Liquid crystal aligning agent containing crosslinking agent and polymer that has site having isocyanate group and/or blocked isocyanate group and site having photoreactivity, liquid crystal alignment film, and liquid crystal display element

Abstract

Provided is a liquid crystal display element that can be baked at a low temperature when forming a liquid crystal alignment film capable of imparting an alignment regulating property and a pretilt angle developing property via a photoalignment method. Further provided is a liquid crystal display element in which the liquid crystal pretilt angles are highly stable, and display burn-in hardly occurs even due to long usage. Further provided are a vertical liquid crystal alignment film to be used in the liquid crystal display element, and a liquid crystal aligning agent with which it is possible to provide the vertical liquid crystal alignment film. A liquid crystal aligning agent of the present invention contains: component (A), which is a polymer including (A-1) a site having an isocyanate group and/or a blocked isocyanate group and (A-2) a site having photoreactivity; component (B), which is a compound having, in a molecule, at least two functional groups of at least one type selected from the group consisting of an amino group and a hydroxyl group; and an organic solvent.

Claims

1. A liquid crystal aligning agent comprising the following component (A), the following component (B), and an organic solvent: Component (A): a polymer comprising a (A-1) site having an isocyanate group and/or a blocked isocyanate group; and a (A-2) site having photoalignment; Component (B): a compound comprising in a molecule of the compound two or more functional groups, each of which is at least one selected from the group consisting of an amino group and a hydroxyl group, wherein the (A-1) site having an isocyanate group and/or a blocked isocyanate group is represented by following formula (1), wherein Ia represents an isocyanate group or a blocked isocyanate group, Sa represents a spacer unit, the bonding pointer left of Sa represents bonding to the backbone of a polymer of the component (A) optionally via a spacer:
—S.sub.a—I.sub.a   (1), wherein the (A-1) site having an isocyanate group and/or a blocked isocyanate group is derived from a monomer represented by the formula (1m),
M.sub.a-M.sub.bS.sub.a—I.sub.a].sub.c   (1m); wherein Ma represents a first polymerizable group, Mb represents a single bond, a divalent heterocycle, a trivalent heterocycle, a tetravalent heterocycle, a substituted or unsubstituted linear or branched alkyl group having a carbon number of 1 to 10, a divalent aromatic group, a trivalent aromatic group, a tetravalent aromatic ring, a divalent alicyclic group, a trivalent alicyclic group, a tetravalent alicyclic group, a divalent condensed cyclic group, a trivalent condensed cyclic group or a tetravalent condensed cyclic group, wherein each group may be unsubstituted, or one or more hydrogen atoms in each group may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group, Sa represents a spacer unit, Ia represents an isocyanate group or a blocked isocyanate group, and c represents an integer of 1 to 3; and wherein Sa in the formula (1) and/or the formula (1m) is represented by the formula (2):
—W.sub.1-A.sub.1-W.sub.2-A.sub.2-W.sub.3—  (2) wherein the bonding left of W.sub.1 represents bonding to Mb, the bonding right of W.sub.3 represents bonding to Ia, W.sub.1, W.sub.2, and W.sub.3 each independently represents a single bond, a divalent heterocycle, —(CH.sub.2).sub.n— wherein n represents 1 to 20, —OCH.sub.2—, —CH.sub.2O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2CF.sub.2— or —C≡C—, wherein one or more non-adjacent CH.sub.2 groups in these substituents may be independently substituted with —O—, —CO—, —CO—O—, —O—CO—, —Si(CH.sub.3).sub.2—O—Si(CH.sub.3).sub.2—, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —OCO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—CO—O—, wherein R represents independently a hydrogen or a linear or branched alkyl group having a carbon number of 1 to 5, A.sub.1 and A.sub.2 each independently represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group, wherein each group may be unsubstituted, or one or more hydrogen atoms in each group may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group.

2. The liquid crystal aligning agent according to claim 1, wherein Ia in the formula (1) is selected from the group consisting of the following structures Ia-1 to Ia-8: ##STR00036## wherein the broken line represents bonding to Sa in the formula (1), and R.sub.6 represents a linear or branched alkyl group having a carbon number of 1 to 10, wherein one or more non-adjacent CH.sub.2 groups may be independently substituted with an oxygen atom.

3. The liquid crystal aligning agent according to claim 1, wherein the (A-2) site having photoalignment is represented by the following formula (3):
—S.sub.b—I.sub.b   (3) wherein Ib is a monovalent organic group comprising a photoreactive group having photoalignment, Sb represents a spacer unit, the bonding pointer left of Sb means bonding to the backbone of the polymer of the component (A) optionally via a spacer.

4. The liquid crystal aligning agent according to claim 1, wherein the (A-2) site having photoalignment is derived from a monomer represented by the following formula (3m):
M.sub.c-M.sub.dS.sub.b—I.sub.b).sub.d   (3m), wherein Mc represents a second polymerizable group, M.sub.d represents a single bond, a divalent heterocycle, a trivalent heterocycle, a tetravalent heterocycle, a substituted or unsubstituted linear or branched alkyl group having a carbon number of 1 to 10, a divalent aromatic group, a trivalent aromatic group, a tetravalent aromatic ring, a divalent alicyclic group, a trivalent alicyclic group, a tetravalent alicyclic group, a divalent condensed cyclic group, a trivalent condensed cyclic group or a tetravalent condensed cyclic group, wherein each group may be unsubstituted, or one or more hydrogen atoms in each group may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group, Sb represents a spacer unit, Ib is a monovalent organic group having a photoreactive group having photoalignment, and d is an integer of 1 to 3.

