JP2000344734A - Hydrophobic compound having excluded volume effect - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound which is effective for controlling the orientation of a liquid-crystalline molecule, by connecting a specific hydrophobic group to an excluded volume effect-having group. SOLUTION: This compound which is obtained by connecting a hydrophobic group to an excluded volume effect-having group, and is expressed by the formula: (Hb-)mL(-Bu)n Hb is a hydrophobic group (for example, teterafluorophenyl) selected from a 1 to 40C fluorinated alkyl, a 6 to 40C fluorinated aryl, and a 1 to 60C alkylated oligosiloxanoxy; Bu is a group containing at least two cyclic structures and having an excluded volume effect (for example, a group of formula I or II); L is a [(m)+(n)]-valent connection group [for example, C2H4-O-CO-O or the like; (m), (n) are each 1 to 12]} (for example, a compound of formula III). The compound has a function for controlling the orientation state of a liquid-crystalline molecule, especially an air interface side liquid- crystalline molecule when an orientation membrane is used, and can uniformly orient liquid-crystalline molecules even on a free interface not having an orientation membrane, when the compound is used as a liquid crystal orientation- accelerating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound having a molecular structure in which a hydrophobic group and a group having an excluded volume effect are linked.

[0002]

2. Description of the Related Art A transmission type liquid crystal display device comprises a liquid crystal cell and two polarizing plates disposed on both sides thereof. In a reflection type liquid crystal display device, a reflection plate, a liquid crystal cell, and one polarizing plate are laminated in this order. The liquid crystal cell includes rod-like liquid crystal molecules, two substrates for enclosing the same, and an electrode layer for applying a voltage to the rod-like liquid crystal molecules. The rod-like liquid crystal molecules are aligned on two substrates by alignment films provided respectively. Since the rod-like liquid crystal molecules are injected into the gap between the two alignment films, the alignment state of the rod-like liquid crystal molecules can be relatively easily controlled by the two alignment films.

In order to increase the viewing angle of a liquid crystal display device or to eliminate coloring, an optical compensation sheet (retardation plate) is often arranged between a liquid crystal cell and a polarizing plate. As the optical compensation sheet, a stretched birefringent film has been conventionally used. However, it has been proposed to use an optical compensation sheet having an optically anisotropic layer formed of liquid crystal molecules on a transparent support, instead of the optical compensation sheet made of a stretched birefringent film. The optically anisotropic layer is formed by aligning liquid crystalline molecules and fixing the alignment state. The alignment state of the liquid crystal molecules is aligned by a single alignment film provided between the transparent support and the optically anisotropic layer.

[0004]

With a single alignment film, it is difficult to uniformly align liquid crystal molecules from the alignment film interface to the air interface (monodomain alignment). If the liquid crystal molecules are not uniformly aligned, light scattering due to disclination occurs. An object of the present invention is to provide a hydrophobic compound effective for controlling the alignment of liquid crystal molecules. Another object of the present invention is to provide a hydrophobic compound useful as a metal surface treating agent.

[0005]

The object of the present invention has been attained by the following hydrophobic excluded volume effect compounds (1) to (6). (1) the following formula (I) represented by the hydrophobic excluded volume effect compound: (I) (Hb-) in _m L (-Bu) _n [Formula, Hb is a fluorine-substituted 1 to 40 carbon atoms Hydrophobicity selected from the group consisting of an alkyl group, a fluorine-substituted aryl group having 6 to 40 carbon atoms, an alkyl group having 6 to 60 carbon atoms, and an alkyl-substituted oligosiloxanoxy group having 1 to 60 carbon atoms. A group; Bu
Is a group having an excluded volume effect including at least two cyclic structures; L is a (m + n) -valent linking group; and m and n are each independently an integer from 1 to 12.] .

(2) In the formula (I), Hb is a fluorine-substituted alkyl group having 1 to 40 carbon atoms or a fluorine-substituted aryl group having 6 to 40 carbon atoms (1)
2. The hydrophobic excluded volume effect compound according to item 1. (3) In the formula (I), m and n are each 1 and L is an -alkylene group-, -O-, -CO-,-
NR -, - SO ₂ - and a divalent linking group selected from the group consisting of hydrophobic excluded volume effect compound described in which R is hydrogen atom or an alkyl group (1). (4) The hydrophobic excluded volume effect compound according to (1), wherein in formula (I), m and n are each independently an integer of 2 to 12, and L is a linking group containing a cyclic structure. (5) The hydrophobic excluded volume effect compound according to (1), wherein in the formula (I), the group having a excluded volume effect of Bu contains a tricyclic or tetracyclic fused ring. (6) The hydrophobic excluded volume effect according to (1), wherein in the formula (I), the group having an excluded volume effect of Bu includes a structure in which at least two rings are bonded by a single bond, a vinylene bond or an ethynylene bond. Compound.

