C ₁₀ Alkyl; R _e is a single bond, or a linear or branched alkyl group of C ₁ to C ₁₀ ; R _a is a single bond, or _a linear or branched alkyl group of C ₁ to C ₁₀ ; Ht is a nitrogen-containing heterocyclic ring; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c each other Can be combined to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; when Y is -COO-, -CONR _d -or -R _e -NR _{When d-} , a1 is 1; and * is a bond; the photoreactive group-containing polysiloxane (B) includes a structure represented by formula (IIa): Formula (IIa) In Formula (IIa), R ₁ is a methylene group, a linear or branched alkylene group, a phenylene group, or a cyclohexyl group from C ₂ to C ₁₀ , and a part of the hydrogen atom of the R ₁ functional group is Substituted or unsubstituted; R ₂ is a methylene group, or a linear or branched alkylene group of C ₂ to C ₁₀ , and a part of hydrogen atoms of the R ₂ functional group is substituted or unsubstituted; R ₃ is a single bond , Methylene, or C ₂ to C ₁₀ linear or branched alkylene, a part of the hydrogen atom of the R ₃ functional group is substituted or unsubstituted; R ₄ is a hydrogen atom or a methyl group; L is -OCO -, -O- or -S-; a is an integer from 0 to 10; b is an integer from 0 to 1; when b is 0, a is not 0; when a is plural, a plurality of R ₂ and L are each Are the same or different; and * is the bond.

The polymer (A) according to the present invention is obtained by reacting a first mixture including a tetracarboxylic dianhydride component (a-1) and a diamine component (a-2).

Specifically, the polymer (A) is selected from the group consisting of a polyamidopolymer, a polyamidopolymer, a polyamidoblock copolymer, and any combination of the aforementioned polymers. Among them, the polyfluorene-based block copolymer includes a polyfluoride-based block copolymer, a polyfluoride-based imide block copolymer, a polyfluoride-based polyimide-block copolymer, or the above-mentioned polymerization. Combination of things. The poly (fluorinated acid) polymer, the poly (fluorinated imine) polymer, and the poly (fluorinated-polyimide) block copolymer in the polymer (A) may be composed of a tetracarboxylic dianhydride component (a-1). And a mixture of diamine component (a-2).

The polymer (A) contains a unit represented by formula (Ia): Formula (Ia) In Formula (Ia), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or a straight or branched chain of C ₁ to C ₁₀ Alkyl; R _e is a single bond, or a linear or branched alkyl group of C ₁ to C ₁₀ ; R _a is a single bond, or _a linear or branched alkyl group of C ₁ to C ₁₀ ; Ht is a nitrogen-containing heterocyclic ring; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c each other Can be combined to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; when Y is -COO-, -CONR _d -or -R _e -NR _{When d-} , a1 is 1; and * is a bond.

Preferably, the polymer (A) comprises a unit represented by formula (Ia-1), formula (Ia-2) or formula (Ia-3): Formula (Ia-1) Formula (Ia-2) Formula (Ia-3) In Formula (Ia-1) to Formula (Ia-3), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or C ₁ to C ₁₀ linear or branched alkyl; R _e is a single bond, or C ₁ to C ₁₀ linear or branched alkyl; R _a is a single bond, or C ₁ to C ₁₀ linear or branched alkyl; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c can be combined with each other to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; when Y is -COO-, -CONR _d -or -R _{When e} -NR _d- , a1 is 1; and * is a bonding point.

The tetracarboxylic dianhydride compound (a-1) includes an aliphatic tetracarboxylic dianhydride compound, an alicyclic tetracarboxylic dianhydride compound, an aromatic tetracarboxylic dianhydride compound, and from formula (I-1) to formula At least one of the tetracarboxylic dianhydride compounds represented by (I-6), or a combination thereof.

Specific examples of the aliphatic tetracarboxylic dianhydride compound, the alicyclic tetracarboxylic dianhydride compound, and the aromatic tetracarboxylic dianhydride compound are listed below, but the present invention is not limited to these specific examples.

Specific examples of the aliphatic tetracarboxylic dianhydride compound may include, but are not limited to, ethane tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, or a combination thereof.

Specific examples of the alicyclic tetracarboxylic dianhydride compound may include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutyl Cyclopeptyl-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, or a combination of the foregoing compounds.

Specific examples of the aromatic tetracarboxylic dianhydride compound may include, but are not limited to, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylpyrenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethanetetracarboxylic dianhydride, 3,3', 4,4'- Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylarsine dianhydride, 4,4'- Bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride (4,4'-bis (3,4-dicarboxy phenoxy) diphenylpropane dianhydride), 3,3 ', 4,4'-perfluoroisoprene Propyldiphthalic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (tris) Phenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (Triphenylphthalic acid) -4,4'- Phenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydromellitate), 1,4-butanediol-bis (anhydromellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane- Bis (anhydrotrimellitic acid ester), 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5- Dioxo-3-furyl) -naphtho [1,2-c] -furan-1,3-dione {(1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro- 2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione)}, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1, 3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene Benzo [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dione (Oxy-3-furyl) -naphthalene [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo Yl-3-furyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl- 5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxo Tetrahydrofuranyl) aromatic tetracarboxylic dianhydride compounds such as 3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride or a combination of the foregoing compounds.

The tetracarboxylic dianhydride compounds represented by formula (I-1) to formula (I-6) are shown below. Formula (I-1) Formula (I-2) Formula (I-3) Formula (I-4) Formula (I-5)

In Formula (I-5), A ¹ represents a divalent group containing an aromatic ring; r represents an integer of 1 to 2; A ² and A ³ may be the same or different, and each may independently represent a hydrogen atom or an alkyl group. Specific examples of the tetracarboxylic dianhydride compound represented by the formula (I-5) include at least one of compounds represented by the formula (I-5-1) to the formula (I-5-3). Formula (I-5-1) Formula (I-5-2) Formula (I-5-3) Formula (I-6)

In Formula (I-6), A ⁴ represents a divalent group containing an aromatic ring; A ⁵ and A ⁶ may be the same or different, and each independently represents a hydrogen atom or an alkyl group. The tetracarboxylic dianhydride compound represented by the formula (I-6) is preferably a compound represented by the formula (I-6-1). Formula (I-6-1)

The tetracarboxylic dianhydride compound (a-1) may be used alone or in combination.

Specific examples of the tetracarboxylic dianhydride compound (a-1) include 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1,2,3,4-cyclobutane tetracarboxylic dianhydride), 1, 2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4,5-cyclohexane Alkanetetracarboxylic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydronaphthalene-1-succinic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylfluorenetetracarboxylic dianhydride, a compound represented by formula (I-1), or a combination thereof.

The total mole number based on the diamine component (a-2) is 100 moles, and the amount of the tetracarboxylic dianhydride component (a-1) is preferably in the range of 80 moles to 120 moles, more preferably 85 mol to 115 mol.

The diamine component (a-2) according to the present invention includes at least one diamine compound (a-2-1) represented by the formula (Ib): Formula (Ib) In Formula (Ib), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or a straight or branched chain of C ₁ to C ₁₀ Alkyl; R _e is a single bond, or a linear or branched alkyl group of C ₁ to C ₁₀ ; R _a is a single bond, or _a linear or branched alkyl group of C ₁ to C ₁₀ ; Ht is a nitrogen-containing heterocyclic ring; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c each other Can be combined to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; and when Y is -COO-, -CONR _d -or -R _e- When NR _d- , a1 is 1.

Preferably, the diamine compound (a-2-1) comprises a compound represented by formula (Ib-1), formula (Ib-2) or formula (Ib-3): Formula (Ib-1) Formula (Ib-2) Formula (Ib-3) In Formula (Ib-1) to Formula (Ib-3), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or C ₁ to C ₁₀ linear or branched alkyl; R _e is a single bond, or C ₁ to C ₁₀ linear or branched alkyl; R _a is a single bond, or C ₁ to C ₁₀ linear or branched alkyl; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c can be combined with each other to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; and when Y is -COO-, -CONR _d -or- When R _e −NR _d −, a1 is 1.

Specific examples of the diamine compound (a-2-1) are , , , , , , , , , , , , , , , , , , or .

In a specific example of the present invention, based on the total usage of the diamine component (a-2) is 100 moles, and the usage of the diamine compound (a-2-1) is 3 to 40 moles, preferably It is 5 to 35 moles, more preferably 5 to 30 moles. If the diamine compound (a-2-1) is not used, the bulk resistance of the obtained liquid crystal alignment agent is low, and the liquid crystal contact angle is high.

Preferably, the diamine component (a-2) of the present invention may further include other diamine compounds (a-2-2).

The other diamine compound (a-2-2) includes an aliphatic diamine compound, an alicyclic diamine compound, an aromatic diamine compound, and has a formula (a-2-2-1) to a formula (a-2- 2-26), a diamine compound, or a combination thereof.

Specific examples of the aliphatic diamine compound include, but are not limited to, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane , 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane , 4,4'-diaminoheptane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1, 9-diamino-5-methylnonane, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) ethyl Alkane, or a combination of the above.

Specific examples of the alicyclic diamine compound include, but are not limited to, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, 1, 3-diaminocyclohexane, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene diamine, tricyclo [6.2.1.02,7] -undecyl Dimethydiamine, 4,4'-methylenebis (cyclohexylamine), or a combination of the foregoing.

Specific examples of the aromatic diamine compound include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl Hydrazone, 4,4'-diaminobenzidineaniline, 4,4'-diaminostilbene stilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminediamine Phenyl ether, 3,3'-diaminochalcone, 1,5-diaminonaphthalene, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethyl Indanes, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylhydroindene, hexahydro-4,7-methyl bridged indenyl dimethylene Diamine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenylphenyl) ) Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 9,10-bis ( 4-aminophenyl) anthracene [9,10-bis (4-aminophenyl) anthracene], 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) , 4,4'-methylene-bis (2-chloroaniline), 4,4 '-(p-phenylene isopropylidene) bisaniline, 4,4'-(m-phenylene isopropylidene) Propyl) bisaniline, 2,2'-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [(4-amino -2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenyl-methylene-1,3-diamine Benzene {5- [4- (4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diamino benzene}, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- ( 4-ethylphenyl) cyclohexane {1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylphenyl) cyclohexane}, or a combination thereof.

The diamine compounds represented by the formula (a-2-2-1) to the formula (a-2-2-30) are shown below. Formula (a-2-2-1)

In formula (a-2-2-1), B ¹ represents , , , , ,or ; B ² represents a group having a steroid (cholesterol) skeleton, a trifluoromethyl group, a fluorine atom, a C ₂ to C ₃₀ alkyl group, or a derivative derived from A monovalent group of a nitrogen atom ring structure.