5. The liquid crystal aligning agent according to claim 4, wherein Sb is the formula (3m) is represented by the following formula (2):
—W.sub.1-A.sub.1-W.sub.2-A.sub.2-W.sub.3—  (2), wherein bonding left of W.sub.1 represents bonding to Md, bonding right of W.sub.3 represents bonding to I.sub.b, W.sub.1, W.sub.2, and W.sub.3 each independently represents a single bond, a divalent heterocycle, —(CH.sub.2).sub.n— wherein n represents 1 to 20, —OCH.sub.2—, —CH.sub.2O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2CF.sub.2— or —C≡C—, wherein one or more non-adjacent CH.sub.2 groups in these substituents may be independently substituted with —O—, —CO—, —CO—O—, —O—CO—, —Si(CH.sub.3).sub.2—O—Si(CH.sub.3).sub.2—, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —OCO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—CO—O— wherein R independently represents a hydrogen or a linear or branched alkyl group having a carbon number of 1 to 5, A.sub.1 and A.sub.2 each independently represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, wherein each group may be unsubstituted, or one or more hydrogen atoms in each group may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.

6. The liquid crystal aligning agent according to claim 3, wherein the photoreactive group of the formula Ib has the group represented by the following formulae (III)-1 to (III)-4: ##STR00037##

7. The liquid crystal aligning agent according to claim 4, wherein the monomer represented by the formula (3m) is a monomer represented by the following formula (3m)-1: ##STR00038## wherein Mc, Md and d are as defined in claim 4, Sb is an alkylene group having a carbon number of 1 to 10 or a divalent aromatic group, Z is an oxygen atom or a sulfur atom, Xa and Xb each represents independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having a carbon number of 1 to 3, R.sub.1 is a single bond, an oxygen atom, —COO— or —OCO—, R.sub.2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent condensed cyclic group, R.sub.3 is a single bond, an oxygen atom, —COO— or —OCO—, R.sub.4 is an alkyl group having a carbon number of 1 to 20 or a monovalent organic group including an alicyclic group having an carbon number of 3 to 20, R.sub.5 represents a fluorine atom or a cyano group, a is an integer of 0 to 3, and b is an integer of 0 to 4.

8. The liquid crystal aligning agent according to claim 1, wherein the first polymerizable group is independently at least one group selected from the group consisting of (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, acrylamide and siloxane.

9. The liquid crystal aligning agent according to claim 4, wherein the monomer represented by the formula (3m) is selected from the group consisting of following formulae MA-1 to MA-5: ##STR00039##

10. The liquid crystal aligning agent according to claim 1, wherein the component (B) is represented by the following formula (4):
(T.sub.mY   (4), wherein T represents an amino group or a hydroxyl group, Y represents an organic group with a valence of m, and m is an integer of 2 or more.

11. The liquid crystal aligning agent according to claim 1, wherein the component (A) is a polymer, which comprises and are formed from any one compound selected from the group consisting of the following formulae MA-1 to MA-5: ##STR00040##

12. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to claim 1.

13. A liquid crystal display element comprising the liquid crystal alignment film according to claim 12.

14. The liquid crystal aligning agent according to claim 4, wherein the second polymerizable group is independently at least one group selected from the group consisting of (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, acrylamide and siloxane.

Description

EXAMPLES

(1) Of the components (A) used in Examples, the structures of the (meth)acrylate compounds, which are the monomers capable of forming a site having photoalignment, are depicted by MA-1 to MA-5 and MA-6 to MA-9. MA-1 to MA-5 are novel compounds not disclosed in literatures, and their synthesis methods are described in detail in following Synthesis Examples 1 to 5. MA-6 and MA-9 were synthesized by known methods and available. MA-7 and MA-8 were manufactured by Tokyo Chemical Industry Co., Ltd. In the formula, “t” means that the cyclohexyl group is in the trans form.

(2) Additionally, of the components (A), the monomer capable of forming a site having an isocyanate group and/or a blocked isocyanate group is described below.

(3) Furthermore, the structure of the components (B) (specific compound) used in Examples are depicted by CR-1 to CR-3. Furthermore, HEMA was polymerized in the below-described Examples 18 and 19, and then the resulting polymer was used as the component (B) (specific compound).

(4) ##STR00029## ##STR00030##

(5) The abbreviations of the organic solvents used in Examples are as follows.

(6) NMP: N-methyl-2-pyrrolidone

(7) BC: butyl cellosolve

(8) THF: tetrahydrofuran

(9) DMF: N,N-dimethylformamide

(10) DMAc: N,N-dimethylacetamide

(11) PGME: propylene glycol monomethyl ether

(12) PGMEA: propylene glycol monomethyl ether acetate

(13) CHN: cyclohexanone

(14) The abbreviation of the polymerization initiator used in Examples is as follows.

(15) AIBN: 2,2′-azobisisobutyronitrile

(16) <Measurement of .sup.1HNMR>

(17) Apparatus: Fourier transformation superconductive nuclear magnetic resonance apparatus (FT-NMR) “INOVA-400” (Varian) 400 MHz.

(18) Solvent: deuterated chloroform (CDCl.sub.3) or deuterated N,N-dimethyl sulfoxide ([D.sub.6]-DMSO).

(19) Reference material: tetramethylsilane (TMS).