[0007]

As a result of the research by the present inventors, a compound in which a hydrophobic group (Hb) and a group having an excluded volume effect (Bu) as defined by the above formula (I) are linked is a liquid crystal molecule. In particular, it has been found that it has a function of controlling the alignment state of the liquid crystal molecules on the air interface side when one alignment film is used. Therefore, when the hydrophobic excluded volume effect compound represented by the formula (I) is used as a liquid crystal alignment accelerator, liquid crystal molecules can be uniformly aligned even at a free interface where an alignment film is not provided. Further, the present inventor has further studied and found that the hydrophobic group (Hb) as defined by the above formula (I)
It has also been found that a compound in which a compound having an excluded volume effect and a group (Bu) having an excluded volume effect have a function of imparting a low surface energy surface to a metal material. Therefore, when the hydrophobic excluded volume effect compound represented by the formula (I) is used as a metal surface treating agent, the metal surface is non-adhesive, water-repellent, moisture-proof, stain-proof, rust-proof, and prevents icing and snow. , Release property or weather resistance.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hydrophobic excluded volume effect compound The hydrophobic excluded volume effect compound is represented by the following formula (I). (I) (Hb-) _m L (-Bu) _{n In the} formula (I), Hb is a fluorine-substituted alkyl group having 1 to 40 carbon atoms, a fluorine-substituted aryl group having 6 to 40 carbon atoms, carbon A hydrophobic group selected from the group consisting of an alkyl group having 6 to 60 atoms and an alkyl-substituted oligosiloxanoxy group having 1 to 60 carbon atoms. A fluorine-substituted alkyl group having 1 to 40 carbon atoms and a fluorine-substituted aryl group having 6 to 40 carbon atoms are preferable, and a fluorine-substituted alkyl group having 1 to 40 carbon atoms is particularly preferable.

[0009] The fluorine-substituted alkyl group may have a cyclic structure or a branch. The fluorine-substituted alkyl group has 1 to 40 carbon atoms. The number of carbon atoms is preferably 2 to 30, more preferably 3 to 20, still more preferably 4 to 15,
Most preferably, it is 6 to 12. The ratio of the fluorine atom replacing the hydrogen atom of the alkyl group is 50 to 1
It is preferably 00%, more preferably 60 to 100%, still more preferably 70 to 100%, still more preferably 80 to 100%, and more preferably 85 to 100%. Most preferred. The fluorine-substituted aryl group has 6 to 40 carbon atoms.
It is. The fluorine-substituted aryl group is preferably a fluorine-substituted phenyl. The proportion of the fluorine atom replacing the hydrogen atom of the aryl group is preferably 50 to 100%, more preferably 60 to 100%, further preferably 70 to 100%,
It is still more preferably 80 to 100%, and 8
Most preferably, it is 5 to 100%.

An alkyl group having 6 to 60 carbon atoms is
It may have a cyclic structure or a branch. The alkyl group preferably has 7 to 50 carbon atoms, and has 8 carbon atoms.
It is more preferably from 40 to 40, further preferably from 9 to 30, and most preferably from 10 to 20. The total number of carbon atoms of the alkyl-substituted oligosiloxanoxy group is 1 to 60. The alkyl-substituted oligosiloxanoxy group is a group represented by the following formula. R ^1- (SiR ² ₂ -O) _q- wherein R ¹ is a hydrogen atom, a hydroxyl or an alkyl group; R ² is a hydrogen atom or an alkyl group and at least one of a plurality of R ² Is an alkyl group;
Then, q is an integer of 2 to 12. It is particularly preferred that R ¹ is hydroxyl. It is particularly preferred that each of the plurality of R ² is an alkyl group. q is 2
It is preferably an integer of from 8 to 8, more preferably 3, 4, 5 or 6. The alkyl group may have a cyclic structure or a branch. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 8, still more preferably 1 to 6, still more preferably 1 to 4, and 1 ( Most preferably, it is methyl) or 2 (ethyl). Below, the example of a hydrophobic group (Hb) is shown.

[0011] (Hb-1) n-C 8 F 17 - (Hb-2) H-C 8 F 16 - (Hb-3) tetrafluorophenyl - (Hb-4) H- C 6 F 12 - (Hb _{-5) H-C 4 F 8} - (Hb-6) HO- (Si (CH 3) 2 -O) 4 - (Hb-7) n-C 12 H 25 -

