JPH03220140A - Optically active substance and liquid crystal composition containing the same substance - Google Patents

Abstract

NEW MATERIAL:An optically active substance expressed by formula I (R is 1-12C alkyl; Q is H, OH or COOH; (p) is 1 or 2; C* is asymmetric carbon atom). EXAMPLE:(-)-4-(3-Trifluoromethylheptyl)phenol. USE:An optically active substance which is not only useful as an optically active intermediate, but also capable of exhibiting high stability and large spontaneous polarization when induced into a liquid crystal compound. PREPARATION:The objective optically active substance expressed by formula VI among formula I is obtained from an optically active substance expressed by formula II through an optically active substance expressed by formulas III to V. Furthermore, when a liquid crystal composition containing the optically active substance expressed by formula I is used for a liquid crystal element, the element has a large spontaneous polarization, a good display characteristic and exhibits a high speed response.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel optically active substance and a liquid crystal composition containing the same.

[Prior Art] Conventionally, many types of optical elements characterized by having optical activity have been known, as exemplified below.

l) A method that utilizes the cholesteric-nematic phase transition effect in the liquid crystal state [Jay Jay Wysocki, A Adams, W Haas [Physics Review Letters J (J, J.

Wysoki, A., Adams and 11.
Haas; Phys, Rev.

Lett, ), 20.1024 (1968) ],
2) One that utilizes the White-Tiller type guest-host effect in the liquid crystal state [D.L. White, G.M.T.
, N, Taylor; J, 8pp1.
Pl+ys, ), 45. 4718 (+974)]
, 3) Chiral smectic C phase, H in liquid crystal state
Those that utilize the ferroelectric effects of phase, F phase, ■ phase, C phase, K phase, and J phase [FA Clark, N.
A, C1ark and S.

T, l, agerwall; Appl, P
hys, LetL, ), :16. 899 (1
980)] 4) By fixing a substance that has a cholesteric phase in a liquid crystal state in a matrix, its selective scattering properties are utilized to utilize it as a notch filter or a bandhus filter [F.C. Cano, "Applied Physics Letters J ( F,,1Kahn
; Appl, Phys, (,ett,), 1
8゜231 (1971)], which is used as a circularly polarized beam splitter using circular polarization characteristics [Nisday Jacob, "Nisp IE J (S, D
.

Jacobs, 5PIE), 37.98 (198
1) ;etc.

A detailed explanation of each method will be omitted; all of them are important as display elements and modulation elements.

Optically active substances are used as the main component of the functional materials constituting these optical elements, or as a relatively small amount, or as an important functional component. For example, Arnold H.
s, Chei+, ), 226.146 (1964
) discloses that the type and temperature range of the liquid crystal phase developed in the liquid crystal state can be controlled by adding other optically active substances or liquid crystal compounds to the above-mentioned optical element materials, especially liquid crystal materials. has been done. It is also expected that a compound with a large dipole can be introduced into a liquid crystal material driven by electric field response to obtain a liquid crystal material with better electric field response.

However, with conventionally known optically active substances, it is not easy to change the length of the group introduced, and many of them are unsuitable for controlling the liquid crystal state.

Many of such optically active functional materials are themselves synthesized via optically active intermediates.

Conventionally, optically active intermediates for synthesizing functional materials required for optical elements characterized by having optical activity include 2-methylbutanol, secondary octyl alcohol,
Secondary butyl alcohol, p-(2-methylphthyl) chloride
Benzoic acid, secondary phenethyl alcohol, amino# derivatives, camphor derivatives, cholesterol derivatives, etc. are known.

However, these have the following drawbacks.

It is difficult to modify the structure of optically active chain hydrocarbon derivatives.
Moreover, with the exception of some items, they are extremely expensive. Amino acid derivatives are relatively inexpensive and their structures can be easily changed, but the hydrogen groups of amines are chemically active and easily cause hydrogen bonds and chemical reactions, which limits the properties of functional materials. However, it is difficult to modify the structure of camphor derivatives and cholesterol derivatives, and they tend to adversely affect the properties of functional materials due to steric hindrance.

In addition, among optical elements characterized by having optical activity, in methods using electro-responsive optical effects in a liquid crystal state, has polar groups been introduced to improve responsiveness? Most optically active intermediates either have low polarity or do not utilize polar groups effectively.

In particular, in ferroelectric liquid crystals, it is known that the response speed is proportional to the spontaneous polarization, and it is desired to increase the spontaneous polarization in order to increase the speed. From this point of view, Piekeler (P.

showed that it is possible to increase spontaneous polarization and speed up the response speed by introducing a chlorine group into an asymmetric carbon (C.R. Academy Science).
C, R, Acad, Sc, Paris), 282
G.