Synthesis Example 1

(20) Synthesis of [MA-1]:

(21) ##STR00031##

(22) 1-bromo-4-(trans-4-propylcyclohexyl)-benzene (150.0 g, 533 mmol), tert-butyl acrylate (102.5 g, 800 mmol), palladium acetate (2.39 g, 11 mmol), tri(o-tolyl)phosphine (6.49 g, 21 mmol), tripropylamine (229.3 g, 1600 mmol), and DMAc (750 g) were placed in a 2-L four-necked flask, and stirred under heating at 100° C. After completion of the reaction, the reaction liquid was filtered to remove insoluble matter, the filtrate was poured into pure water (3.8 L), and neutralized with 12 N—HCl aqueous solution. After neutralization, ethyl acetate (2.5 L) was poured thereinto, and extraction was carried out. Anhydrous magnesium sulfate was added to the extracted organic layer, the mixture was dried by dehydration, and anhydrous magnesium sulfate was filtrated. The filtrate thus obtained was evaporated to remove the solvent with a rotary evaporator, and the crude product was subjected to repulping washing with cold methanol (180 g), thereby to obtain 144.0 g of [MA-1-1] (white solid) (yield: 82%).

(23) [MA-1-1] (144.0 g, 441 mmol) and formic acid (1000 g) were placed in a 2-L four-necked flask, and stirred under heating at 50° C. After completion of the reaction, the reaction liquid was poured into pure water (3.0 L), the precipitate was filtrated. The crude product thus obtained was subjected to repulping washing with ethyl acetate (200 g), thereby to obtain 111.1 g of [MA-1-2] (white solid) (yield: 92%). The result of .sup.1H-NMR of the objective is given below. This result confirms that the solid thus obtained is the desired [MA-1-2].

(24) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ12.34 (s, 1H), 7.53-7.60 (m, 3H), 7.25-7.27 (d, 2H), 6.44-6.48 (d, 1H), 2.45-2.51 (t, 1H), 1.76-1.83 (t, 4H), 1.28-1.48 (m, 5H), 1.15-1.21 (m, 2H), 0.97-1.07 (m, 2H), 0.87-0.89 (t, 3H).

(25) [MA-1-2] (30.0 g, 110 mmol), 2-hydroxyethyl methacrylate (17.2 g, 132 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (25.7 g, 165 mmol), 4-dimethylaminopyridine (1.35 g, 11 mmol), and THF (150 g) were placed in a 2-L four-necked flask, and stirred at room temperature. After completion of the reaction, the reaction liquid was poured into ethyl acetate (1.0 L), extraction was carried out using pure water (800 mL). Anhydrous magnesium sulfate was added to the extracted organic layer, the mixture was dried by dehydration, and anhydrous magnesium sulfate was filtrated. The filtrate thus obtained was evaporated to remove the solvent with a rotary evaporator. The residue thus obtained was isolated by silica gel column chromatography (ethyl acetate:hexane=1:5 volume ratio), thereby to obtain 26.8 g of [MA-1] (white solid) (yield: 55%). The result of .sup.1H-NMR of the objective is given below. This result confirmed that the solid thus obtained is the desired [MA-1].

(26) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ7.62-7.66 (m, 3H), 7.25-7.27 (d, 2H), 6.58-6.62 (d, 1H), 6.05 (s, 1H), 5.70 (s, 1H), 4.37-4.42 (m, 4H), 2.44-2.48 (t, 1H), 1.88 (s, 3H), 1.76-1.82 (t, 4H), 1.24-1.47 (m, 5H), 1.15-1.21 (m, 2H), 0.96-1.06 (m, 2H), 0.85-0.89 (t, 3H).

Synthesis Example 2

(27) Synthesis of [MA-2]:

(28) ##STR00032##

(29) 1-bromo-4-(trans-4-pentyl cyclohexyl)-benzene (150.0 g, 485 mmol), tert-butyl acrylate (93.24 g, 728 mmol), palladium acetate (2.18 g, 9.7 mmol), tri(o-tolyl)phosphine (5.90 g, 20 mmol), tripropylamine (208.5 g, 1455 mmol), and DMAc (750 g) were placed in a 2-L four-necked flask, and stirred under heating at 100° C. After completion of the reaction, the reaction liquid was filtered to remove insoluble matter, the filtrate was poured into pure water (3.8 L), and neutralized with a 12 N—HCl aqueous solution. After neutralization, ethyl acetate (2.5 L) was poured, and extraction was carried out. To the extracted organic layer, anhydrous magnesium sulfate was added and dried by dehydration, and the anhydrous magnesium sulfate was filtered. The filtrate thus obtained was evaporated to remove the solvent with a rotary evaporator, and the crude product was subjected to repulping washing with cold methanol (190 g), thereby to obtain 137.0 g of [MA-2-1] (white solid) (yield: 79%).

(30) [MA-2-1] (137.0 g, 384 mmol), formic acid (1000 g) were placed in a 2-L four-necked flask, and stirred under heating at 50° C. After completion of the reaction, the reaction liquid was poured into pure water (3.0 L), and the precipitate was filtrated. The crude product thus obtained subjected to repulping washing using ethyl acetate (200 g), thus obtaining 111.8 g of [MA-2-2] (white solid) (yield: 96%). The result of .sup.1H-NMR of the objective is given below. This result confirmed that the solid thus obtained is the desired [MA-2-2].

(31) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ12.34 (s, 1H), 7.53-7.60 (m, 3H). 7.25-7.27 (d, 2H), 6.44-6.48 (d, 1H), 2.45-2.51 (t, 1H), 1.77-1.83 (t, 4H), 1.38-1.48 (m, 2H), 1.17-1.34 (m, 9H), 0.97-1.07 (m, 2H), 0.87-0.89 (t, 3H).