In the formula (I), Bu is a group having an excluded volume effect containing at least two cyclic structures. The cyclic structure includes an aliphatic ring, an aromatic ring, and a heterocyclic ring. The ring having a cyclic structure is preferably a 5-, 6-, or 7-membered ring, more preferably a 5- or 6-membered ring, and most preferably a 6-membered ring. The relationship between the two ring structures includes fused ring formation, spiro bond, single bond, and bond via a divalent linking group. Preference is given to condensed ring formation, a single bond and a bond via a divalent linking group. When at least two cyclic structures form a fused ring, it is preferably a tricyclic fused ring or a tetracyclic fused ring. When at least two cyclic structures are bonded via a divalent linking group, examples of the divalent linking group include -O-, -C
O-, -alkylene group-, vinylene bond (-CH = CH
-), Ethynylene bonds (-C≡C-) and combinations thereof. The divalent linking group is preferably a vinylene bond or an ethynylene bond, and more preferably an ethynylene bond. In the ring of the cyclic structure,
The substituent may be bonded. Examples of the substituent include a halogen atom, hydroxyl, cyano, nitro, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms),
Substituted alkyl groups (eg, carboxyalkyl groups, alkoxyalkyl groups), alkoxy groups, substituted alkoxy groups (eg, oligoalkoxy groups), alkenyloxy groups (eg, vinyloxy), acyl groups (eg, acryloyl,
Methacryloyl), acyloxy groups (eg, acryloyloxy, benzoyloxy) and epoxy groups (eg, epoxyethyl). Hereinafter, examples of the group (Bu) having an excluded volume effect will be described.

[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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In the formula (I), L is a (m + n) -valent linking group. In the formula (I), m and n are each independently an integer of 1 to 12. m and n are
Each is preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, still more preferably 1 to 3,
Most preferably, it is 1. If in formula (I), m and n are each 1, L is - alkylene group -, - O -, - CO -, - NR -, - SO ₂ - and selected from the group consisting of Preferably, the divalent linking group is a divalent linking group. R is a hydrogen atom or an alkyl group. L preferably contains at least one polar group (group other than -alkylene group-). The alkylene group preferably has 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and preferably 1 to 2 carbon atoms.
It is more preferably 0, still more preferably 1 to 15, and most preferably 1 to 12. The alkyl group preferably has 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, further preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms. Most preferably, it is from 12 to 12.

When m is 2 or more, a plurality of hydrophobic groups (H
b) may be different. When n is 2 or more, the groups (Bu) having a plurality of excluded volume effects may be different. When m or n is 2 or more, the linking group (L) can form a chain structure or a cyclic structure. When the linking group (L) has a chain structure, a plurality of hydrophobic groups (Hb) or a plurality of groups having a excluded volume effect (Bu) can be bonded to the main chain linking group (L) as a side chain. . When the linking group (L) has a cyclic structure, a plurality of hydrophobic groups (Hb) or a plurality of groups having a excluded volume effect (Bu) can be bonded to the linking group (L) of the cyclic structure as a substituent. When m and n are each independently an integer of 2 to 12, L is preferably a linking group containing a cyclic structure. Hereinafter, examples of the linking group (L) are shown. (L-1) which is a divalent linking group
In (L-11), the left side is bonded to a hydrophobic group (Hb), and the right side is bonded to a group (Bu) having an excluded volume effect. The polyvalent linking groups (L-12) to (L-17) include a hydrophobic group (Hb) and a group (B) having an excluded volume effect.
u).

(L-1) -SO ₂ -N (nC ₃ H ₇ )
_{-C 2 H 4 -O-CO-} O- (L-2) -SO 2 -N (n-C 3 H 7) -C 2 H 4 -
O-CO-NH- (L- 3) -SO 2 -N (n-C 3 H 7) -C 2 H 4 -
_{O-CO-O-CH 2} - (L-4) -SO 2 -NH-C 2 H 4 -O-CO-NH
_{- (L-5) -SO 2} -NH-C 2 H 4 -O-CO-O- (L-6) -CO-NH-C 2 H 4 -O-CO-O- (L-7) - CO-NH- (L-8) -NH-C 2 H 4 -O-CO-O- (L-9) -CO-NH-C 2 H 4 -O-CO-NH- (L-10) - _{SO 2 -N (n-C 3} H 7) -C 6 H 12 -
O-CO-NH- (L- 11) -C 2 H 4 -O-CO-O-

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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The hydrophobic excluded volume effect compound is a compound obtained by combining the above-described hydrophobic group (Hb), a group having an excluded volume effect (Bu), and a linking group (L). There is no particular limitation on these combinations. Hereinafter, specific examples of the hydrophobic excluded volume effect compound represented by the formula (I) will be shown. The hydrophobic group (Hb), the group having an excluded volume effect (Bu), and the linking group (L) in each example are the numbers of the examples described above.

I-1: (Hb-1)-(L-1)-(Bu-1) I-2: (Hb-1)-(L-2)-(Bu-2) I-3: ( Hb-1)-(L-1)-(Bu-3) I-4: (Hb-1)-(L-1)-(Bu-4) I-5: (Hb-1)-(L- 3)-(Bu-5) I-6: (Hb-1)-(L-1)-(Bu-6) I-7: (Hb-1)-(L-1)-(Bu-7) I-8: (Hb-1)-(L-3)-(Bu-1) I-9: (Hb-1)-(L-4)-(Bu-2) I-10: (Hb-1) )-(L-5)-(Bu-8) I-11: (Hb-1)-(L-2)-(Bu-9) I-12: (Hb-1)-(L-5)- (Bu-10) I-13: (Hb-1)-(L-6)-(Bu-11) I-14: (Hb-2)-(L-7)-(Bu-7)