639 (1976)).

However, the chlorine group introduced into the asymmetric carbon is not only chemically unstable but also has a large atomic radius, which reduces the stability of the liquid crystal phase. There is.

[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned circumstances, and its essential purpose is to provide a liquid crystalline compound that is useful as a suitable optically active intermediate. The object of the present invention is to provide an optically active substance that exhibits high stability and large spontaneous polarization when induced.

Another object of the present invention is to have large spontaneous polarization by containing the optically active substance. Another object of the present invention is to provide a liquid crystal composition that exhibits high-speed response and provides good display characteristics.

[Means for Solving the Problems] That is, the first invention of the present invention has the following general formula (I) (wherein,
R is an alkyl group having carbon atoms P1 to P12, Q is -H1- or -COOH, P is 1 or 2, and C'' is an asymmetric carbon atom.

A second aspect of the present invention is a liquid crystal composition containing at least one optically active substance represented by the general formula (I).

The present invention will be explained in detail below.

The optically active substance of the present invention has a structure represented by the general formula (I), or R in the formula (1) has a carbon number of 1 to 12, preferably a carbon number of 3 to 1O1, more preferably a carbon number of 4. ~6 alkyl group is shown. The alkyl group may be linear or branched, and the alkyl group may be substituted or unsubstituted.

The optically active substance represented by the general formula (1) of the present invention is:
It is a compound that can be used in a very wide range because various derivatives can be synthesized through ester bonds, ether bonds, urethane bonds, carbonate bonds, etc. without losing its optical activity.

Furthermore, the optically active substance of the present invention is LB (Langsui
When producing a monomolecular cumulative film by the r-Blodgett method, it is possible to easily control the hydrophobic groups.
It is a compound that can be stably formed into a film.

Next, the method for producing the optically active substance represented by the general formula (I) is preferably carried out in Japanese Patent Application No. 183485/1983 and Japanese Patent Application No. 17624 filed by the present applicant.
Optically active 3-trifluoromethylalkanoic acid or optically active 3-trifluoromethylalkanoic acid of the following general formula (II) shown in the specifications of No.
- It can be produced from optically active intermediates such as trifluoromethylalkanol.

1) When Q=OH (in the formula, R is an alkyl group having 1 to 12 carbon atoms, M is -
CH2C-, -CH2CH2-1C8 indicate an asymmetric carbon atom) The main production methods are shown below.

1) If Q=)I ii) If Q = COO1i ( ■ -1) ( ■ -2) ( D -3) ( ■ -4) ( ■-5) (however, R is an alkyl group having 1 to 12 carbon atoms, r is 0 or 1 * indicates an asymmetric carbon atom) Examples of compounds that can be produced as described above are shown below.

( ■ -6) ( ■ -7) ( Knee 8) ( I-9) ( I -10) ( ■ 11) ( ■ =12) ( ■ -13) ( ■ -14) ( ■ l5) ( ■ 21 ) ( ■ 22) ( ■ -23) ( ■ 24) ( Knee 25) ( ■ -16) ( Knee 17) ( ■ -18) ( I -19) ( ■ -20) ( ■ -26) ( ■ - 27) ( ■ -28) ( ■ -29) ( ■ -30) ( ■ 3I) ( ■ -32) ( ■ -33) ( ■ 34) ( ■ -35) ( ■ 41) ( ■ -42) ( ■ -43) ( ■ =44) ( ■ -45) ( ■ -36) ( ■ -37) ( ■ -38) ( ■ -39) ( ■ 40) ( ■ 46) ( ■ -47) ( ■ - 48) ( ■ -49) ( ■ -50) ( ■ 51) ( ■ 52) ( ■ -53) ( ■ 54) ( ■ 55) ( ■ 61) ( ■ -62) ( ■ 63) ( ■ 64) ( ■ -65) ( ■ 56) ( ■ 57) ( ■ 58) ( ■ 59) ( ■ -60) ( ■ -66) ( ■ -67) ( Eero 8) ( Eero 9) ( ■ -70) ( 1-71) (I-72) The optically active substance represented by the general formula (I) thus obtained is useful as an intermediate for producing a functional material forming an optical element. It is also used as an intermediate in the synthesis of various optically active substances.

Next, the liquid crystal composition of the present invention can be obtained by blending the optically active substance represented by the general formula (I) with a liquid crystal compound. By adding the optically active substance to a liquid crystal composition comprising a liquid crystal compound, various properties such as high-speed response of the composition can be improved, and good display properties can be obtained.