(32) [MA-2-2] (30.0 g, 100 mmol), 2-hydroxyethyl methacrylate (15.6 g, 119 mmol), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride (EDC) (28.7 g, 150 mmol), 4-dimethylaminopyridine (1.22 g, 10 mmol), and THF (150 g) were placed in a 2-L four-necked flask, and stirred at room temperature. After completion of the reaction, the reaction liquid was poured into ethyl acetate (1.0 L), extraction was carried out using pure water (800 mL). To the extracted organic layer, anhydrous magnesium sulfate was added and dried by dehydration, and the anhydrous magnesium sulfate was filtered. The filtrate thus obtained was evaporated to remove the solvent with a rotary evaporator. The residue thus obtained was isolated by silica gel column chromatography (ethyl acetate:hexane=1:5 volume ratio), thereby to obtain 36.6 g of [MA-2] (white solid) (yield: 88%). The result of .sup.1H-NMR of the objective is given below. The result confirmed that the solid thus obtained is the desired [MA-2].

(33) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ7.62-7.66 (m, 3H), 7.25-7.27 (d, 2H), 6.58-6.62 (d, 1H), 6.04 (s, 1H), 5.70 (s, 1H), 4.36-4.42 (m, 4H), 2.48-2.52 (t, 1H), 1.88 (s, 3H), 1.76-1.83 (t, 4H), 1.36-1.44 (m, 2H), 1.18-1.31 (m, 9H), 1.00-1.03 (m, 2H), 0.85-0.88 (t, 3H).

Synthesis Example 3

(34) Synthesis of [MA-3]:

(35) ##STR00033##

(36) 1-bromo-4-(trans-4-heptyl cyclohexyl)-benzene (150.0 g, 445 mmol), tert-butyl acrylate (85.5 g, 667 mmol), palladium acetate (0.90 g, 8.9 mmol), tri(o-tolyl)phosphine (5.41 g, 18 mmol), tripropylamine (191.1 g, 1334 mmol), and DMAc (750 g) were placed in a 2-L four-necked flask, and stirred under heating at 100° C. After completion of the reaction, the reaction liquid was filtered to remove insoluble matter, the filtrate was poured into pure water (3.8 L), and neutralized with a 12 N—HCl aqueous solution. After neutralization, ethyl acetate (2.5 L) was poured, and extraction was carried out. To the extracted organic layer, anhydrous magnesium sulfate was added and dried by dehydration, and the anhydrous magnesium sulfate was filtered. The filtrate thus obtained was evaporated to remove the solvent with a rotary evaporator, the crude product was subjected to repulping washing with cold methanol (180 g), thereby to obtain 151.6 g of [MA-3-1] (white solid) (yield: 89%).

(37) [MA-3-1] (151.6 g, 394 mmol) and formic acid (1061 g) were placed in a 2-L four-necked flask, and stirred under heating at 50° C. After completion of the reaction, the reaction liquid was poured into pure water (3.0 L), and the precipitate was filtrated. The crude product thus obtained was subjected to repulping washing with ethyl acetate (500 g), thereby to obtain 121.7 g of [MA-3-2] (white solid) (yield: 94%). The result of .sup.1H-NMR of the objective is given below. The result confirmed that the solid thus obtained is the desired [MA-3-2].

(38) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ12.34 (s, 1H), 7.53-7.59 (m, 3H), 7.25-7.27 (d, 2H), 6.44-6.48 (d, 1H), 2.44-2.51 (t, 1H), 1.77-1.82 (t, 4H), 1.37-1.48 (m, 2H), 1.17-1.28 (m, 13H), 0.97-1.07 (m, 2H), 0.86-0.88 (t, 3H).

(39) [MA-3-2] (30.0 g, 91 mmol), methacrylic acid 2-hydroxyethyl (14.3 g, 110 mmol), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride (EDC) (26.3 g, 137 mmol), 4-dimethylaminopyridine (1.12 g, 9.1 mmol), and THF (150 g) were placed in a 2-L four-necked flask, and stirred at room temperature. After completion of the reaction, the reaction liquid was poured into ethyl acetate (1.0 L), extraction was carried out using pure water (800 mL). To the extracted organic layer, anhydrous magnesium sulfate was added and dried by dehydration, and the anhydrous magnesium sulfate was filtered. The filtrate thus obtained was evaporated to remove the solvent with a rotary evaporator. The residue thus obtained was isolated by silica gel column chromatography (ethyl acetate:hexane=1:5 volume ratio), thereby to obtain 34.5 g of [MA-3] (white solid) (yield: 86%). The result of .sup.1H-NMR of the objective is given below. The result confirmed that the solid thus obtained is the desired [MA-3].

(40) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ7.61-7.66 (m, 3H), 7.24-7.26 (d, 2H), 6.57-6.61 (d, 1H), 6.04 (s, 1H), 5.69 (s, 1H), 4.36-4.42 (m, 4H), 2.43-2.52 (t, 1H), 1.88 (s, 3H), 1.76-1.82 (t, 4H), 1.36-1.46 (m, 2H), 1.15-1.29 (m, 13H), 0.95-1.05 (m, 2H), 0.84-0.87 (t, 3H).

Synthesis Example 4

(41) Synthesis of [MA-4]:

(42) ##STR00034##

(43) 1-trans[1,1′-bicyclohexyl]-4-yl-4-bromobenzene (200.0 g, 623 mmol), acrylic acid (67.3 g, 934 mmol), palladium acetate (2.80 g, 12.4 mmol), tri(o-tolyl)phosphine (7.58 g, 25 mmol), tripropylamine (267.5 g, 1867 mmol) and DMAc (400 g) was placed in a 1-L four-necked flask, and stirred under heating at 100° C. After completion of the reaction, the reaction liquid was filtered to remove insoluble matter, the filtrate was poured into pure water (2.0 L), neutralized with 12 N—HCl aqueous solution, and the precipitate was filtrated. The crude product thus obtained was subjected to repulping washing with methanol (200 g), thereby to obtain 154.1 g of [MA-4-1] (white solid) (yield: 79%). The result of .sup.1H-NMR of the objective is given below. The result confirmed that the solid thus obtained is the desired [MA-4-1].