I-15: (Hb-3)-(L-8)-(Bu-1) I-16: (Hb-4)-(L-9)-(Bu-2) I-17: ( Hb-5)-(L-6)-(Bu-8) I-18: (Hb-1)-(L-10)-(Bu-9) I-19: (Hb-1)-(L- 5)-(Bu-12) I-20: (Hb-6)-(L-11)-(Bu-12) I-21: (Hb-7)-(L-7)-(Bu-7) I-22: (Hb-1) _3- (L-12)-(Bu-2) ₃ I-23: (Hb-1) _3- (L-13)-(Bu-2) ₃ I-24: _{(Hb-1) 3 - (} L-14) - (Bu-1) 3 I-25: (Hb-1) 4 - (L-15) - (Bu-1) 4 I-26: (Hb-1 _{) 4 - (L-16)} - (Bu-2) 4 I-27: (Hb-1) 2 - (L-17) - (Bu-1) I-28: (Hb-5) - (L- 7)-(Bu-2)

[Liquid Crystal Alignment Acceleration Function] The compound represented by the formula (I) can be localized on the air interface side after being mixed and applied with liquid crystal. To be unevenly distributed on the air interface side,
It is necessary to be incompatible with the liquid crystal, that is, to separate from the liquid crystal. The hydrophobic group (Hb) functions to cause phase separation from the liquid crystal. Furthermore, in order to promote the alignment of the liquid crystal,
A partial structure that is relatively rigid and has properties close to the molecular polarization characteristics of the liquid crystal is required. Group having an excluded volume effect (Bu)
Corresponds to such a partial structure. It is presumed that the compound represented by the formula (I) exists near the air interface with the hydrophobic group (Hb) directed toward the air and the group (Bu) having an excluded volume effect directed toward the liquid crystal. As a general tendency, when the group having an excluded volume effect (Bu) has a planar structure (for example, when it contains a tricyclic fused ring or a tetracyclic fused ring), it exhibits a horizontal alignment effect on a rod-like liquid crystal. . When the group having an excluded volume effect (Bu) has a planar structure, for a discotic liquid crystal, depending on whether the group having an excluded volume effect (Bu) is hydrophilic or hydrophobic, The horizontal or vertical alignment effect is shown. In the case where the group (Bu) having an excluded volume effect has a structure protruding like a pile on the liquid crystal side (for example, including a structure in which at least two rings are bonded by a single bond, a vinylene bond, or an ethynylene bond), A vertical alignment effect is exhibited for both the rod-shaped liquid crystal and the discotic liquid crystal.

As described above, the electrostatic attraction between molecules and the repulsion due to the excluded volume effect between the liquid crystal and the compound represented by the formula (I) are determined by the molecular structure of the compound, particularly the group having the excluded volume effect. By changing (Bu), it can be controlled freely. That is, by appropriately selecting the type of the compound represented by the formula (I), the tilt angle of the liquid crystal molecule on the air interface side is not limited to the type of the liquid crystal molecule,
Can be arbitrarily controlled. The compound used as the liquid crystal alignment accelerator is preferably used in an amount of 0.01 to 20% by mass, more preferably 0.1 to 5% by mass of the amount of the liquid crystal.

[Metal Surface Treatment Function] The hydrophobic group (Hb) of the compound represented by the formula (I) has a function of imparting a low surface energy surface to a metal material. Therefore, when the metal surface is treated with the compound represented by the formula (I), the non-adhesive, water-repellent, moisture-proof, antifouling, rust-proof, anti-icing / anti-snow properties, mold release properties and weather resistance are improved. The composite function can be more effectively expressed. The conventional metal surface treatment agent has a problem that the coating of the treatment agent on the metal surface is easily peeled or broken. The group (Bu) having the excluded volume effect of the compound represented by the formula (I) has excellent affinity with the metal surface. Therefore, the treatment agent formed on the metal surface (formula (I)
Is also superior to conventional metal surface treatment agents.

[0036]

[Embodiment 1]

[0037]

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(Synthesis of Compound (A)) In a 1-liter three-necked flask equipped with a stirrer, 25.7 g (0.151 mol) of p-hydroxybiphenyl and 304.9 g (1.51 mol) of 1,3-dibromopropane were added. ), Potassium carbonate 4
6.2 g (0.332 mol) and 300 ml of N, N-dimethylformamide were added, and the mixture was stirred at 130 ° C. for 5 hours. After cooling to room temperature, the mixture was extracted and washed with ethyl acetate / saturated saline. The ethyl acetate phase was separated, collected, and dried over anhydrous sodium sulfate. After the ethyl acetate was distilled off, the remaining 1,3-dibromopropane was further distilled off using a vacuum pump. Then silica gel was added to the stationary phase, hexane /
The product was purified by column chromatography using methylene dichloride (1/1) as a developing phase, and further recrystallized from methanol. Yield 17.7 g (40% yield). CDCl
¹ H-NMR using ₃ as a solvent: 2.3 ppm. Multiplet,
2H; 3.7 ppm. Doublet, 2H; 4.2 ppm. Double
t, 2H; 7.0 ppm. doublet, 2H; 7.3 ppm. doub
let, 1H; 7.4 ppm. triplet, 2H; 7.6 ppm. tr
iplet, 4H