Specific examples of the compound represented by the formula (a-2-2-1) include, but are not limited to, 2,4-diaminophenyl ethyl formate, 3,5-diamino 3,5-diaminophenyl ethyl formate, 2,4-diaminophenyl propyl formate, 3,5-diaminophenyl propyl formate 3,5-diaminophenyl propyl formate), 1-dodecoxy-2,4-diaminobenzene, 1-dodecoxy-2,4-diaminobenzene Aminobenzene (1-hexadecoxy-2,4-diaminobenzene), 1-octadecoxy-2,4-diaminobenzene (1-octadecoxy-2,4-diaminobenzene), from the formula (a-2- 2-1-1) to at least one of the compounds represented by formula (a-2-2-1-6), or a combination of the aforementioned compounds. Formula (a-2-2-1-1) Formula (a-2-2-1-2) Formula (a-2-2-1-3) Formula (a-2-2-1-4) Formula (a-2-2-1-5) Formula (a-2-2-1-6) Formula (a-2-2-2)

In the formula (a-2-2-2), and B ¹ in the formula (a-2-2-1) B same as ^1, B ³ and B ⁴ each independently represents a divalent aliphatic ring, a divalent aromatic ring Or a divalent heterocyclic group; B ⁵ represents a C ₃ to C ₁₈ alkyl group, a C ₃ to C ₁₈ alkoxy group, a C ₁ to C ₅ fluoroalkyl group, and a C ₁ to C ₅ fluoroalkoxy group , Cyano or halogen atom.

Specific examples of the compound represented by the formula (a-2-2-2) include at least among the compounds represented by the formula (a-2-2-2-1) to the formula (a-2-2-2-13). one of them. Specifically, the compounds represented by the formula (a-2-2-2-1) to the formula (a-2-2-2-13) are shown below. Formula (a-2-2-2-1) Formula (a-2-2-2-2) Formula (a-2-2-2-3) Formula (a-2-2-2-4) Formula (a-2-2-2-5) Formula (a-2-2-2-6) Formula (a-2-2-2-7) Formula (a-2-2-2-8) Formula (a-2-2-2-9) Formula (a-2-2-2-10) Formula (a-2-2-2-11) Formula (a-2-2-2-12) Formula (a-2-2-2-13)

In the formulae (a-2-2-2-10) to (a-2-2-2-13), s represents an integer of 3 to 12. Formula (a-2-2-3)

(A-2-2-3) In the formula, B ⁶ each independently represent a hydrogen atom, C ₁ to C ₅ of acyl, C ₁ to C ₅ alkyl group of, C ₁ to C ₅ alkoxy group or a halogen atom of And B ⁶ in each repeating unit may be the same or different; u represents an integer of 1 to 3.

Specific examples of the compound represented by the formula (a-2-2-3) include when u is 1: p-diaminebenzene, m-diaminebenzene, o-diaminebenzene, or 2,5-diaminotoluene Etc .; when u is 2: 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3 , 3'-dichloro-4,4'-diaminobiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro- 4,4'-diamino-5,5'-dimethoxybiphenyl or 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, etc .; or when u is 3 o'clock: 1,4-bis (4'-aminophenyl) benzene and the like.

Specific examples of the compound represented by the formula (a-2-2-3) preferably include p-diaminobenzene, 2,5-diaminotoluene, 4,4'-diaminobiphenyl, 3,3 '-Dimethoxy-4,4'-diaminobiphenyl, 1,4-bis (4'-aminophenyl) benzene or a combination thereof. Formula (a-2-2-4)

In the formula (a-2-2-4), v represents an integer of 2 to 12. Formula (a-2-2-5)

In the formula (a-2-2-5), w represents an integer of 1 to 5. The compound represented by the formula (a-2-2-5) is preferably 4,4'-diamino-diphenylsulfide. Formula (a-2-2-6)

In formula (a-2-2-6), B ⁷ and B ⁹ each independently represent a divalent organic group, and B ⁷ and B ⁹ may be the same or different; B ⁸ represents a derivative derived from pyridine, pyrimidine, triazine, A divalent group of a cyclic structure containing a nitrogen atom such as piperidine or piperazine. Formula (a-2-2-7)

In the formula (a-2-2-7), B ¹⁰ , B ¹¹ , B ¹² and B ¹³ each independently represent a C ₁ to C ₁₂ hydrocarbon group, and B ¹⁰ , B ¹¹ , B ¹² and B ¹³ may be the same or Different; X1 each independently represents an integer from 1 to 3; X2 represents an integer from 1 to 20. Formula (a-2-2-8)

In the formula (a-2-2-8), B ¹⁴ represents an oxygen atom or a cyclohexyl group; B ¹⁵ represents a methylene (-ethylene) group; B ¹⁶ represents a phenylene group or a cyclohexane group B ¹⁷ represents a hydrogen atom or a heptyl group.

Specific examples of the compound represented by the formula (a-2-2-8) include a compound represented by the formula (a-2-2-8-1), a compound represented by the formula (a-2-2-8-2) Compound or a combination of the above. Formula (a-2-2-8-1) Formula (a-2-2-8-2)

The compounds represented by the formula (a-2-2-9) to the formula (a-2-2-25) are shown below. Formula (a-2-2-9) Formula (a-2-2-10) Formula (a-2-2-11) Formula (a-2-2-12) Formula (a-2-2-13) Formula (a-2-2-14) Formula (a-2-2-15) Formula (a-2-2-16) Formula (a-2-2-17) Formula (a-2-2-18) Formula (a-2-2-19) Formula (a-2-2-20) Formula (a-2-2-21) Formula (a-2-2-22) Formula (a-2-2-23) Formula (a-2-2-24) Formula (a-2-2-25)

In formulae (a-2-2-17) to (a-2-2-25), B ^{18 is} preferably a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkoxy group; B ¹⁹ Preferred is a hydrogen atom, a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₁₀ alkoxy group. Formula (a2-2-26)

In formula (a2-2-26), B ²⁰ and B ²² each independently represent a single bond, -O-, -COO-, or -OCO-; B ²¹ is an alkylene group having 1 to 3 carbon atoms; B23 is a single Bond or alkylene having 1 to 3 carbons. d and g each independently represent 0 or 1; e represents an integer from 0 to 2; f represents an integer from 1 to 20; wherein d and e are not 0 at the same time.

In the formula (a2-2-26), the divalent group represented by "-B ^20- (B ²¹ -B ²² ) g-" is preferably an alkylene group having 1 to 3 carbon atoms, * -O- , * -COO- or * -O-C2H4-O- (where * represents a bond to a diaminophenyl group.). The group represented by "-C _f H _{2f + 1} " is preferably linear. The positions of two amine groups in the diaminophenyl group with respect to other groups are preferably the 2, 4-position or the 3, 5-position.

Specific examples of the compound represented by the formula (a2-2-26) include compounds represented by the following formula (a2-2-26-1) to (a2-2-26-4): Formula (a-2-2-26-1) Formula (a-2-2-26-2) Formula (a-2-2-26-3) Formula (a-2-2-26-4) Formula (a-2-2-26-5)

This other diamine compound (a-2-2) can be used individually or in combination of multiple types.

Specific examples of the other diamine compound (a-2-2) preferably include, but are not limited to, 1,2-diaminoethane, 3,3'-diaminochalcone, 4,4'-di Amino stilbene, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 5- [4 -(4-n-pentylcyclohexyl) cyclohexyl] phenylmethylene-1,3-diaminobenzene, 1,1-bis [4- (4-aminophenoxy) phenyl]- 4- (4-ethylphenyl) cyclohexane, ethyl 2,4-diaminophenylcarboxylate, 1-octadecyloxy-2,4-diaminobenzene, and the formula (a-2 A compound represented by -2-1-1), a compound represented by formula (a-2-2-1-2), a compound represented by formula (a-2-2-1-4), and a compound represented by formula (a- 2-2-1-5), compound represented by formula (a-2-2-2-1), compound represented by formula (a-2-2-2-11), p-diamine Benzene, m-diamine benzene, o-diamine benzene, compounds represented by formula (a-2-2-8-1), from formula (a-2-2-26) to formula (a-2-2 -30), or a combination thereof.

In a specific example of the present invention, based on the total usage of the diamine component (a-2) is 100 moles, the usage of the other diamine compound (a-2-2) is 60 to 97 moles, It is preferably 65 to 95 moles, and more preferably 70 to 95 moles. [ Method for preparing polymer (A) ]

The polymer (A) may include at least one of polyamidic acid and polyamidoimine. The polymer (A) may further include a polyfluorene-based block copolymer. The methods for preparing the various polymers described above are further described below. ＜ Method for preparing polyamic acid ＞

The method for preparing the polyamidic acid is to first dissolve a first mixture in a solvent, wherein the first mixture includes a tetracarboxylic dianhydride component (a-1) and a diamine component (a-2), and The polycondensation reaction is performed at a temperature of from 100 ° C to 100 ° C. After reacting for 1 hour to 24 hours, the reaction solution is distilled under reduced pressure using an evaporator to obtain polyamic acid. Alternatively, the reaction solution is poured into a large amount of a lean solvent to obtain a precipitate. Then, the precipitate is dried under reduced pressure to obtain polyamic acid.

The solvent used in the polycondensation reaction may be the same as or different from the solvent in the liquid crystal alignment agent described below, and the solvent used in the polycondensation reaction is not particularly limited as long as it can dissolve the reactant and the product. The solvent preferably includes, but is not limited to (1) an aprotic polar solvent, such as: N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide, Aprotic polar solvents such as N, N-dimethylformamide, dimethylmethylene sulfoxide, γ-butyrolactone, tetramethylurea or hexamethyl phosphate triamine; or (2) phenolic solvents, For example: m-cresol, xylenol, phenol or halogenated phenols. The use amount of the solvent used in the polycondensation reaction is preferably 200 parts by weight to 2000 parts by weight, and more preferably 300 parts by weight to 1800 parts by weight based on the total use amount of the first mixture.

It is worth noting that in the polycondensation reaction, an appropriate amount of a lean solvent can be used in combination with the solvent, wherein the lean solvent does not cause the polyamic acid to precipitate. The lean solvent can be used singly or in combination, and it includes but is not limited to (1) alcohols, such as: methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butane Alcohols or alcohols such as triethylene glycol; (2) ketones, such as: ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; (3) esters, such as: Esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, or ethylene glycol ethyl ether acetate; (4) ethers, such as diethyl ether, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, or diethylene glycol dimethyl ether Ethers such as alkyl ethers; (5) halogenated hydrocarbons, such as: dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, or o-dichloro Halogenated hydrocarbons such as benzene; or (6) hydrocarbons, for example: hydrocarbons such as tetrahydrofuran, hexane, heptane, octane, benzene, toluene or xylene, or any combination of the above solvents. Based on the used amount of the diamine component (a-2) being 100 parts by weight, the use amount of the lean solvent is preferably 0 to 60 parts by weight, and more preferably 0 to 50 parts by weight. <Method for preparing polyfluorene imine>

The method for preparing polyimide is obtained by heating the polyamidic acid prepared by the method for preparing polyamidic acid in the presence of a dehydrating agent and a catalyst. During the heating process, the arsenic acid functional group in the polyarsenic acid can be converted into the arsonimine functional group (that is, arsonimation) through a dehydration ring-closing reaction.

The solvent used in the dehydration ring-closing reaction may be the same as the solvent (C) in the liquid crystal alignment agent, so it will not be repeated here. The amount of the solvent used in the dehydration ring-closing reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight, based on 100 parts by weight of the polyamic acid used.