(44) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ12.36 (s, 1H), 7.52-7.59 (m, 3H). 7.25-7.27 (d, 2H), 6.44-6.48 (d, 1H), 2.44-2.50 (t, 1H), 1.79-1.82 (m, 4H), 1.61-1.70 (m, 5H), 1.40-1.42 (d, 2H), 1.14-1.20 (m, 7H), 0.97-1.02 (m, 2H).

(45) [MA-4-1] (100.0 g, 320 mmol), 2-hydroxyethyl methacrylate (45.8 g, 352 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (92.0 g, 480 mmol), 4-dimethylaminopyridine (3.91 g, 32 mmol), and THF (1000 g) were placed in a 2-L four-necked flask, and stirred at room temperature. After completion of the reaction, the reaction liquid was poured into ethyl acetate (0.5 L), and extraction was carried out using pure water (400 mL). To the extracted organic layer, anhydrous magnesium sulfate was added and dried by dehydration, and the anhydrous magnesium sulfate was filtered. The filtrate thus obtained was evaporated to remove the solvent with a rotary evaporator. The residue thus obtained was isolated by silica gel column chromatography (ethyl acetate:hexane=1:5 volume ratio), thereby to obtain 109.8 g of [MA-4] (white solid) (yield: 80%). The result of .sup.1H-NMR of the objective is given below. The result confirmed that the solid thus obtained is the desired [MA-4].

(46) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ7.62-7.66 (m, 3H), 7.25-7.27 (d, 2H), 6.58-6.62 (d, 1H), 6.04 (s, 1H), 5.70 (s, 1H), 4.38-4.41 (m, 4H), 2.43-2.51 (t, 1H), 1.88 (s, 3H), 1.79-1.82 (m, 4H), 1.60-1.69 (m, 5H), 1.39-1.42 (d, 2H), 1.13-1.20 (m, 7H), 0.96-1.02 (m, 2H).

Synthesis Example 5

(47) Synthesis of [MA-5]:

(48) ##STR00035##

(49) 4-hydroxybenzoic acid tert-butyl (37.1 g, 191 mmol), 1,1,1-trifluoro-4-iodobutane (50.0 g, 210 mmol), potassium carbonate (39.7 g, 287 mmol), and DMF (300 g) were placed in a 500-mL four-necked flask, and stirred under heating at 100° C. After completion of the reaction, the reaction liquid was poured into pure water (1.5 L), and the precipitate was filtrated. The crude product thus obtained was subjected to repulping washing with hexane (300 g), thereby to obtain 42.2 g of [MA-5-1] (white solid) (yield: 73%).

(50) [MA-5-1] (42.2 g, 139 mmol) and formic acid (300 g) were placed in a 500-mL four-necked flask, and stirred under heating at 50° C. After completion of the reaction, the reaction liquid was poured into pure water (1.5 L), and the precipitate was filtrated. The crude product thus obtained was subjected to repulping washing with acetonitrile (80 g), thereby to obtain 31.9 g of [MA-5-2] (white solid) (yield: 92%).

(51) [MA-5-2] (31.9 g, 129 mmol), trans-p-tert-butyl coumarate (42.5 g, 193 mmol), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride (EDC) (37.0 g, 193 mmol), 4-dimethylaminopyridine (1.59 g, 13 mmol), and THF (300 g) were placed in a 500-mL four-necked flask, and stirred at room temperature. After completion of the reaction, the reaction liquid was poured into pure water (1.5 L), and the precipitate was filtrated. The crude product thus obtained was subjected to repulping washing with methanol (180 g), thereby to obtain 43.6 g of [MA-5-3] (white solid) (yield: 75%).

(52) [MA-5-3] (43.6 g, 97 mmol) and formic acid (300 g) were placed in a 500-mL four-necked flask, and stirred under heating at 50° C. After completion of the reaction, the reaction liquid was poured into pure water (1.5 L), and the precipitate was filtrated. The crude product thus obtained was subjected to repulping washing with acetonitrile (500 g), thereby to obtain 36.6 g of [MA-5-4] (white solid) (yield: 96%). The result of .sup.1H-NMR of the objective is given below. The result confirmed that the solid thus obtained is the desired [MA-5-4].

(53) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ12.46 (s, 1H), 8.08-8.10 (d, 2H), 7.78-7.81 (d, 2H), 7.61-7.65 (d, 1H), 7.31-7.34 (d, 2H), 7.13-7.16 (d, 2H), 6.53-6.57 (d, 1H), 4.16-4.19 (t, 2H), 2.40-2.47 (m, 2H), 1.95-2.02 (m, 2H).

(54) [MA-5-4] (15.0 g, 38 mmol), 2-hydroxyethyl methacrylate (5.47 g, 42 mmol), 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide hydrochloride (EDC) (10.9 g, 57 mmol), 4-dimethylaminopyridine (0.46 g, 3.8 mmol), and THF (150 g) were placed in a 500-mL four-necked flask, and stirred at room temperature. After completion of the reaction, the reaction liquid was poured into ethyl acetate (0.6 L), and extraction was carried out using pure water (500 mL). To the extracted organic layer, anhydrous magnesium sulfate was added and dried by dehydration, and the anhydrous magnesium sulfate was filtered. The filtrate thus obtained was evaporated to remove the solvent with a rotary evaporator. The residue thus obtained was isolated by silica gel column chromatography (ethyl acetate:hexane=1:1 volume ratio), thereby to obtain 16.8 g of [MA-5] (white solid) (yield: 87%). The result of 1H-NMR of the objective is given below. The result confirmed that the solid thus obtained is the desired [MA-5].