[0039]

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(Synthesis of Compound (B)) Compound (A) 17.47 was placed in a 100 ml three-necked flask equipped with a stirrer.
g (0.06 mol) and triethanolamine 8.7
After adding 6 ml (0.066 mol) and stirring at 150 ° C. for 3 hours, the reaction system solidified. Methanol was added to dissolve, and the insoluble matter was filtered off. Purification was performed by column chromatography using silica gel as a stationary phase and hexane / methylene dichloride (5/1) as a developing phase. Yield 10.7g
(Yield 41%). ¹ H-N using DMSO-d ₆ as a solvent
MR: 2.2 ppm. Multiplet, 2H; 3.6 ppm. Multi
plet, 8H; 3.8 ppm. triplet, 6H; 4.1 ppm. t
riplet, 2H; 7.0 ppm. doublet, 2H; 7.3 ppm.
doublet, 1H; 7.4 ppm. triplet, 2H; 7.6 pp
m. doublet, 4H

[0041]

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(Synthesis of Compound (C)) A 1-liter three-necked flask equipped with a stirrer was charged with a fluorine-based surfactant (Megafac F-104, manufactured by Dainippon Ink and Chemicals, Inc.).
5 g (0.17 mol) and 50.4 g of triphosgene
(0.17 mol), and tetrahydrofuran 3
90 ml was added and stirred to dissolve. Stirring was continued at room temperature for 3 hours and served overnight at room temperature. When tetrahydrofuran was distilled off under reduced pressure, an excess of triphosgene was precipitated, and this was filtered off to obtain 103.2 g of a viscous oil. This viscous oil was purified single upstream. 3.2-3.4mmH
g / 172-186 ° C. Yield 81.9 g (yield 74
%). ¹ H-NMR using CDCl ₃ as a solvent: 1.0 pp
m. triplet, 3H; 1.7 ppm. multiplet, 2H;
3 to 3.9 ppm. Multiplet, 4H; 4.5 ppm. Triple
t, 2H

[0043]

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(Synthesis of Compound (I-27)) Compound (B) 4.4 was placed in a 100 ml three-necked flask equipped with a stirrer.
g (0.01 mol), N, N-dimethylacetamide 3
0 ml and pyridine 0.97 ml (0.012 mol)
Was added and stirred to dissolve. 7.77 g of compound (C)
(0.012 mol) was added dropwise, and the mixture was stirred at room temperature for 20 minutes and then at 70 ° C. for 3 hours. At this time, compound (B)
Was left, so 0.97 ml of pyridine and 7.77 g of compound (C) were further added, and the mixture was stirred at 70 ° C. for 2 hours. Extraction and washing were performed with ethyl acetate / saturated saline, and the ethyl acetate phase was separated and dried over anhydrous sodium sulfate.
Ethyl acetate was distilled off, and the residue was purified by column chromatography using silica gel as a stationary phase and methylene dichloride / methanol (5/1) as a mobile phase. Yield 0.34 g (2% yield). ¹ H-NMR using CDCl ₃ as a solvent: 0.9
ppm. triplet, 6H; 1.5 to 1.7 ppm.
4H; 2.3 to 2.4 ppm. Multiplet, 2H;
3.5 ppm. Multiplet, 6H; 3.7-4.0 ppm. Mul
tiplet, 6H; 4.0-4.4 ppm. multiplet, 12
H; 4.7 ppm. Triplet, 4H; 7.0 ppm. Doublet,
2H; 7.4 ppm. Doublet, 1H; 7.5 ppm. Triplet
t, 2H; 7.6ppm.triplet, 4H

[Embodiment 2]

[0046]

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(Synthesis of Compound (I-1)) In a 100 ml three-necked flask equipped with a stirrer, 3.4 g (0.02 mol) of p-hydroxybiphenyl, 20 ml of tetrahydrofuran and 1.94 ml (0.024 mol) of pyridine were added. Was added and stirred and dissolved. A solution prepared by dissolving 15.55 g (0.024 mol) of the compound (C) synthesized in Example 1 in 10 ml of tetrahydrofuran was added dropwise at room temperature. After the addition, the mixture was stirred at room temperature for 1 hour. The mixture was extracted and washed with ethyl acetate / dilute hydrochloric acid, and then washed with saturated saline. The ethyl acetate phase was separated and dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography using silica gel as a stationary phase and hexane / chloroform (2/1) as a developing phase. Yield: 5.7 g (37% yield). CD
¹ H-NMR using Cl ₃ as a solvent: 1.0 ppm. Triple
t, 3H; 1.7 to 1.8 ppm. multiplet, 2H;
3 to 4.0 ppm. Multiplet, 4H; 4.4 ppm. Triple
t, 2H; 7.2 to 7.6 ppm. multiplet, 9H