In order to obtain a better degree of polyimidation of the polyimide, the operating temperature of the dehydration ring-closing reaction is preferably 40 ° C to 200 ° C, and more preferably 40 ° C to 150 ° C. If the operating temperature of the dehydration ring-closing reaction is lower than 40 ° C, the imidization reaction is not complete, and the degree of imidization of the polyacid is reduced. However, if the operating temperature of the dehydration ring-closing reaction is higher than 200 ° C, the weight average molecular weight of the obtained polyfluorene imine is low.

The dehydrating agent used in the dehydration ring-closure reaction may be selected from acid anhydride compounds, and specific examples thereof include acid anhydride compounds such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. Based on 1 mole of polyamic acid, the amount of dehydrating agent used is 0.01 to 20 moles. The catalyst used in the dehydration ring-closing reaction may be selected from (1) pyridine compounds, such as pyridine, trimethylpyridine, or dimethylpyridine; and (2) tertiary amine compounds, such as: Tertiary amines such as triethylamine. Based on the amount of dehydrating agent used is 1 mole, the amount of catalyst used can be 0.5 to 10 moles.

The fluorene imidization rate of the polymer (A) may be 30% to 80%, preferably 35% to 85%, and more preferably 35% to 75%. If the fluorenimidization ratio of the polymer (A) is within the above range, the liquid crystal contact angle of the obtained liquid crystal alignment agent is low. <Method for preparing polyfluorene-based block copolymers>

The polyimide-based block copolymer is selected from the group consisting of a polyimide block copolymer, a polyimide block copolymer, a polyimide-polyimide block copolymer, or the above-mentioned polymerization. Any combination of things.

The method for preparing a polyfluorene-based block copolymer is preferably firstly dissolving a starting material in a solvent and carrying out a polycondensation reaction, wherein the starting material includes at least one polyamic acid and / or at least one polyfluorene Imine, and may further include a carboxylic anhydride component and a diamine component.

The carboxylic acid anhydride component and the diamine component in the starting material may be the same as the tetracarboxylic dianhydride component (a-1) and the diamine component (a-2) used in the method for preparing a polyamic acid. In addition, the solvent used in the polycondensation reaction may be the same as the solvent (C) in the liquid crystal alignment agent described below, and details are not described herein again.

The used amount of the solvent used in the polycondensation reaction is preferably 200 to 2000 parts by weight, and more preferably 300 to 1800 parts by weight based on the used amount of the starting material. The operating temperature of the polycondensation reaction is preferably 0 ° C to 200 ° C, and more preferably 0 ° C to 100 ° C.

The starting materials preferably include, but are not limited to, (1) two polyamido acids having different terminal groups and different structures; (2) two polyimines having different terminal groups and different structures; (3) ) Polyamines and polyimines having different terminal groups and structures; (4) Polyamines, carboxylic anhydride components, and diamine components, of which the carboxylic anhydride component and the diamine component are At least one of them is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyfluorinated acid; (5) the polyfluorene imine, the carboxylic acid anhydride component, and the diamine component, wherein At least one of the component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyimide; (6) the polyamidic acid, the polyimide, and the carboxylic acid anhydride component And a diamine component, wherein at least one of the carboxylic acid anhydride component and the diamine component is different from the structure of the carboxylic acid anhydride component and the diamine component used to form the polyamic acid or polyimide; ( 7) Two kinds of polyfluorinated acid, carboxylic anhydride and diamine components with different structures; (8) Two kinds of polyfluorinated imine, carboxylic anhydride and diamine components with different structures; (9) Polyamines and diamines whose terminal groups are acid anhydride groups and have different structures; (10) Polyamines and carboxylic anhydrides whose terminal groups are amine groups and have different structures; (11) A kind of polyfluorene imine and diamine components whose terminal groups are acid anhydride groups and different structures; or (12) two kinds of polyfluorene imine and carboxylic acid anhydride components whose terminal groups are amine groups and different structures.

As long as the efficacy of the present invention is not affected, the polyamidic acid, polyamidoimide, and polyamidoimide block copolymer are preferably terminally modified polymers after molecular weight adjustment. By using a terminal-modified polymer, the coating performance of the liquid crystal alignment agent can be improved. The method for preparing the terminal-modified polymer can be prepared by adding a polyfunctional compound while the polyamic acid is undergoing a polycondensation reaction.

Specific examples of monofunctional compounds include, but are not limited to (1) monobasic anhydrides, such as: maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecyl Monobasic anhydrides such as alkyl succinic anhydride or n-hexadecyl succinic anhydride; (2) monoamine compounds such as: aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecanylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecanylamine, Monoamine compounds such as n-octadecylamine or n-eicosylamine; or (3) monoisocyanate compounds, such as monoisocyanate compounds such as phenyl isocyanate or naphthyl isocyanate.

The weight average molecular weight of the polymer (A) of the present invention is 10,000 to 100,000; preferably 20,000 to 80,000; more preferably 30,000 to 70,000.

The polysiloxane (B) containing a photoreactive group is obtained by reacting a second mixture, and the second mixture may include an epoxy-containing polysiloxane (b-1) and an ethylenically unsaturated compound ( b-2). The photoreactive group-containing polysiloxane (B) includes a structure represented by formula (IIa): Formula (IIa) In Formula (IIa), R ₁ is a methylene group, a linear or branched alkylene group, a phenylene group, or a cyclohexyl group from C ₂ to C ₁₀ , and a part of the hydrogen atom of the R ₁ functional group is Substituted or unsubstituted; R ₂ is a methylene group, or a linear or branched alkylene group of C ₂ to C ₁₀ , and a part of hydrogen atoms of the R ₂ functional group is substituted or unsubstituted; R ₃ is a single bond , Methylene, or C ₂ to C ₁₀ linear or branched alkylene, a part of the hydrogen atom of the R ₃ functional group is substituted or unsubstituted; R ₄ is a hydrogen atom or a methyl group; L is -OCO -, -O- or -S-; a is an integer from 0 to 10; b is an integer from 0 to 1; when b is 0, a is not 0; when a is plural, a plurality of R ₂ and L are each Are the same or different; and * is the bond.

In an embodiment of the present invention, the second mixture further includes a side chain compound (b-3). In the above embodiment, the photoreactive group-containing polysiloxane (B) prepared by the reaction of the second mixture may include a structure represented by the formula (IVa): E ¹ -L ⁰ -L ^1- * (IVa) in the formula (IVa), E ¹ is a C ₁ to C ₃₀ alkyl group, a C ₃ to C ₁₀ cycloalkyl group substituted or unsubstituted by a C ₁ to C ₂₀ alkyl group or an alkoxy group, Or a _C17 to _C51 hydrocarbon group containing a steroid skeleton, part of the hydrogen atoms of the alkyl and alkoxy groups of E ¹ are substituted or unsubstituted; L ⁰ is a single bond, * -O- *, * -COO- * Or * -OCO- *; L ¹ is a single bond, an alkylene group of C ₁ to C ₂₀ , a phenylene group, a biphenylene group, a cyclohexyl group, a dicyclohexyl group or the following formula (IV-1) or A group represented by formula (IV-2): Formula (IV-1) Formula (IV-2) When L ¹ is a single bond, L ⁰ is a single bond; and * is a bond.

When the second mixture includes an epoxy-containing polysiloxane (b-1), an ethylenically unsaturated compound (b-2), and a side chain compound (b-3), the epoxy-containing polysiloxane The oxane (b-1) and the ethylenically unsaturated compound (b-2) may be reacted first, and then the side chain compound (b-3) is added for reaction; or, the epoxy group-containing polysiloxane The alkane (b-1), the ethylenically unsaturated compound (b-2), and the side chain compound (b-3) can be reacted together.

Specific examples and synthesis methods of the epoxy group-containing polysiloxane (b-1), the ethylenically unsaturated compound (b-2), and the side chain compound (b-3) will be described below.

The epoxy group-containing polysiloxane (b-1) contains an epoxy group such as a glycidyl group, a glycidyloxy group, an epoxycyclohexyl group, or a cyclic group. Oxetanyl group.

The epoxy group-containing polysiloxane (b-1) contains an epoxy group-containing group including a group represented by formula (III-1), a group represented by formula (III-2), and a group represented by formula (III-2) III-3) at least one of the groups represented by

Specifically, the group represented by formula (III-1) is shown below. Formula (III-1)

In formula (III-1), B represents an oxygen atom or a single bond; c represents an integer of 1 to 3; d represents an integer of 0 to 6; wherein when d represents 0, B is a single bond.

The group represented by formula (III-2) is shown below. Formula (III-2)

In Formula (III-2), e represents an integer of 0 to 6.

The radical represented by the formula (III-3) is shown below. Formula (III-3)

In formula (III-3), D represents a C ₂ to C ₆ alkylene group; E represents a hydrogen atom or a C ₁ to C ₆ alkyl group.

The epoxy group-containing group preferably includes a group represented by the formula (III-1-1), a group represented by the formula (III-2-1), and a group represented by the formula (III-3-1) At least one of them. Formula (III-1-1) Formula (III-2-1) Formula (III-3-1)

The epoxy group-containing polysiloxane (b-1) of the present invention includes a copolymer obtained by hydrolyzing and partially condensing a third mixture, the third mixture comprising a compound represented by formula (III-4) Silane monomer (b-1-1); Si (R _f ) _p (OR _g ) _4-p Formula (III-4) In formula (III-4), R _f is a hydrogen atom, C ₁ to C ₁₀ Alkyl, C ₂ to C ₁₀ alkenyl, C ₆ to C ₁₅ aryl, epoxy-containing alkyl or epoxy-containing alkoxy, and at least one R _f is epoxy-containing alkane group or an alkoxy group-containing epoxy groups; when p is plural, R _f are each the same or different; R _g is a hydrogen atom, C ₁ to C ₆ alkyl group of, C ₁ to C ₆ acyl or C of An aryl group of ₆ to C ₁₅ ; when 4-p is plural, each of R _g is the same or different; and p is an integer of 1 to 3.

In more detail, when R _f in the formula (III-4) represents an alkyl group of C ₁ to C ₁₀ , specifically, R _f is, for example, methyl, ethyl, n-propyl, isopropyl, n- Butyl, third butyl, n-hexyl or n-decyl. R _f may be an alkyl group having another substituent on the alkyl group. Specifically, R _{f is,} for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-aminopropyl, 3- Thiopropyl or 3-isocyanatopropyl.

When R _f in the formula (III-4) represents an alkenyl group of C ₂ to C ₁₀ , specifically, R _{f is,} for example, a vinyl group. R _f may be an alkenyl group having another substituent on the alkenyl group. Specifically, R _{f is,} for example, 3-propenyloxypropyl or 3-methacryloxypropyl.

When R _f in the formula (III-4) represents an aryl group of C ₆ to C ₁₅ , specifically, R _f is, for example, a phenyl group, a tolyl group, or a naphthyl group. R _f may be an aryl group having another substituent on the aryl group. Specifically, R _f is, for example, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl (1 -(o-hydroxyphenyl) ethyl), 2- (p-hydroxyphenyl) ethyl (2- (o-hydroxyphenyl) ethyl) or 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl ( 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyl).