(55) 1H NMR (400 MHz, [D.sub.6]-DMSO): δ8.07-8.11 (d, 2H), 7.84-7.86 (d, 2H), 7.70-7.74 (d, 1H), 7.32-7.34 (d, 2H), 7.13-7.16 (d, 2H), 6.68-6.72 (d, 1H), 6.05 (s, 1H), 5.71 (s, 1H), 4.37-4.44 (m, 4H), 4.16-4.19 (t, 2H), 2.42-2.49 (m, 2H), 1.95-2.02 (m, 2H), 1.88 (s, 3H).
<Measurement of Polymer Molecular Weight>

(56) The molecular weight of each polymer in Synthesis Examples was measured as described below using a normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd., and a column (KD-803, KD-805) manufactured by Showa Denko K.K.

(57) Column temperature: 50° C.

(58) Eluate: N,N′-dimethylformamide (as an additive, 30 mmol/L of lithium bromide monohydrate (LiBr.H.sub.2O), 30 mmol/L of phosphoric acid-anhydrous crystal (o-phosphoric acid), and 10 mL/L of tetrahydrofuran (THF))

(59) Flow rate: 1.0 mL/minute

(60) Standard sample for preparing calibration curve: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight: about 9,000,000, 150,000, 100,000, and 30,000), and polyethylene glycol manufactured by Polymer laboratories Ltd. (molecular weight: about 12,000, 4,000, and 1,000).

Example 1

(61) MA2 (6.19 g, 15.0 mmol) and MOI-BP (8.80 g, 35.0 mmol) were dissolved in CHN (61.6 g), deaerated with a diaphragm pump, and AIBN (0.41 g, 2.5 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (1000 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (B). The number average molecular weight of the polymer was 43600, and the weight average molecular weight was 131200.

(62) To the methacrylate polymer powder (B) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (B1).

(63) [Preparation of Liquid Crystal Cell]

(64) The liquid crystal aligning agent (B1) obtained in Example 1 was applied by spin coating to the ITO surface of a glass substrate with a transparent electrode made of an ITO film, and dried for 120 seconds on a hot plate at 50° C., and then baked for 20 minutes on a hot plate at 120° C., thereby to form a liquid crystal alignment film having a film thickness of 100 nm. Subsequently, the coating film surface was irradiated with 50 mJ/cm.sup.2 of 313 nm linearly polarized ultraviolet light at an irradiation intensity of 4.3 mW/cm.sup.2 through a polarizing plate from an angle inclined 40° toward the normal direction of the substrate, thereby to obtain a substrate with a liquid crystal alignment film. The linearly polarized light UV was prepared by passing a 313 nm bandpass filter through ultraviolet light of a high pressure mercury lamp, and then passing a 313 nm polarizing plate.

(65) Two pieces of the above-described substrate were provided, 4 μm bead spacers were spread on the liquid crystal alignment film of one substrate, and then a sealing agent (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was applied. Subsequently, the other substrate was bonded thereto in such a manner that the liquid crystal alignment film surfaces are faced to each other and the alignment direction was 180°, and then the sealing agent was heat-cured at 120° C. for 90 minutes, thereby to prepare empty cells. Into the empty cells, negative liquid crystal (MLC-3022, manufactured by Merck Ltd.) was injected by a reduced pressure injection method, thereby to prepare liquid crystal cells.

(66) [Evaluation of Pretilt Angle]

(67) The pretilt angles of the liquid crystal cells was measured by the Mueller Matrix method using “AxoScan” of AxoMetrix. The result is summarized in Table 1.

(68) [Evaluation of Liquid Crystal Alignment]

(69) After preparing liquid crystal cells, they were subjected to isotropic phase treatment at 120° C. for 1 hour, and then the cell was observed with a polarization microscope; alignment was regarded as good when there was no alignment faulty such as light void and generation of domains, and when uniform driving of liquid crystal was achieved upon application of a voltage to the liquid crystal cells. The result is summarized in Table 1.

Examples 2 to 4

(70) Liquid crystal cells were obtained in a manner similar to [Preparation of liquid crystal cell] in Example 1, except that the irradiation amount of polarized ultraviolet light was changed to 20, 100, and 400 mJ/cm.sup.2. Additionally, the pretilt angles and liquid crystal cell alignment were evaluated in the same manner as in Example 1.

Examples 5 and 6

(71) Liquid crystal cells were obtained in a manner similar to [Preparation of liquid crystal cell] in Example 1, except that the baking temperature of the liquid crystal alignment film in Example 1 was changed to 100° C. (Example 5) and 140° C. (Example 6). Additionally, the pretilt angles and liquid crystal cell alignment were evaluated in the same manner as in Example 1.

Example 7

(72) A liquid crystal aligning agent was prepared in a manner similar to Example 1, except that the addition amount of CR-1 to be introduced was changed to 0.3 g, and the pretilt angles and liquid crystal cell alignment were evaluated.