[Embodiment 3]

[0049]

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(Synthesis of Compound (D)) In a 300 ml three-necked flask equipped with a stirrer and a reflux condenser, 31.9 g (0.312 mol) of ethynylbenzene and 52.5 g (0.26 mol) of p-nitrobromobenzene were added. Mol), 0.55 g (0.78 mmol) of bis (triphenylenephosphine) palladium (II) dichloride, 1.09 g of triphenylphosphine, 0.18 g (0.94 mmol) of copper iodide and 150 ml of triethylamine. The mixture was heated and stirred at 100 ° C. for 2 hours. After cooling to room temperature, the mixture was extracted and washed with ethyl acetate / dilute sulfuric acid. After further washing with saturated saline, it was dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and recrystallized from methanol (1.2 L). Yield 44.8 g (77% yield).

[0051]

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(Synthesis of Compound (E)) Reduced iron 1 was placed in a 300 ml three-necked flask equipped with a stirrer and a reflux condenser.
3.9 g (0.25 mol), isopropyl alcohol 6
0 ml, water 24 ml and ammonium chloride 0.50 g
(9.3 mmol), and 13.9 g of the compound (D) was gradually added while heating and stirring at 90 ° C. After heating and stirring for 30 minutes, tetrahydrofuran 120 ml
Was added, and the mixture was filtered through celite with heating. 70
When the solution was concentrated under reduced pressure to a volume of ml, a yellow substance was deposited. This was filtered off and poured into 150 ml of water. The precipitated crystals were taken out of the furnace and recrystallized with 60 ml of methanol to obtain 8.2 g of compound (E) (yield: 69%).

[0053]

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(Synthesis of Compound (I-2)) Compound (E) 3.8 was placed in a 100 ml three-necked flask equipped with a stirrer.
7 g (0.02 mol), 30 ml of N, N-dimethylacetamide and 1.94 ml (0.024 mol) of pyridine were added and dissolved by stirring. While stirring, 15.55 g (0.024 mol) of the compound (C) synthesized in Example 1 was added dropwise. After stirring at room temperature for 10 minutes, dilute hydrochloric acid 200m
l. The precipitated crystals were taken out of the furnace and recrystallized from tetrahydrofuran / methanol to give compound (I-2)
8.38 g (52% yield) was obtained. ¹ H-NMR using CDCl ₃ as a solvent: 1.0 ppm. Triplet, 3H; 1.7
ppm. multiplet, 2H; 3.3 to 3.9 ppm. multiple
t, 4H; 4.4 ppm. triplet, 2H; 6.7 ppm. sing
let, 1H; 7.3 to 7.6 ppm. multiplet, 9H

[Application Example 1] (Preparation of Optically Anisotropic Element) Thickness 100 μm, size 27
A 0 mm × 100 mm triacetyl cellulose film (Fujitac, manufactured by Fuji Photo Film Co., Ltd.) was used as a transparent support. N-methyl-2
A 5% by weight solution was prepared by dissolving in a mixed solvent of -pyrrolidone and 2-butanone. The obtained solution was applied on a transparent support using a bar coater. When the coating layer is 80
Dry with warm air at ℃ for 10 minutes, rubbing the surface,
An alignment film was formed.

[0056]

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A coating solution having the following composition was applied on the alignment film by an extrusion method, and heated to 130 ° C.
The discotic liquid crystalline compound was aligned.

塗布 Liquid crystal layer coating solution ───────デ ィ ス 100 parts by weight of the following discotic liquid crystalline compound Compound (I-1) synthesized in Example 2 5.0 parts by weight Photopolymerization initiator (Irgacure 907, manufactured by Nippon Ciba Geigy Co., Ltd.) 0.2 parts by weight 2-butanone 185 parts by weight ──────────────────

[0059]

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While the coating layer was heated to 130 ° C., it was irradiated with ultraviolet rays for 4 seconds to polymerize the terminal vinyl groups of the discotic liquid crystalline compound and fix the alignment state. Thus, an optically anisotropic element was produced. The in-plane retardation of the optically anisotropic element was measured, and the average tilt angle of the discotic liquid crystal molecules was determined from the angle dependence to be 88 °. In addition, when the alignment state of the discotic liquid crystal molecules was confirmed with a polarizing microscope, all the molecules were uniformly aligned (monodomain alignment), and no alignment defect was observed. When the above experiment was further repeated twice, the average tilt angle of the discotic liquid crystal molecules slightly changed (89 ° in the second test and 88 ° in the third test).
However, no alignment defect was found in any of the alignment states of the discotic liquid crystal molecules.