When R _f in formula (III-4) represents an epoxy-containing alkyl group or an epoxy-containing alkoxy group, a specific example of R _f is the aforementioned epoxy-containing polysiloxane ( b-1) contains epoxy groups, which will not be repeated here.

In addition, when R _{g of the} formula (III-4) represents a C ₁ to C ₆ alkyl group, specifically, R _g is, for example, methyl, ethyl, n-propyl, isopropyl, or n-butyl. When R _g in the formula (III-4) represents a fluorenyl group of C ₁ to C ₆ , specifically, R _{g is,} for example, an ethenyl group. When R _g in the formula (III-4) represents an aryl group of C ₆ to C ₁₅ , specifically, R _{g is,} for example, a phenyl group.

Specific examples of the silane monomer (b-1-1) include 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, and 3- (N-allyl-N-glycidyl) Aminopropyltrimethoxysilane, 3-glycidyletherpropyltrimethoxysilane, 3-glycidyletherpropyltriethoxysilane, 3-glycidyletherpropylmethyldimethoxy Silane, 3-glycidyl ether propyl methyl diethoxy silane, 3-glycidyl ether propyl dimethyl methoxy silane, 3-glycidyl ether propyl dimethyl ethoxy silane, 2-glycidyl ether ethyltrimethoxysilane, 2-glycidyl ether ethyltriethoxysilane, 2-glycidyl ether ethylmethyldimethoxysilane, 2-glycidyl ether ethyl Methyl methyl diethoxysilane, 2-glycidyl ether ethyl dimethyl methoxysilane, 2-glycidyl ether ethyl dimethyl ethoxysilane, 4-glycidyl ether butyl trimethyl Oxysilane, 4-glycidyl ether butyl triethoxy silane, 4-glycidyl ether butyl methyl dimethoxy silane, 4-glycidyl ether butyl methyl diethoxy silane, 4-glycidyl Ether butyl Dimethylmethoxysilane, 4-glycidyl ether butyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) propyltriethoxy Silane, ((3-ethyl-3-glycidyl) methoxy) propyltrimethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propyltriethoxy Silane, ((3-ethyl-3-glycidyloxy) methoxy) propylmethyldimethoxysilane, or ((3-ethyl-3-glycidyl) methoxy) propane Dimethylmethoxysilane, commercially available products such as DMS-E01, DMS-E12, DMS-E21, EMS-32 (manufactured by JNC), or a combination of the aforementioned compounds.

Specific examples of the silane monomer (b-1-1) represented by the formula (III-4) include 3-glycidyl ether propyltrimethoxysilane and 2-glycidyl ether ethyltrimethoxysilane , 4-glycidyl ether butyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy Silane, ((3-ethyl-3-glycidyl) methoxy) propyltrimethoxysilane, ((3-ethyl-3-glycidyl) methoxy) propyltriethyl Oxysilane, DMS-E01, DMS-E12, or a combination of these compounds.

Based on the total amount of monomers in the third mixture being 1 mole, the amount of the silane monomer (b-1-1) used is 0.6 to 1 mole, preferably 0.65 to 1 mole , More preferably 0.7 to 1 mole.

The third mixture for reacting to form the epoxy-containing polysiloxane (b-1) preferably further contains another silane monomer (b-1-2) represented by formula (III-5): Si (R _h ) _q (OR _i ) _4-q Formula (III-5) In Formula (III-5), R _h is a hydrogen atom, a C ₁ to C ₁₀ alkyl group, and a C ₂ to C ₁₀ alkenyl group , An aryl group of C ₆ to C ₁₅ or an alkyl group containing an acid anhydride group; when q is plural, each of R _h is the same or different; R _i is a hydrogen atom, an alkyl group of C ₁ to C ₆ , and C ₁ to C the C ₆ acyl group or an aryl group of ₆ to C _15; and when 4-q is plural, R _i are each the same or different; and p is an integer of 1-3.

When R _h in formula (III-5) represents a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₁₀ alkenyl group, and a C ₆ to C ₁₅ aryl group, specific examples and preferred examples thereof include the aforementioned R _f As shown, it will not be repeated here.

When _Rh in the formula (III-5) represents an alkyl group containing an acid anhydride group, the alkyl group is preferably a C ₁ to C ₁₀ alkyl group. Specifically, the acid-anhydride-containing alkyl group is, for example, ethylsuccinic anhydride represented by formula (III-5-1), propylsuccinic anhydride represented by formula (III-5-2), or formula ( III-5-3). It is worth mentioning that the acid anhydride group is a group formed by dicarboxylic acid by intramolecular dehydration. The dicarboxylic acid is, for example, succinic acid or glutaric acid. Formula (III-5-1) Formula (III-5-2) Formula (III-5-3)

When R _i in formula (III-5) represents a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorenyl group, or a C ₆ to C ₁₅ aryl group, specific examples and preferred examples thereof include the aforementioned R _g As shown, it will not be repeated here.

The other silane monomer (b-1-2) represented by the formula (III-5) may be used alone or in combination, and the other silane monomer (b-1-2) represented by the formula (III-5) contains Compounds of silicon atoms. The compound having one silicon atom includes a silane compound having four hydrolyzable groups, a silane compound having three hydrolyzable groups, a silane compound having two hydrolyzable groups, and a silane having one hydrolyzable group. Compound, or a combination thereof.

Specific examples of the silane compound having four hydrolyzable groups include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane , Tetra-second butoxysilane, or a combination thereof.

Specific examples of the silane compound having three hydrolyzable groups include methyltrimethoxysilane (MTMS for short), methyltriethoxysilane, methyltriisopropoxysilane, methyltriisosilane Methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyl Tri-n-butoxysilane (n-propyltrimethoxysilane), n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane (n -butyltrimethoxysilane), n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane decyltrimethoxysilane), vinyltrimethoxysilane, vinyltriethoxysilane, 3-propenyloxypropyl 3-acryoyloxypropyltrimethoxysilane, 3-methylacryloyloxypropyltrimethoxysilane (MPTMS), 3-methylacryloyloxypropyltrimethoxysilane (3-methylacryloyloxypropyltrimethoxysilane) methylacryloyloxypropyltriethoxysilane), phenyltrimethoxysilane (PTMS), phenyltriethoxysilane (PTES), p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxybenzene (1- (p-hydroxyphenyl) ethyltrimethoxysilane), 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5 -(P-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane (4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane), trifluoromethyltrimethoxysilane, trifluoromethyltrimethoxysilane Trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane methoxysilane), 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (triphenoxysilyl) propylsuccinic anhydride ( 3-triphenoxysilyl propyl succinic anhydride), a commercially available product manufactured by Shin-Etsu Chemical Co., Ltd .: 3- (trimethoxysilyl propyl succinic anhydride) (trade name X-12-967), Commercial products manufactured by WACKER: 3- (triethoxysilyl) propyl succinic anhydride (trade name: GF-20), 3- (trimethoxysilyl) (3- (trimethoxysilyl) propyl glutaric anhydride (TMSG), 3- (triethoxysilyl) propyl glutaric anhydride), 3- (trimethoxysilyl) 3- (triphenoxysilyl) propyl glutaric anhydride) or a combination thereof.

Specific examples of the silane compound having two hydrolyzable groups include methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane , Di-n-butyldimethoxysilane, or a combination thereof.

Specific examples of the silane compound having one hydrolyzable group include methoxydimethylsilane, methoxytrimethylsilane, methoxymethyldiphenylsilane, tri-n-butylethoxysilane, or A combination of the above compounds.

The other silane monomer (b-1-2) of the structure represented by the formula (III-5) is preferably tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, thiomethyltrimethoxysilane, thiomethyltrimethoxysilane Ethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, or a combination of the above.

Based on the total amount of the monomers in the third mixture being 1 mole, the usage amount of the silane monomer (b-1-2) is 0 to 0.7 moles, preferably 0 to 0.6 moles , More preferably 0 to 0.5 mole.

The third mixture may further include a commercially available silane monomer, and specific examples thereof include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, and X-21-5843. , X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X -22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40 -2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250 , X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (made by Shin-Etsu Chemical); glass resin (GLASS RESIN, manufactured by Showa Denko); SH804, SH805, SH806A, SH840, SR2400 , SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (made by Toray Dow Corning); FZ3711, FZ3722 (made by NUC); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS -S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42 , DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (made by JNC); MS51, MS56 (made by Mitsubishi Chemical); and GR100, GR650, GR908, GR950 (Manufactured by Showa Denko) and other condensates. [ Preparation method of epoxy group-containing polysiloxane (b-1) ]

The polycondensation reaction of the epoxy group-containing polysiloxane compound can be formed by a general method. For example, an organic solvent, water, or a catalyst is optionally further added to the silane compound or a mixture thereof, and then an oil bath is used. The heating is performed at 50 ° C to 150 ° C, and the heating time is preferably 0.5 hours to 120 hours. During heating, the mixed solution may be stirred or placed under reflux conditions.

The organic solvent is not particularly limited, and may be the same as or different from the solvent (C) contained in the liquid crystal alignment agent of the present invention.

Specific examples of the organic solvent include hydrocarbon compounds such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, cyclohexanone, and 2-butanone , 2-hexanone and other ketone solvents; ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and other esters Solvents; Ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane (dioxane); 1-hexanol, 4-methyl 2-pentanol, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, etc. Alcohol solvents; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, trimethylamine hexamethyl phosphate, 1,3-dimethyl Amidamine-based solvents such as 2-imidazolidinone, or a combination of the above organic solvents.

These organic solvents may be used alone or in combination.

The use amount of the organic solvent is preferably 10 to 1200 parts by weight, and more preferably 30 to 1000 parts by weight, based on 100 parts by weight of all the silane compounds.

The hydrolyzable group is 1 mol based on all the silane compounds, and the amount of water used is preferably 0.5 mol to 2 mol.

The catalyst is not particularly limited. Preferably, the catalyst is selected from the group consisting of an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, or a combination thereof.

Specific examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid, polybasic acid anhydride, or a combination thereof.

Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, or a combination thereof.

Specific examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, triethylamine Tertiary organic amines such as n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and other tertiary organic amines such as tetramethylammonium hydroxide Amines, etc., or a combination of the above.

The amount of catalyst used varies depending on the reaction conditions such as type, temperature, etc., and can be appropriately set. For example, based on 1 mol of all silane compounds, the addition amount of the catalyst is 0.01 mol to 5 mol, preferably 0.03 to 3 mol, more preferably 0.05 to 1 mol.

From the viewpoint of stability, after the completion of the polycondensation reaction, the organic solvent layer fractionated from the reaction liquid is preferably washed with water. When performing this washing | cleaning, it is preferable to wash | clean with water containing a small amount of salt, for example, about 0.2 weight% of ammonium nitrate aqueous solution etc. The washing can be performed until the water layer after the washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the organic solvent is removed to obtain an epoxy group-containing Polysiloxane (b-1).