Examples 8 and 9

(73) A liquid crystal aligning agent was prepared in a manner similar to Example 1, except that the specific compound to be introduced was changed from CR-1 to CR-2, and the addition amount was changed to 0.15 g and 0.3 g, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 10

(74) A liquid crystal aligning agent was prepared in a manner similar to Example 1, except that the specific compound to be introduced was changed from CR-1 to CR-3, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 11

(75) MA2 (4.13 g, 10.0 mmol) and MOI-BP (2.51 g, 10.0 mmol) were dissolved in CHN (27.2 g), deaerated with a diaphragm pump, and AIBN (0.17 g, 1.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (400 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (C). The number average molecular weight of the polymer was 41300, and the weight average molecular weight was 121100.

(76) To the methacrylate polymer powder (C) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (C1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 12

(77) MA3 (4.41 g, 10.0 mmol) and MOI-BP (2.51 g, 10.0 mmol) were dissolved in CHN (28.3 g), deaerated with a diaphragm pump, and AIBN (0.17 g, 1.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (400 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (D). The number average molecular weight of the polymer was 42100, and the weight average molecular weight was 128500.

(78) To the methacrylate polymer powder (D) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (D1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 13

(79) MA2 (2.48 g, 6.0 mmol) and MOI (2.17 g, 14.0 mmol) were dissolved in CHN (19.3 g), deaerated with a diaphragm pump, and AIBN (0.17 g, 1.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (300 mL) composed of diethyl ether and hexane=4/6, and the precipitate thus obtained was filtrated. The precipitate was washed with a mixed solvent of diethyl ether and hexane=4/6, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (E). The number average molecular weight of the polymer was 25000, and the weight average molecular weight was 102000.

(80) To the methacrylate polymer powder (E) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGMEA (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (E1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Examples 14 and 15

(81) The pretilt angles and liquid crystal cell alignment were evaluated in a manner similar to Example 13, except that the baking conditions for the liquid crystal alignment film in Example 13 were changed to 100° C. for 20 minutes (Example 14) and 140° C. for 5 minutes (Example 15).

Example 16

(82) MA2 (2.48 g, 6.0 mmol) and MOI-DEM (4.41 g, 14.0 mmol) were dissolved in CHN (28.2 g), deaerated with a diaphragm pump, and AIBN (0.17 g, 1.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 12 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (400 mL) of methanol and pure water=1.5/8.5, and the precipitate thus obtained was filtrated. The precipitate was washed with a mixed solvent composed of methanol and pure water=1.5/8.5, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (F). The number average molecular weight of the polymer was 36400, and the weight average molecular weight was 117200.

(83) To the methacrylate polymer powder (F) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (F1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 17

(84) MA2 (2.48 g, 6.0 mmol), MOI-BP (2.51 g, 10.0 mmol), and CHMI (0.72 g, 4.0 mmol) were dissolved in CHN (33.3 g), deaerated with a diaphragm pump, and AIBN (0.17 g, 1.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 15 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (500 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (G). The number average molecular weight of the polymer was 26500, and the weight average molecular weight was 87100.

(85) To the methacrylate polymer powder (G) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (G1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 18

(86) HEMA (19.5 g, 150.0 mmol) was dissolved in PGME (83.2 g), deaerated with a diaphragm pump, and AIBN (1.25 g, 7.5 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 80° C. for 12 hours, thereby to obtain the polymer solution of methacrylate (H). The number average molecular weight of the polymer was 4800, and the weight average molecular weight was 5700.

(87) Subsequently, to the methacrylate polymer powder (B) (1.5 g) obtained in Example 1, CHN (18.0 g) was added, and the mixture was stirred at room temperature for 5 hours. To the solution, the polymer solution (H) obtained above (7.5 g) (the mass of the HEMA-derived polymer in 7.5 g of the polymer solution (H): 1.5 g) and PGME (3.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (H1). Since the HEMA-derived polymer has two or more hydroxyl groups, in the present example, the polymer was used as the component (B): specific compound of the present invention.

(88) Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 19

(89) To the methacrylate polymer powder (B) (1.0 g) obtained in Example 1, CHN (14.9 g) was added, and the mixture was stirred at room temperature for 5 hours. To the solution, the polymer solution (H) obtained in Example 18 (11.7 g) (the mass of the HEMA-derived polymer in 7.5 g of the polymer solution (H): 2.3 g) and PGME (5.5 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (H2). Since the HEMA-derived polymer has two or more hydroxyl groups, in the present example, the polymer was used as the component (B): specific compound of the present invention.

(90) Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 20

(91) MA2 (3.30 g, 8.0 mmol), MOI-BP (7.04 g, 28.0 mmol), and MA6 (1.77 g, 4.0 mmol) were dissolved in CHN (49.7 g), deaerated with a diaphragm pump, and AIBN (0.33 g, 2.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (700 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (J). The number average molecular weight of the polymer was 57000, and the weight average molecular weight was 115000.

(92) To the methacrylate polymer powder (J) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (J1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 21

(93) MA2 (4.13 g, 10.0 mmol), MOI-BP (7.04 g, 28.0 mmol), and MA7 (0.68 g, 2.0 mmol) were dissolved in CHN (48.7 g), deaerated with a diaphragm pump, and AIBN (0.33 g, 2.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (700 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (K). The number average molecular weight of the polymer was 40000, and the weight average molecular weight was 138000.

(94) To the methacrylate polymer powder (K) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (K1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 22

(95) MA2 (4.95 g, 12.0 mmol), MOI-BP (6.03 g, 24.0 mmol), and MA8 (0.67 g, 4.0 mmol) were dissolved in CHN (47.9 g), deaerated with a diaphragm pump, and AIBN (0.33 g, 2.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (700 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (L). The number average molecular weight of the polymer was 37000, and the weight average molecular weight was 123000.