Reference Example 1 An optically anisotropic element was produced in the same manner as in Application Example 1, except that Compound (I-1) was not added. The in-plane retardation of the optically anisotropic element was measured, and the average tilt angle of the discotic liquid crystal molecules was determined from the angle dependence to be 75 °. In addition, when the alignment state of the discotic liquid crystal molecules was confirmed with a polarizing microscope, it was confirmed that countless fine alignment defects having a sea-island pattern existed. When the above experiment was further repeated twice, the average tilt angle of the discotic liquid crystalline molecules fluctuated (72 ° for the second time and 80 ° for the third time).
In each case, it was recognized that countless fine orientation defects having a sea-island pattern were present.

[Application Example 2] (Preparation of Optical Compensation Sheet) Thickness 100 μm, size 27
A 0 mm × 100 mm triacetyl cellulose film (Fujitac, manufactured by Fuji Photo Film Co., Ltd.) was used as a transparent support. The polyimide used in Example 1 was replaced with N-
It was dissolved in a mixed solvent of methyl-2-pyrrolidone and 2-butanone to prepare a 5% by weight solution. The resulting solution is
The composition was coated on the transparent support using a bar coater. The coating layer was dried with hot air at 80 ° C. for 10 minutes, and the surface was rubbed to form an alignment film.

A coating solution having the following composition was applied on the alignment film by an extrusion method and heated to 130 ° C.
The discotic liquid crystalline compound was aligned.

<< Coating Liquid for Optically Anisotropic Layer >>デ ィ ス 100 parts by weight of the discotic liquid crystalline compound used in Application Example 1 The following chiral 1.8 parts by weight Compound (I-1) synthesized in Example 5.0 5.0 parts by weight Photopolymerization initiator (Irgacure 907, manufactured by Nippon Ciba Geigy Co., Ltd.) 0.2 parts by weight 2-butanone 185 parts by weight ───────────────────────────────────

[0065]

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While the coating layer was heated to 130 ° C., it was irradiated with ultraviolet rays for 4 seconds to polymerize the terminal vinyl groups of the discotic liquid crystalline compound and fix the alignment state. Thus, an optical compensation sheet was produced. When the retardation and the film thickness of the optical compensation sheet were measured using an ellipsometer, the retardation per 2 μm thickness was 1
It was 80 nm. In addition, when the alignment state of the discotic liquid crystal molecules was confirmed with a polarizing microscope, all the molecules were uniformly aligned (monodomain alignment), and no alignment defect was observed. When the above experiment was further repeated twice, the retardation per 2 μm thickness slightly changed (176 nm in the second time, 170 n in the third time).
m), but no alignment defect was observed in any of the alignment states of the discotic liquid crystal molecules.

Reference Example 2 An optical compensatory sheet was prepared in the same manner as in Application Example 2, except that Compound (I-1) was not added. When the retardation and the film thickness of the optical compensation sheet were measured using an ellipsometer, the retardation per 2 μm thickness was 155 nm. In addition, when the alignment state of the discotic liquid crystal molecules was confirmed with a polarizing microscope, it was confirmed that countless fine alignment defects having a sea-island pattern existed. When the above experiment was further repeated twice, the retardation per 2 μm thickness varied (155 nm in the second time, 150 nm in the third time), and the alignment state of the discotic liquid crystal molecules was a sea-island pattern. It was recognized that countless fine alignment defects existed.

[Application Example 3] (Production of liquid crystal display device) Twist angle is 240 °, Δnd
Are placed under the 880 nm STN liquid crystal cell, two optical compensatory sheets prepared in Application Example 2 are facing the optically anisotropic layer side, and the director of discotic liquid crystalline molecules of the optically anisotropic layer ( The discotic liquid crystal molecules were stuck together so that the discotic liquid crystal molecules had the same normal direction. The optical compensation sheet was attached to the liquid crystal cell such that the discotic liquid crystal molecules and the director of the rod-like liquid crystal molecules of the liquid crystal cell coincided on the surface where the optical compensation sheet and the liquid crystal cell were bonded. Further, a pair of polarizing plates were attached in a crossed Nicol arrangement to produce an STN liquid crystal display device. When the manufactured STN liquid crystal display device was compared with the STN liquid crystal display device without the optical compensation sheet, a remarkable effect of improving the viewing angle by the optical compensation sheet was recognized.

[Application Example 4] (Production of Optically Anisotropic Element) Thickness 100 μm, size 27
A 0 mm × 100 mm triacetyl cellulose film (Fujitac, manufactured by Fuji Photo Film Co., Ltd.) was used as a transparent support. The polyimide used in Example 1 was replaced with N-
It was dissolved in a mixed solvent of methyl-2-pyrrolidone and 2-butanone to prepare a 5% by weight solution. The resulting solution is
The composition was coated on the transparent support using a bar coater. The coating layer was dried with hot air at 80 ° C. for 10 minutes, and the surface was rubbed to form an alignment film.

On the alignment film, a coating solution having the following composition was applied by an extrusion method.