When the polysiloxane (B) containing a photoreactive group is not used or the polysiloxane (b-1) containing an epoxy group is not used, The volume resistance of the prepared liquid crystal alignment agent is low, and the liquid crystal contact angle is too high.

The ethylenically unsaturated compound (b-2) of the present invention may include a structure of the following formula (IIb). Formula (IIb) In formula (IIb), R ₁ is a methylene group, a linear or branched alkylene group, a phenylene group, or a cyclohexyl group from C ₂ to C ₁₀ , and a part of the hydrogen atom of the functional group of R ₁ is Substituted or unsubstituted; R ₂ is a methylene group, or a linear or branched alkylene group of C ₂ to C ₁₀ , and a part of hydrogen atoms of the R ₂ functional group is substituted or unsubstituted; R ₃ is a single bond , Methylene, or C ₂ to C ₁₀ linear or branched alkylene, a part of the hydrogen atom of the R ₃ functional group is substituted or unsubstituted; R ₄ is a hydrogen atom or a methyl group; L is -OCO -, -O- or -S-; a is an integer from 0 to 10; b is an integer from 0 to 1; when b is 0, a is not 0; when a is plural, a plurality of R ₂ and L are each For the same or different.

Specifically, examples of the compound of the above formula (IIb) may include acrylic acid, methacrylic acid, 2-propenyloxyethyl-2-hydroxyethyl phthalic acid, 4- (2-methyl-acrylic acid) Benzoic acid, 2-propenyloxyethylhexylhydrophthalic acid, 2-propenyloxyethylhexylhydrophthalic acid, 2-propenyloxyethylhexylhydrophthalic acid, methacrylic acid Dicarboxylic acid, phthalic acid monohydroxyethyl acrylate. One or more of the above examples can be used. Examples of commercially available products of the above compounds are acrylic acid and methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), Lightester HO-MS, Lightester HO-HH, HOA-MPL, HOA-MS, HOA-HH (Kyoeisha) Chemical Co., Ltd.), M-5400 (East Asia Synthesis Co., Ltd.).

Examples of the compound of the above formula (IIb) may also include compounds of the following formula (IIb-1) to (IIb-16). Formula (IIb-1) Formula (IIb-2) Formula (IIb-3) Formula (IIb-4) Formula (IIb-5) Formula (IIb-6) Formula (IIb-7) Formula (IIb-8) Formula (IIb-9) Formula (IIb-10) Formula (IIb-11) Formula (IIb-12) Formula (IIb-13) Formula (IIb-14) Formula (IIb-15) Formula (IIb-16)

In the formulae (IIb-10) to (IIb-16), R ⁴ represents a hydrogen atom or a methyl group, t1 is an integer of 1 to 10, and t2 + t3 is an integer of 1 to 10.

If the ethylenically unsaturated compound (b-2) is not used, the bulk resistance of the obtained liquid crystal alignment agent is low, and the liquid crystal contact angle is high.

Based on the total amount of monomers in the third mixture being 1 mol, the amount of the ethylenically unsaturated compound (b-2) used is 0.1 mol to 0.5 mol, preferably 0.15 mol to 0.5 mol. More preferably, it is 0.15 mol to 0.45 mol. If the use amount of the ethylenically unsaturated compound (b-2) is within the above range, the liquid crystal contact angle of the obtained liquid crystal alignment agent is low.

The side chain compound (b-3) of the present invention includes a structure represented by formula (IVb): E ¹ -L ⁰ -L ¹ -Z Formula (IVb) In formula (IVb), E ¹ is C ₁ to C ₃₀ An alkyl group, a C ₃ to C ₁₀ cycloalkyl group substituted or unsubstituted with a C ₁ to C ₂₀ alkyl group or an alkoxy group, or a C ₁₇ to C ₅₁ hydrocarbon group containing a steroid skeleton, the E ¹ to Part of the hydrogen atom of the alkyl group and alkoxy group is substituted or unsubstituted; L ⁰ is a single bond, * -O- *, * -COO- * or * -OCO- *; L ¹ is a single bond, C ₁ to C ₂₀ alkylene, phenylene, phenylene, cyclohexyl, dicyclohexyl or a group represented by the following formula (IV-1) or (IV-2): Formula (IV-1) Formula (IV-2) When L ¹ is a single bond, L ⁰ is a single bond; * is a bond; and Z is a monovalent organic group that reacts with an epoxy group to form a bonding group.

The linear or branched C ₁ to C ₃₀ alkyl group described by E ^{1 in} the above formula (IVb) may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl , N-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethyl Butyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-heptyl, 5 -Methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl, 2 , 4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1,3-dimethylpentyl, 2 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3,3-trimethyl Butyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2- Methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl , N-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n- Eighteen bases, n-nineteen bases, etc.

The C ₃ to C ₁₀ cycloalkyl group described by E ^{1 in} the above formula (IVb) may be, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl Wait. These cycloalkyl groups described above may be substituted with or without C ₁ to C ₂₀ alkoxy groups. For specific examples of the C ₁ to C ₂₀ alkoxy group, reference may be made to the specific examples given in the description of the C ₁ to C ₃₀ alkyl group described above. For specific examples of the C ₁ to C ₂₀ alkoxy group, reference may be made to the specific examples of the alkyl group mentioned in the description of the C ₁ to C ₃₀ alkyl group, and the group obtained by bonding with an oxygen atom. The alkyl group and the alkoxy group described in E ¹ may have at least a part of hydrogen atoms substituted, and examples of the group for replacing a hydrogen atom include a nitrile group, a fluorine atom, and a trifluoromethyl group.

The hydrocarbon group of C ₁₇ to C ₅₁ containing a steroid skeleton as described in E ^{1 in} the above formula (IVb) may be, for example, a group represented by the following formula (S-1) to (S-3), wherein * 5 represents a bond between the above group and L ⁰ of formula (IVb). Formula (S-1) Formula (S-2) Formula (S-3)

Preferably, E ¹ may be selected from C ₁ to C ₂₀ alkyl groups, C ₁ to C ₂₀ fluoroalkyl groups, groups of the above formula (S-1), and groups of the above formula (S-3) A group of people. Z is preferably a carboxyl group. The alkylene group of C ₁ to C ₂₀ described in L ^{1 in} the above formula (IVb) may be, for example, removing one hydrogen atom from each of the groups mentioned in the aforementioned alkyl group of C ₁ to C ₃₀ And the resulting group.

The compound represented by the above formula (IVb) is preferably a compound represented by the following formulae (IVb-1) to (IVb-8). Formula (IVb-1) Formula (IVb-2) Formula (IVb-3) Formula (IVb-4) Formula (IVb-5) Formula (IVb-6) Formula (IVb-7) Formula (IVb-8)

In formulae (IVb-1) to (IVb-8), u is an integer from 1 to 5, v is an integer from 1 to 18, w is an integer from 1 to 20, k is an integer from 1 to 5, and p is 0 or 1. q is an integer from 1 to 18, r is an integer from 0 to 18, and j is an integer from 1 to 18. s and t are each independently an integer of 0 to 2. However, s and t are not 0 at the same time.

Preferably, v in the above formula (IVb-1) is an integer of 1 to 18, but an integer of 1 to 12 is more preferable. W of the above formula (IVb-2) is preferably an integer of 5 to 20, but more preferably 10 to 18. W of the above formula (IVb-3) is preferably an integer of 1 to 17, but an integer of 3 to 12 is more preferable. W of the above formula (IVb-4) is preferably an integer of 1 to 15, but an integer of 1 to 8 is more preferable. W of the above formula (IVb-8) is preferably an integer of 1 to 15, but an integer of 1 to 8 is more preferable. In the above formulae (IVb-5) and (IVb-6), r is preferably an integer of 0 to 15, but an integer of 0 to 8 is more preferable. In the above formula (IVb-6), q may be an integer of 1 to 12, but an integer of 1 to 5 is more preferable. J in the above formula (IVb-8) is preferably an integer of 1 to 15, but an integer of 1 to 8 is more preferable.

Among the above compounds, at least one of the above formulae (IVb-2) to (IVb-5), (IVb-7), and (IVb-8) is preferable. Specifically, the following formulae (IVb-1 ') to (IVb-8') are preferable. Formula (IVb-1 ') Formula (IVb-2 ') Formula (IVb-3 ') Formula (IVb-4 ') Formula (IVb-5 ') Formula (IVb-6 ') (IVb-7 ') Formula (IVb-8 ')

Based on the total amount of monomers in the third mixture being 1 mole, the amount of the side chain compound (b-3) used is 0.05 to 0.3 mole, preferably 0.08 to 0.3 mole, 0.08 mole to 0.27 mole is more preferred. If the amount of the side chain compound (b-3) used is within the above range, the liquid crystal contact angle of the obtained liquid crystal alignment agent is low.

Based on the use amount of the polymer (A) is 100 parts by weight, the use amount of the photoreactive group-containing polysiloxane (B) is 3 to 60 parts by weight, preferably 5 to 60 parts by weight Of course, it is more preferably 5 parts by weight to 55 parts by weight. [ Preparation method of photoreactive group-containing polysiloxane (B) ]

The photoreactive group-containing polysiloxane (B) used in the present invention can be obtained by allowing the above-mentioned epoxy group-containing polysiloxane (b-1) to be mixed with an ethylenically unsaturated compound (b-2) and a side chain. Compound (b-3) is synthesized by reaction in the presence of a catalyst.

As the catalyst, an organic salt or a known compound such as a hardening accelerator that can accelerate the reaction between the epoxy compound and the acid anhydride can be used.

Examples of the organic salt include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; triethylamine, tri-n-propylamine, and tri-n-butylamine. Tertiary organic amines such as amines, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, and tertiary organic amines such as tetramethylammonium hydroxide. Among these organic amines, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine, or tetramethylammonium hydroxide, etc. are preferred. Grade organic amine.

Specific examples of the hardening accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptylimidazole, 2-n-alkylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyano (Ethyl) -2-5-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2 -Phenyl-4,5-bis [(2'-cyanoethoxy) methyl] imidazole, l- (2-cyanoethyl-2-n-undecylimidazolium trimellitate , 1- (2-cyanoethyl) -2-phenylimidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitic acid Salt, 2, 4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-S-triazine, 2,4-diamino-6- (2'-n-deca Monoalkylimidazole) ethyl-S-triazine, 2,4-diamino-6- [2'- -4'-methylimidazolyl- (1 ')] ethyl-S-triazine, trimeric isocyanate adduct of 2-methylimidazole, triphenyl isocyanate addition of 2-phenylimidazole Imidazole compounds such as trimeric isocyanate adducts of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-S-triazine; diphenyl Organophosphorus compounds such as phosphine, triphenylphosphine, and triphenyl phosphite; benzyl triphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, Ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium acetate- O, O-diethylphosphodithiosulfate (tetra-n-butyl phosphonium-O, O-diethyl phosphorodithionate), tetra-n-butylphosphonium benzotriazole, tetra-n-butylphosphonium benzotriazolate, tetra Tertiary phosphonium salts such as n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, etc .; 1,8-diazabicyclo [5.4.0] Diazabicyclic olefins such as monoene-7 or its organic acid salts; zinc octoate, tin octoate, acetamidine Organometallic compounds such as aluminum acetylacetone complex; tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride, etc. Grade ammonium salts; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and tin tetrachloride; dicyandiamide or the addition of amines and epoxy resins Latent hardening accelerators with high melting point dispersion, such as amine addition molding accelerators such as products; microcapsules that cover the surface of the hardening accelerators such as imidazole compounds, organic phosphorus compounds, or quaternary phosphonium salts with polymers Latent Hardening Accelerator; Amine Salt Latent Hardening Accelerator; Lactoacid, Bronsted Acid Salt, and other high-temperature dissociation-type thermal cationic polymerization latent hardening accelerator, etc. Wait.