(96) To the methacrylate polymer powder (L) (1.5 g) thus obtained, CHN (18.0 g) was added, and the mixture was dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (L1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Example 23

(97) MA2 (4.95 g, 12.0 mmol), MOI-BP (6.03 g, 24.0 mmol), and MA9 (0.87 g, 4.0 mmol) were dissolved in CHN (48.7 g), deaerated with a diaphragm pump, and AIBN (0.33 g, 2.0 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (700 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (M). The number average molecular weight of the polymer was 38000, and the weight average molecular weight was 128000.

(98) CHN (18.0 g) was added to the methacrylate polymer powder (M) (1.5 g) thus obtained, and dissolved by stirring at room temperature for 5 hours. To the solution, CR-1 (0.15 g) and PGME (18.0 g) were added, and the mixture was stirred to obtain the liquid crystal aligning agent (M1). Subsequently, liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

Comparative Example 1

(99) MA2 (6.19 g, 15.0 mmol) and MOI-BP (8.80 g, 35.0 mmol) were dissolved in CHN (61.6 g), deaerated with a diaphragm pump, and AIBN (0.41 g, 2.5 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (1000 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with methanol, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (B). The number average molecular weight of the polymer was 43600, and the weight average molecular weight was 131200.

(100) CHN (18.0 g) and PGME (18.0 g) were added to the methacrylate polymer powder (B) (1.5 g) thus obtained, and the mixture was dissolved under stirring at room temperature for 5 hours, thereby to obtain the liquid crystal aligning agent (B2).

(101) [Preparation of Liquid Crystal Cells]

(102) Liquid crystal cells were prepared in a manner similar to [Preparation of liquid crystal cell] in Example 1, except that the liquid crystal aligning agent (B2) obtained in Comparative Example 1 was used in place of the liquid crystal aligning agent (B1) obtained in Example 1. [Evaluation of pretilt angles] and [Evaluation of liquid crystal cell alignment]

(103) The pretilt angles were measured in the same manner as in Example 1. Additionally, liquid crystal cell alignment was evaluated in the same manner as in Example 1. The results are summarized in Table 1.

Comparative Example 2

(104) MA5 (5.06 g, 10.0 mmol) was dissolved in NMP (20.6 g), deaerated with a diaphragm pump, and AIBN (0.08 g, 0.5 mmol) was added and deaerated again. Thereafter, the mixture was allowed to react at 55° C. for 13 hours, thereby to obtain a polymer solution of methacrylate. The polymer solution was added dropwise into a mixed solvent (300 mL) composed of methanol and pure water=5/5, and the precipitate thus obtained was filtrated. The precipitate was washed with a mixed solvent composed of methanol and pure water=5/5, and vacuum-dried in an oven at 40° C., thereby to obtain the methacrylate polymer powder (I). The number average molecular weight of the polymer was 39400, and the weight average molecular weight was 119800.

(105) To the methacrylate polymer powder (I) (1.5 g) thus obtained, CHN (18.0 g) and PGME (18.0 g) were added, and the mixture was dissolved under stirring at room temperature for 5 hours, thereby to obtain the liquid crystal aligning agent (I1). Subsequently, comparative liquid crystal cells were prepared in a manner similar to Example 1, and the pretilt angles and liquid crystal cell alignment were evaluated.

(106) Examples show that the combination of the specific polymer and the specific compound of the present invention allowed to obtain good pretilt angles even by baking at low temperatures of 140° C. or lower.

(107) On the other hand, as indicated by Comparative Examples, good pretilt angles and liquid crystal alignment were not obtained only by the specific polymer alone. The reason for this is likely that the anisotropy imparted to the side chains by photoreaction was disappeared by curing of the sealing agent and heating during isotropic phase treatment.

(108) TABLE-US-00001 TABLE 1 Specific compound amount Baking Exposure Pretilt Liquid Specific % by mass/ conditions dose angle crystal Polymer compound polymer ° C./min. (mJ/cm.sup.2) (°) alignment Ex. 1 B CR-1 10 120/20 50 88.2 Good Ex. 2 B CR-1 10 120/20 20 88.3 Good Ex. 3 B CR-1 10 120/20 100 87.9 Good Ex. 4 B CR-1 10 120/20 400 88.3 Good Ex. 5 B CR-1 10 100/20 50 88.4 Good Ex. 6 B CR-1 10 140/20 50 88.1 Good Ex. 7 B CR-1 20 120/20 50 88.2 Good Ex. 8 B CR-2 5 120/20 50 88.5 Good Ex. 9 B CR-2 10 120/20 50 88.2 Good Ex. 10 B CR-3 10 120/20 50 88.1 Good Ex. 11 C CR-1 10 120/20 50 88.5 Good Ex. 12 D CR-1 10 120/20 50 88.6 Good Ex. 13 E CR-1 10 120/20 50 87.9 Good Ex. 14 E CR-1 10 100/20 50 88.1 Good Ex. 15 E CR-1 10 140/5  50 88.1 Good Ex. 16 F CR-1 10 120/20 50 88.5 Good Ex. 17 G CR-1 10 120/20 50 88.3 Good Ex. 18 B H 100 120/20 50 89.2 Good Ex. 19 B H 230 120/20 50 88.9 Good Ex. 20 J CR-1 10 120/20 50 89.4 Good Ex. 21 K CR-1 10 120/20 50 89.4 Good Ex. 22 L CR-1 10 120/20 50 89.3 Good Ex. 23 M CR-1 10 120/20 50 89.4 Good Comp. 1 B — 0 120/20 50 90 Bad Comp. 2 I — 0 120/20 50 89.8 Bad