塗布 Liquid crystal layer coating solution ─────── ４− 100 parts by weight of 4-methoxybenzylidene-4-butylaniline (MBBA, rod-like liquid crystalline compound) Compound (I-2) synthesized in Example 3 3.0 parts by weight 2-butanone 185 parts by weight ─────────

The coating layer was heated to a nematic phase forming temperature to vertically orient the rod-like liquid crystalline molecules, thereby producing an optically anisotropic element. In the heated state, under crossed Nicols, the alignment state of the rod-like liquid crystalline molecules was confirmed with a polarizing microscope.
All the molecules were uniformly oriented (monodomain orientation), and no orientation defect was observed.

Reference Example 3 An optically anisotropic element was produced in the same manner as in Application Example 4, except that Compound (I-2) was not added. In a heated state, the alignment state of the rod-like liquid crystalline molecules was confirmed under a crossed Nicols with a polarizing microscope. As a result, it was recognized that countless fine alignment defects having a sea-island pattern were present.

[Application Example 5] To 1 liter of chloroform,
0.8 g of compound (I-24) was added, mixed well, and dissolved. A small iron plate was immersed in the obtained solution for 5 minutes, pulled up, and air-dried. In order to evaluate the metal surface treatment effect on the sample iron plate, the contact angle (wetting property) to water was measured by a standard method. Further, at a temperature of 80 ° C,
After standing at a relative humidity of 90% for 500 hours (forced test), the contact angle (wetting property) to water was measured in the same manner. The following results were obtained. Contact angle of sample iron plate surface before metal surface treatment: 8 ゜ Contact angle of sample iron plate surface after metal surface treatment: 115 ゜ Contact angle of sample iron plate surface after compulsory test: 109 ゜For evaluation, an uncured epoxy resin was sandwiched between two sample iron plates, and the sample iron plate was peeled off after the curing of the epoxy resin was completed. Furthermore, when the epoxy resin was sandwiched between the two iron plates after the peeling, and the treatment of peeling after the curing was continuously performed five times, the following results were obtained. Peeling of sample iron plate before metal surface treatment: Not possible Peeling of sample iron plate after metal surface treatment: Easy Peeling of sample iron plate after five consecutive treatments: Easy

[Application Example 6] The treatment liquid prepared in the same manner as in Application Example 5 was applied to a mold for duplicating an optical disk. When the mold is immersed in the treatment solution, the metal surface treatment agent is firmly bonded to the surface of the mold and a coating made of an extremely thin metal surface treatment agent that does not adversely affect the very fine irregularities on the mold surface. Was formed. When the optical disk was repeatedly duplicated using this mold, the release of the optical disk from the mold was good.

[Application Example 7] The treatment liquid prepared in the same manner as in Application Example 5 was applied to the nozzle surface of an ink jet printer. The nozzle of the printer was immersed in the treatment liquid, dried while lightly flowing nitrogen gas, and then printing was performed. As a result, the wetting of the nozzle surface was reduced, the ejection direction of the ink was stabilized, and the dot formation was good.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C23C 26/00 C23C 26/00 Z G02F 1/1337 520 G02F 1/1337 520 // C09K 19/56 C09K 19 / 56 (72) Inventor Mitsuyoshi Ichihashi 200, Onakazato, Fujinomiya City, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd. 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (6)

[Claims] 1. A hydrophobic excluded volume effect compound represented by the following formula (I): (I) (Hb-) _m L (-Bu) _n [wherein Hb has 1 to 40 carbon atoms. Selected from the group consisting of a fluorine-substituted alkyl group, a fluorine-substituted aryl group having 6 to 40 carbon atoms, an alkyl group having 6 to 60 carbon atoms, and an alkyl-substituted oligosiloxanoxy group having 1 to 60 carbon atoms. A hydrophobic group; Bu
Is a group having an excluded volume effect including at least two cyclic structures; L is a (m + n) -valent linking group; and m and n are each independently an integer from 1 to 12.] . 2. The hydrophobic exclusion according to claim 1, wherein in the formula (I), Hb is a fluorine-substituted alkyl group having 1 to 40 carbon atoms or a fluorine-substituted aryl group having 6 to 40 carbon atoms. Volume effect compounds. 3. In the formula (I), m and n are each 1 and L is an -alkylene group-, -O-, -C
O -, - NR -, - SO 2 - and a divalent linking group selected from the group consisting of hydrophobic excluded volume effect of claim 1 R is a hydrogen atom or an alkyl group Compound. 4. The hydrophobic excluded volume effect according to claim 1, wherein in the formula (I), m and n are each independently an integer of 2 to 12, and L is a linking group containing a cyclic structure. Compound. 5. The hydrophobic excluded volume effect compound according to claim 1, wherein in the formula (I), the group having a excluded volume effect of Bu contains a tricyclic or tetracyclic fused ring. 6. The hydrophobic exclusion according to claim 1, wherein in the formula (I), the group having an excluded volume effect of Bu has a structure in which at least two rings are bonded by a single bond, a vinylene bond or an ethynylene bond. Volume effect compounds.