Specific examples of the hardening accelerator are preferably quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

Specific examples of the hardening accelerator are preferably quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

The reaction temperature is preferably 0 ° C to 200 ° C, and more preferably 50 ° C to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, and more preferably from 0.5 to 20 hours.

The synthesis reaction of the photoreactive group-containing polysiloxane (B) can be performed in the presence of an organic solvent, if necessary. The organic solvent is not particularly limited, and may be the same as the organic solvent used in the preparation of the epoxy-containing polysiloxane (b-1) and the solvent (C) contained in the liquid crystal alignment agent of the present invention. Or not the same. Specific examples of the organic solvent are preferably 2-butanone, 2-hexanone, methyl isobutyl ketone, n-butyl acetate, or a combination thereof.

The weight-average molecular weight of the photoreactive group-containing polysiloxane (B) of the present invention is 2,000 to 20,000; preferably 3,000 to 18,000; more preferably 5,000 to 15,000.

The solvent used in the liquid crystal alignment agent of the present invention is not particularly limited, as long as it is a soluble polymer (A), a photoreactive group-containing polysiloxane (B), and any other component and does not react therewith. That is, it is preferably the same as the solvent used in the synthesis of the polyamic acid, and at the same time, the lean solvent used in the synthesis of the polyamino acid can also be used in combination.

Specific examples of the solvent (C) include, but are not limited to, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, 4-hydroxy-4-methyl-2-pentanone, and ethylene glycol Monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, Ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Or N, N-dimethylformamide or N, N-dimethyl acetamide. The solvent (C) may be used alone or in combination.

Based on 100 parts by weight of the polymer (A), 800 to 3000 parts by weight of the solvent (C) is used, preferably 1,000 to 3000 parts by weight, and more preferably 1000 to 2500 parts by weight.

To the extent that the efficacy of the present invention is not affected, the liquid crystal alignment agent may optionally add an additive (D), wherein the additive (D) includes a compound having at least two epoxy groups, a silane compound having a functional group, Or a combination.

Compounds having at least two epoxy groups include, but are not limited to, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-di Bromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl- M-xylylenediamine, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4 '-Diaminodiphenylmethane, 3- (N, N-diepoxypropyl) aminopropyltrimethoxysilane, or a combination of the above compounds.

The compound having at least two epoxy groups may be used alone or in combination.

The use amount of the compound having at least two epoxy groups may be 0 to 40 parts by weight, and preferably 0.1 to 30 parts by weight based on the use amount of the polymer (A).

Specific examples of the silane compound having a functional group include, but are not limited to, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2 -Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Dimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxy Silyl, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylene Triamine, 10-trimethoxysilyl-1,4,7-triazine, 10-triethoxysilyl-1,4,7-triazine, 9-trimethoxysilyl- 3,6-Diazinyl acetate, 9-triethoxysilyl-3,6-diazinyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis ( Ethylene) -3-aminopropyl trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxysilane Silane, or combinations of the above compounds.

The silane compound having a functional group may be used alone or in combination.

Based on the use amount of the polymer (A) being 100 parts by weight, the use amount of the silane compound having a functional group may be 0 to 10 parts by weight, and preferably 0.5 to 10 parts by weight.

The use amount of the additive (D) is preferably 0.5 to 50 parts by weight, and more preferably 1 to 45 parts by weight based on the total use amount of the polymer (A). [ Manufacturing method of liquid crystal alignment agent ]

The present invention also provides a method for manufacturing a liquid crystal alignment agent, which comprises a mixed polymer (A), a polysiloxane containing a photoreactive group (B), and a solvent (C).

The method for preparing the liquid crystal alignment agent of the present invention is not particularly limited, and it can be prepared by a general mixing method. For example, the polymer (A) prepared in the above manner and the polysiloxane (B) containing a photoreactive group are first mixed uniformly to form a mixture. Next, the solvent (C) is added under the condition of a temperature of 0 ° C. to 200 ° C., and the additive (D) is optionally added. Finally, the stirring is continued with a stirring device until dissolved. In addition, it is preferable to add the solvent (C) at a temperature of 20 ° C to 60 ° C.

At 25 ° C, the viscosity of the liquid crystal alignment agent of the present invention is usually 15 cps to 35 cps, preferably 17 cps to 33 cps, and more preferably 20 cps to 30 cps. [ Manufacturing method of liquid crystal alignment film and liquid crystal display element ]

The present invention further provides a liquid crystal alignment film, which is formed by the aforementioned liquid crystal alignment agent.

The invention further provides a method for manufacturing a liquid crystal alignment film, which comprises forming the liquid crystal alignment film from a liquid crystal alignment agent, wherein the liquid crystal alignment agent is formed by the aforementioned method for manufacturing a liquid crystal alignment agent.

The present invention also provides a liquid crystal display device including the aforementioned liquid crystal alignment film.

The present invention also provides a method for manufacturing a liquid crystal display element. The liquid crystal display element includes a liquid crystal alignment film. The manufacturing method includes forming the liquid crystal alignment film from a liquid crystal alignment agent. The liquid crystal alignment agent is made of the aforementioned liquid crystal alignment agent. Formed by manufacturing methods.

The liquid crystal alignment film of the present invention is formed by using the liquid crystal alignment agent prepared as described above. The liquid crystal display element of the present invention includes a liquid crystal alignment film formed of the liquid crystal alignment agent. The operation mode of the liquid crystal display element is not particularly limited, and it may be a vertical alignment type.

The liquid crystal alignment film and the method for manufacturing a liquid crystal display element of the present invention may include: coating the liquid crystal alignment agent of the present invention on a pair of conductive films of a substrate having a conductive film, and then heating the substrate to form a coating film. The first step; the second step of arranging the pair of substrates with the coating film formed thereon to construct a liquid crystal cell; and arranging the pair of substrates with a conductive film with light when the voltage is applied to the liquid crystal cell The third step. [First Step: Formation of Coating Film]

In this step, two substrates provided with a patterned transparent conductive film are used as a pair, and the liquid crystal alignment agent of the present invention is coated on the surface of the substrate on which the transparent conductive film is formed, preferably a lithography The liquid crystal alignment agent is applied by a printing method, a spin coating printing method, a roll coating method, or an inkjet method. The substrate referred to here may be, for example, glass such as float glass, soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, poly (alicyclic olefin) And other plastic transparent substrates. The transparent conductive film provided on the surface of the substrate can be a NESA film (registered trademark of American PPG Corporation) formed of tin oxide (SnO ₂ ), or an indium oxide and tin oxide (In ₂ O ₃ -SnO ₂ ) ITO film. The patterned transparent conductive film can be formed by, for example, first forming an unpatterned transparent conductive film, then photo-etching a pattern forming method, and using a mask having a predetermined pattern when the transparent conductive film is formed. Reached. When applying the liquid crystal alignment agent, in order to provide good adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate on which the coating film is formed may be previously coated with a functional silane compound and a functional titanium compound. Wait before processing.

After the liquid crystal alignment agent is applied, in order to prevent the applied liquid crystal alignment agent from dripping, it is preferable to perform prebake. The pre-baking temperature may be 30 ° C to 200 ° C, preferably 40 ° C to 150 ° C, and more preferably 40 ° C to 100 ° C. The pre-baking time may be from 0.25 to 10 minutes, preferably from 0.5 to 5 minutes. After that, the solvent is completely removed, and the substrate is subjected to a step of sintering (post-baking) in order to form the necessary polymer and the structure of the amino acid to be thermally imidized. The post-baking temperature may be 80 ° C to 300 ° C, preferably 120 ° C to 250 ° C. The post-baking time may be 5 minutes to 200 minutes, preferably 10 minutes to 100 minutes. Therefore, the thickness of the formed film can be 0.001 μm to 1 μm, and preferably 0.005 μm to 0.5 μm.

The heating step after the liquid crystal alignment agent is applied can remove the organic solvent, thereby forming a coating film of the liquid crystal alignment film. At this time, the polymer contained in the liquid crystal alignment agent of the present invention includes a polyfluorene acid or a fluorene imine polymer having a fluorene imine structure and a fluorin acid structure. Thereafter, the formed coating film is further heated, and the polymer undergoes a dehydration ring-closing reaction to form a fluorinated coating film. The coating film formed by the above method can be directly used as a liquid crystal alignment film, but a predetermined rubbing treatment can also be performed. [Second step: construction of liquid crystal cells]

In this step, two substrates on which the above-mentioned liquid crystal alignment film is formed are provided, and a liquid crystal layer containing a liquid crystal compound and a photopolymerizable compound is disposed between the two substrates disposed oppositely to form a liquid crystal cell. Examples of the method for manufacturing the liquid crystal cell include the following two methods.

The first method is a conventional method (vacuum injection method). First, two substrates are arranged opposite to each other so that a gap (cell gap; Cell Gap) is formed between the oppositely arranged liquid crystal alignment films. The two substrates are bonded together with an adhesive, and a liquid crystal compound and a photopolymerizable compound are injected and filled in a cell gap defined by the substrate surface and the adhesive, and then the injection holes are sealed to obtain a liquid crystal. Cell.

The second method is called One Drop Filling (ODF). For example, a UV-curable adhesive is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed. Next, after a mixture of a liquid crystal compound and a photopolymerizable compound is dropped at a predetermined position of the liquid crystal alignment film, the liquid crystal alignment film and the liquid crystal alignment film of the other substrate are disposed opposite to each other, and the two substrates are bonded together so that the liquid crystal is on the substrate. Diffuses over the entire surface, and then irradiates the entire substrate with ultraviolet light to harden the adhesive to produce liquid crystal cells. Regardless of which method is used, after the liquid crystal cell is formed, the substrate is heated to a temperature at which the liquid crystal compound used is converted to an isotropic temperature, and then slowly cooled to room temperature to remove the flow alignment during liquid crystal filling.

As the above-mentioned adhesive, an epoxy resin as a hardener and a spacer can be used, which contains alumina balls. The liquid crystal compound is preferably a nematic liquid crystal having negative dielectric anisotropy. For example, dicyanophenyl liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azo oxide liquid crystal, and biphenyl liquid crystal can be used. , Phenylcyclohexyl liquid crystal, terphenyl liquid crystal and the like. In addition, in order to make the response speed of the liquid crystal display device of the PSA mode faster, it is preferable to use an alkenyl liquid crystal in combination, which is a monofunctional liquid crystal compound having one alkenyl or fluoroalkenyl group. The alkenyl liquid crystal may be a conventional alkenyl liquid crystal, for example, a compound represented by the following formula (L1-1) to formula (L1-9).

As the photopolymerizable compound, a compound having a functional group capable of performing a radical polymerization reaction, such as an acryl group, a methacryl group, or a vinyl group, can be used. Among these, from the viewpoint of reactivity, a compound having a functional group of at least two of an acrylamide group and a methacryl group is preferably used. In addition, from the viewpoint of maintaining the alignment stability of the liquid crystal molecules, the photopolymerizable compound is a liquid crystal skeleton, and a compound having at least two of a cyclohexane ring and a benzene ring is preferably used. As the photopolymerizable compound, a conventional photopolymerizable compound can be used. The photopolymerizable compound is preferably used in an amount of 0.1% to 0.5% by weight based on the entire weight of the liquid crystal compound. The thickness of the liquid crystal layer is preferably 1 μm to 5 μm. [Third step: exposure step]

After the liquid crystal cell is constructed, a voltage is applied between the conductive films of the pair of substrates, and at the same time, light is irradiated. The voltage applied here can be, for example, 5V to 50V DC or AC. In addition, the irradiated light may be, for example, ultraviolet light and visible light including light having a wavelength of 150 nm to 800 nm, but ultraviolet light including light having a wavelength of 300 nm to 400 nm is more preferable. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, and the like can be used. In addition, a light source can be used in combination with a filter, a diffraction grating, and the like to obtain the above-mentioned ultraviolet light in the preferred wavelength range.

The irradiation amount of light may be 1,000 J / m ² or more and less than 100,000 J / m ² , and preferably 1000 J / m ² to 50,000 J / m ² . For example, it is known that when manufacturing a liquid crystal display element in the PSA mode, a light irradiation amount of 100,000 J / m ² is required. However, the liquid crystal display element of the present invention can use an irradiation light amount of less than 100,000 J / m ² or even less than 50,000 J / m ² To obtain a liquid crystal display element having a predetermined pretilt angle characteristic, and reduce the manufacturing cost of the liquid crystal display element. Furthermore, it is possible to suppress deterioration of electrical properties and deterioration of reactivity of liquid crystal molecules due to strong light irradiation.

Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell, so that the liquid crystal display element of the present invention can be manufactured. The above polarizing plate can be exemplified by a polarizing film of polyvinyl alcohol extending alignment and absorbing iodine liquid, called "H film", and a polarizing film formed by sandwiching the above polarizing film with a cellulose acetate protective film. board.

The liquid crystal display element of the present invention can be applied to various devices, such as: watches, portable game consoles, word processors, notebook computers, navigation systems, video cameras, PDAs, digital cameras, mobile phones, smart phones, and various screens. , LCD TV, electronic signage and other display devices.

The following examples are used to explain the present invention in detail, but it is not meant to limit the present invention to the contents disclosed in these examples. [ Preparation of Polymer (A) ] <Synthesis Example A-1-1>

A 500 ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, in a four-necked conical flask, add 0.005 moles of a-2-1-1 shown in Table 1, 0.04 moles of p-diaminebenzene (abbreviated as a-2-2-1), and 0.005 moles. A-2-2-5 and 80 g of N-methyl-2-pyrrolidone (NMP) shown in Table 1 of the ear were stirred at room temperature until dissolved. Next, 0.05 mol of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (abbreviated as a-1-2) and 20 g of NMP were added and reacted at room temperature for 2 hours. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-1-1). <Synthesis example A-1-2 and comparative synthesis examples A-3-1 to A-3-2>

Synthesis Example A-1-2 and Comparative Synthesis Examples A-3-1 to A-3-2 The polymer was prepared by the same procedure as Synthesis Example A-1-1, except that the tetracarboxylic acid was changed The types and amounts of dianhydride compounds or diamine compounds are shown in Tables 1 and 2. <Synthesis example A-2-1>

A 500 ml four-necked conical flask was provided with a nitrogen inlet, a stirrer, a condenser tube, and a thermometer, and nitrogen was introduced. Then, in a four-necked conical flask, 0.0015 moles of a-2-1-1 shown in Table 1, 0.0435 moles of p-diaminebenzene (abbreviated as a-2-2-1), and 0.005 moles were added. Ear a-2-2-4 and 80 g of NMP as shown in Table 1, and stir at room temperature until dissolved. Next, 0.05 mol of 2,3,5-tricarboxycyclopentylacetic dianhydride (abbreviated as a-1-1) and 20 g of NMP were added. After reacting at room temperature for 6 hours, 97 g of NMP, 2.55 g of acetic anhydride, and 19.75 g of pyridine were added, the temperature was raised to 60 ° C., and stirring was continued for 2 hours to carry out the imidization reaction. After the reaction is completed, the reaction solution is poured into 1500 ml of water to precipitate a polymer. Then, the obtained polymer was filtered, and repeatedly washed with methanol and filtered three times, put into a vacuum oven, and dried at a temperature of 60 ° C. to obtain a polymer (A-2-1). <Synthesis Examples A-2-2 to A-2-12 and Comparative Synthesis Examples A-3-2 to A-3-4>

Synthesis Examples A-2-2 to A-2-12 and Comparative Synthesis Examples A-3-2 to A-3-4. The polymer was prepared in the same procedure as in Synthesis Example A-2-1, except for the differences. The reason is: change the type of tetracarboxylic dianhydride compound or diamine compound and the amount used, as shown in Table 1 and Table 2; and change the type and amount of catalyst used in the dehydrating agent and dehydration ring-closing reaction. Table 1: Table 2: In Tables 1 and 2: [ Preparation of polysiloxane containing photoreactive group (B)] <Synthesis Example B-1>

A 500 ml three-necked flask was equipped with a stirrer, a condenser, and a thermometer. Then, in a three-necked flask, 1.00 mol of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter referred to as ECETS) and 600 g of propylene glycol monomethyl ether (hereinafter referred to as PGME), and triethylamine (hereinafter referred to as TEA) aqueous solution (20 g TEA / 200 g H ₂ O) was added within 30 minutes while stirring at room temperature. Next, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 30 minutes, and then the oil bath was heated to 90 ° C. within 30 minutes. When the internal temperature of the solution reached 75 ° C., the mixture was continuously heated and stirred for 6 hours . After the reaction is completed, the organic layer is taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution to obtain a solution of an epoxy-containing polysiloxane compound.

Next, 0.50 mole of the ethylenically unsaturated compound b-2-1 and 0.2 g of a hardening accelerator UCAT 18X (manufactured by SAN-APRO) were added to a solution of an epoxy-containing polysiloxane compound. Then, the three-necked flask was immersed in an oil bath at 30 ° C. and stirred for 10 minutes, and then the oil bath was heated to 115 ° C. within 30 minutes. When the internal temperature of the solution reached 100 ° C., heating and stirring were continued for 24 hours. After the reaction is completed, the organic layer is taken out, washed with water, dried with magnesium sulfate, and the solvent is removed to obtain a polysiloxane (B-1) containing a photoreactive group. <Synthesis example B-2 to synthesis example B-10 and comparative synthesis example B'-1 to comparative synthesis example B'-3>

Synthesis Example B-2 to Synthesis Example B-10 and Comparative Synthesis Example B'-1 to Comparative Synthesis Example B'-3 In the same procedure as in Synthesis Example B-1, the photoreactive group-containing polysiloxane was prepared. And the difference lies in that: the type of the reactant of the polysiloxane (B) containing a photoreactive group and its use amount, the type of the catalyst and the solvent and their use amount, the reaction temperature and the polycondensation time (See Table 3-1 and Table 3-2). Table 3-1: Table 3-2: In Table 3-1 and Table 3-2: [ Preparation of liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element ] <Example 1>

Weigh 100 parts by weight of polymer (A-2-1), 3 parts by weight of photoreactive group-containing polysiloxane (B-1), and 1200 parts by weight of N-methyl-2-pyrrolidone (referred to as C-1) and 300 parts by weight of ethylene glycol n-butyl ether (abbreviated as C-2), and continued stirring with a stirring device at room temperature until dissolved, to form the liquid crystal alignment agent of Example 1.

The liquid crystal alignment agent was evaluated for each detection item, and the results are shown in Table 4. <Examples 2 to 16 and Comparative Examples 1 to 8>

Examples 2 to 16 and Comparative Examples 1 to 8 were used to prepare the liquid crystal alignment agent in the same steps as in Example 1. The difference was that the types and amounts of polymer composition, solvent, and additives were changed, as shown in the table. 4 and 5. These liquid crystal alignment agents were evaluated for each test item, and the results are shown in Tables 4 and 5. Table 4: table 5: In Tables 4 and 5: [ Evaluation method ] <body impedance>

The prepared liquid crystal alignment agent was dropped into an aluminum dish with a diameter of 32 mm and baked on a hot plate to obtain a film having a film thickness of about 0.01 mm. Continue to measure the resistance value of the film with a resistance meter (AGILENT 4339b High resistance meter), clamp the positive and negative electrodes of the instrument to both ends of the aluminum plate containing the film, and record the measured resistance value at a voltage of 50 volts. Its evaluation standard As follows: ○: Resistance value ≧ 1.0 × 10 ¹² ╳: Resistance value ＜ 1.0 × 10 ¹² ＜ Contact angle of liquid crystal ＞

The above-mentioned liquid crystal alignment agent was applied on a transparent electrode surface of a glass substrate provided with an electrode structure on an ITO surface by a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), and heated at 80 ° C. for 1 minute on a hot plate Pre-baked) to remove solvent. After that, it was heated on a hot plate at 200 ° C for 10 minutes (post-baking) to form a coating film having an average film thickness of 800Å. 7 μl of MLC-2038 liquid crystal (manufactured by Merck) was dropped on the substrate and left for 30 seconds, and then a contact angle measuring device (DropMaster 700) manufactured by Kyowa Interface Chemical Co., Ltd. was used to measure the contact angle by the θ / 2 method The measurement standards are as follows: ◎: liquid crystal contact angle ≦ 13 ° ○: 13 °> liquid crystal contact angle ≧ 15 ° ╳: liquid crystal contact angle> 15 °.

The above embodiments are only for explaining the principle of the present invention and its effects, but not for limiting the present invention. Modifications and changes made by those skilled in the art to the above embodiments still do not violate the spirit of the present invention. The scope of rights of the present invention should be listed in the scope of patent application described later.

Claims (19)

A liquid crystal alignment agent, comprising: a polymer (A), which is selected from the group consisting of a polyacrylic acid polymer, a polyimide polymer, a polyimide block copolymer, or any combination of the foregoing polymers; containing Photoreactive polysiloxane (B); and solvent (C); wherein the polymer (A) comprises a unit represented by formula (Ia): Formula (Ia) In Formula (Ia), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or a straight or branched chain of C ₁ to C ₁₀ Alkyl; R _e is a single bond, or a linear or branched alkyl group of C ₁ to C ₁₀ ; R _a is a single bond, or _a linear or branched alkyl group of C ₁ to C ₁₀ ; Ht is a nitrogen-containing heterocyclic ring; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c Bici Can be combined to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; when Y is -COO-, -CONR _d -or -R _e -NR _{When d-} , a1 is 1; and * is a bond; the photoreactive group-containing polysiloxane (B) includes a structure represented by formula (IIa): Formula (IIa) In Formula (IIa), R ₁ is methylene, a linear or branched alkylene, C ₂ to C ₁₀ , phenylene, or cyclohexylene ), Part of the hydrogen atom of the R ₁ functional group is substituted or unsubstituted; R ₂ is a methylene group, or a linear or branched alkylene group of C ₂ to C ₁₀ , and a part of the hydrogen atom of the R ₂ functional group is Substituted or unsubstituted; R ₃ is a single bond, a methylene group, or a linear or branched alkylene group of C ₂ to C ₁₀ , and a part of the hydrogen atom of the R ₃ functional group is substituted or unsubstituted; R ₄ Is a hydrogen atom or a methyl group; L is -OCO-, -O-, or -S-; a is an integer from 0 to 10; b is an integer from 0 to 1; when b is 0, a is not 0; when a When it is plural, each of R ₂ and L is the same or different; and * is a bond. The liquid crystal alignment agent according to claim 1, wherein the polymer (A) includes a unit represented by formula (Ia-1), (Ia-2), or (Ia-3): Formula (Ia-1) Formula (Ia-2) Formula (Ia-3) In Formula (Ia-1) to Formula (Ia-3), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or C ₁ to C ₁₀ linear or branched alkyl; R _e is a single bond, or C ₁ to C ₁₀ linear or branched alkyl; R _a is a single bond, or C ₁ to C ₁₀ linear or branched alkyl; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c can be combined with each other to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; when Y is -COO-, -CONR _d -or -R _{When e} -NR _d- , a1 is 1; and * is a bonding point. According to the liquid crystal alignment agent of claim 1, the photoreactive group-containing polysiloxane (B) includes a structure represented by formula (IVa): E ^1- L ^0- L ^1- * (IVa) Formula (IVa ), E ¹ is a C ₁ to C ₃₀ alkyl group, a C ₃ to C ₁₀ cycloalkyl group substituted or unsubstituted by a C ₁ to C ₂₀ alkyl group or alkoxy group, or C containing a steroid skeleton A hydrocarbon group of ₁₇ to C ₅₁ , part of the hydrogen atoms of the alkyl group and alkoxy group of E ¹ are substituted or unsubstituted; L ⁰ is a single bond, * -O- *, * -COO- *, or * -OCO- ＊; L ¹ is a single bond, an alkylene group of C ₁ to C ₂₀ , a phenylene group, a biphenylene group, a cyclohexyl group, a dicyclohexyl group, or the following formula (IV-1) or (IV-2) The groups shown: Formula (IV-1) Formula (IV-2) When L ¹ is a single bond, L ⁰ is a single bond; and * is a bond. The liquid crystal alignment agent according to claim 1, wherein the fluorenimidization rate of the polymer (A) is 30% to 80%. A liquid crystal alignment film is formed using the liquid crystal alignment agent according to any one of claims 1 to 4. A liquid crystal display element includes the liquid crystal alignment film as claimed in claim 5. A method for manufacturing a liquid crystal alignment agent includes the following steps: (i) preparing a polymer by reacting a first mixture including a tetracarboxylic dianhydride component (a-1) and a diamine component (a-2) ( A), wherein the polymer (A) is selected from the group consisting of a polyamidopolymer, a polyamidopolymer, a polyamidoblock copolymer, or a combination thereof; wherein the diamine group Part (a-2) includes at least one diamine compound (a-2-1) represented by formula (Ib): Formula (Ib) In Formula (Ib), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or a straight or branched chain of C ₁ to C ₁₀ Alkyl; R _e is a single bond, or a linear or branched alkyl group of C ₁ to C ₁₀ ; R _a is a single bond, or _a linear or branched alkyl group of C ₁ to C ₁₀ ; Ht is a nitrogen-containing heterocyclic ring; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c Bici Can be combined to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; and when Y is -COO-, -CONR _d -or -R _e- When NR _d- , a1 is 1; (ii) a photo-reactive group-containing polysiloxane (B) is obtained by reacting a second mixture, and the second mixture includes an epoxy-containing polysiloxane ( b-1) and an ethylenically unsaturated compound (b-2), and the ethylenically unsaturated compound (b-2) includes a structure as shown in formula (IIb): Formula (IIb) In formula (IIb), R ₁ is a methylene group, a linear or branched alkylene group, a phenylene group, or a cyclohexyl group from C ₂ to C ₁₀ , and a part of the hydrogen atom of the functional group of R ₁ is Substituted or unsubstituted; R ₂ is a methylene group, or a linear or branched alkylene group of C ₂ to C ₁₀ , and a part of hydrogen atoms of the R ₂ functional group is substituted or unsubstituted; R ₃ is a single bond , Methylene, or C ₂ to C ₁₀ linear or branched alkylene, a part of the hydrogen atom of the R ₃ functional group is substituted or unsubstituted; R ₄ is a hydrogen atom or a methyl group; L is -OCO -, -O- or -S-; a is an integer from 0 to 10; b is an integer from 0 to 1; when b is 0, a is not 0; when a is plural, a plurality of R ₂ and L are each Are the same or different; and (iii) the polymer (A), the photoreactive group-containing polysiloxane (B), and the solvent (C) are mixed. The method for producing a liquid crystal alignment agent according to claim 7, wherein the diamine compound (a-2-1) includes a compound represented by formula (Ib-1), formula (Ib-2), or formula (Ib-3) : Formula (Ib-1) Formula (Ib-2) Formula (Ib-3) In Formula (Ib-1) to Formula (Ib-3), Y is a single bond, -COO-, -CONR _d -or -R _e -NR _d- ; R _d is a hydrogen atom, or C ₁ to C ₁₀ linear or branched alkyl; R _e is a single bond, or C ₁ to C ₁₀ linear or branched alkyl; R _a is a single bond, or C ₁ to C ₁₀ linear or branched alkyl; R _b is a C ₁ to C ₁₀ straight chain or branched chain of oxyalkyl, nitrile group or carbonyl group; R _c is a linear or branched C ₁ to C ₁₀ alkyl group; or R _b and R _c can be combined with each other to form a single ring; a1 is an integer from 0 to 1; a2 is an integer from 0 to 2; when Y is a single bond, a1 is 0; and when Y is -COO-, -CONR _d -or- When R _e −NR _d −, a1 is 1. According to the method for manufacturing a liquid crystal alignment agent according to claim 7, the second mixture further includes a side chain compound (b-3), and the side chain compound (b-3) includes a structure such as formula (IVb): E ¹ -L ⁰ -L ¹ -Z in formula (IVb) of formula (IVb), E ¹ is a C ₁ to C ₃₀ alkyl group, the substituted C ₁ to the sum to C ₂₀ alkyl or alkoxy, or unsubstituted C ₃ to A cycloalkyl group of C ₁₀ or a hydrocarbon group of C ₁₇ to C ₅₁ containing a steroid skeleton. Part of the hydrogen atom of the alkyl group and alkoxy group of E ¹ is substituted or unsubstituted; L ⁰ is a single bond, * -O -*, * -COO- * or * -OCO- *; L ¹ is a single bond, an alkylene group of C ₁ to C ₂₀ , a phenylene group, a phenylene group, a cyclohexyl group, a dicyclohexyl group or the following A group represented by formula (IV-1) or formula (IV-2): Formula (IV-1) Formula (IV-2) When L ¹ is a single bond, L ⁰ is a single bond; * is a bond; and Z is a monovalent organic group that reacts with an epoxy group to form a bonding group. The method for producing a liquid crystal alignment agent according to claim 7, wherein the epoxy group-containing polysiloxane (b-1) includes a group represented by the formula (III-1) and a group represented by the formula (III-2) And at least one of the radicals represented by formula (III-3): Formula (III-1) In Formula (III-1), B is an oxygen atom or a single bond; c is an integer of 1 to 3; and d is an integer of 0 to 6; when d is 0, B is a single bond; Formula (III-2) In Formula (III-2), e is an integer of 0 to 6; Formula (III-3) In formula (III-3), D is an alkylene group of C ₂ to C ₆ ; and E is a hydrogen atom or an alkyl group of C ₁ to C ₆ . The method for manufacturing a liquid crystal alignment agent according to claim 10, further comprising obtaining a epoxy-containing polysiloxane (b-1) from a third mixture by hydrolyzing and partially condensing, and the third mixture includes a Silane monomer (b-1-1) represented by formula (III-4): Si (R _f ) _p (OR _g ) _4-p formula (III-4) In formula (III-4), R _f is Hydrogen atom, C ₁ to C ₁₀ alkyl group, C ₂ to C ₁₀ alkenyl group, C ₆ to C ₁₅ aryl group, epoxy group-containing alkyl group or epoxy group-containing alkoxy group, and at least one R _f is an alkyl group containing an epoxy group or an alkoxy group containing an epoxy group; when p is plural, R _{f is} each the same or different; R _g is a hydrogen atom, an alkyl group of C ₁ to C ₆ , C Fluorenyl from ₁ to C ₆ or aryl from C ₆ to C ₁₅ ; when 4-p is plural, each of R _g is the same or different; and p is an integer from 1 to 3. The method for producing a liquid crystal alignment agent according to claim 7, wherein the diamine compound (a-2-1) represented by the formula (Ib) is based on a total amount of 100 mols of the diamine component (a-2). ) Is used in an amount of 3 to 40 moles. The method for manufacturing a liquid crystal alignment agent according to claim 11, wherein the amount of the silane monomer (b-1-1) used is 0.6 mol to 1 based on the total amount of the monomers in the third mixture. Mor. The method for manufacturing a liquid crystal alignment agent according to claim 7, wherein the amount of the ethylenically unsaturated compound (b-2) is 0.1 mol to 0.5 based on the total amount of the monomers in the third mixture. Mor. The method for manufacturing a liquid crystal alignment agent according to claim 9, wherein the amount of the side chain compound (b-3) is 0.05 mol to 0.3 mol based on the total amount of the monomers in the third mixture. . The method for manufacturing a liquid crystal alignment agent according to claim 7, wherein step (iii) is based on a use amount of the polymer (A) of 100 parts by weight, and a use amount of the photoreactive group-containing polysiloxane (B) 3 parts by weight to 60 parts by weight, and the amount of the solvent (C) used is 800 parts by weight to 3000 parts by weight. The method for producing a liquid crystal alignment agent according to claim 7, wherein the fluorinated ratio of the polymer (A) is 30% to 80%. A method for manufacturing a liquid crystal alignment film includes forming the liquid crystal alignment film from a liquid crystal alignment agent, wherein the liquid crystal alignment agent is formed by the method for manufacturing a liquid crystal alignment agent according to any one of claims 7 to 17. A manufacturing method of a liquid crystal display element, the liquid crystal display element comprising a liquid crystal alignment film, the manufacturing method comprising forming the liquid crystal alignment film from a liquid crystal alignment agent, wherein the liquid crystal alignment agent is selected from It is formed by the manufacturing method of a liquid crystal aligning agent.