For example, the optically active substance represented by the general formula (1) is
By adding it to nematic liquid crystals, it is effective in preventing the occurrence of reverse domains in TN type cells. In this case, it is desirable to add the optically active substance of general formula (I) in a proportion of 0.01 to 50% by weight, preferably 0.1 to 10% by weight of the resulting liquid crystal composition.

Furthermore, by adding it to a nematic liquid crystal or a chiral nematic liquid crystal, the chiral nematic liquid crystal can be used as a liquid crystal composition in a phase change type liquid crystal element or a white dacy type guest-host type liquid crystal element. In this case, it is desirable to add the optically active substance of general formula (I) in a proportion of 0.1 to 80% by weight, preferably 0.1 to 20% by weight of the resulting liquid crystal composition.

Further, the optically active substance of the general formula (I) may be added to a liquid crystal composition exhibiting a ferroelectric chiral smectic liquid crystal state by itself, for example, in an amount of 0.01 to 8
By adding it in a proportion of 0% by weight, preferably 1 to 50% by weight, properties such as durability can be improved.

It can also be added to a smectic liquid crystal composition to provide a liquid crystal composition exhibiting a ferroelectric chiral smectic phase. In this case, 0.01 of the obtained liquid crystal composition
It is desirable to add the optically active substance of general formula (1) in a proportion of 80% by weight, preferably 1 to 50% by weight. In order to provide a chiral smectic liquid crystal composition, when the optically active substance of the general formula (I) is added and used, it becomes possible to obtain a large spontaneous polarization, shorten the response time, You can lower the threshold voltage.

Next, specific examples of compounds serving as constituent components of the ferroelectric chiral smectic liquid crystal composition and the smectic liquid crystal composition used in the present invention are listed below.

(2) (3) (4) (5) (6) (13) (14) (15) (16) (17) (18) (7) (8) (9) (lO) (11) (12 ) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (37) (38) (39) (40) ( 41) (42) (31) (32) (33) (34) (35) (36) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53) (60) (61) (62) (63) (64) (65) (54) (55) (56) (57) (58) (59) (66) (67) (68 ) (69) (71) (72) (73) (74) (75) (76) (77) (89) (78) (79) (80) (81) (82) (8 pieces) (90) (91) (92) (9) (94) Su (95) (96) (97) (98) (99) (105) (+06) (107) (108) (109) υ υ (100) ( 101) (102) (103) (104) (110) (Ill) (112) (113) (114) N υ υ (II5) (II6) (117) (118) (+19) (120) (126) (127) (+28) (129) (130) (131) Mouth (121) (122) (123) (124) (125) (1:12) (133) (134) (1:+5) (136) (137) (+38) 0 (139) (140) (141) (142) (143) (tSO) (151) (152) (153) (154) (155) C8゜Hz+0+CHg0+0CsH-s(144) (145 ) (146) (147) (148) (149) (156) (157) (158) (159) (160) (161) (162) (163) (164) (165) (166) (172) ( +73) (174) (175) (175) (177) (167) (168) (169) (170) (171) (178) (179) (181) (182) - υ [Action] Optics of the present invention The active substance has a structure represented by the general formula (I), and since a group having a large dipole moment is introduced into an asymmetric carbon atom, it can exhibit an excellent electric field response.

Further, since the liquid crystal composition of the present invention contains the optically active substance represented by the general formula (I), it has large spontaneous polarization and exhibits high-speed response.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Production of (-)-4-(3-1-trifluoromethylheptyl)phenol (-)-4-(3-trifluoromethylheptyl)phenol was produced according to the following steps.

Step 1) Production of (-)-4-(3-)-lifluoromethylheptanoyl)anisole Add (+)-3 to a mixture of 4.5 ml of carbon disulfide, 0.33 g of anisole, and 0.6 g of aluminum chloride. -4 m of thionyl chloride in 0.6 g of trifluoromethylhebutanoic acid
The acid chloride obtained by reacting with R was added, heated to 50°C, and stirred for 1 hour. After the reaction was completed, the mixture was cooled with ice, made acidic by adding hydrochloric acid, and extracted with diethyl ether. The obtained ether layer was washed with an aqueous sodium bicarbonate solution and dried over anhydrous sodium sulfate. Purification is performed by vacuum distillation to obtain the desired 4-(3-trifluoromethylheptanoyl).
0.48 g of anisole was obtained.

(Yield 55%) (bp, 140-150°C 10.451-Hg) Specific optical rotation [α]2'-19,8° (C: 1.22.Ct(
Cj'3) [α]'':', 5-50.1° (C3,22
, CHCl3) Step 2) Production of 4-(:1-)-lifluoromethylheptyl)anisole 0.1 g of lithium aluminum hydride was mixed with 2.5 x 2 of dry diethyl ether, and while stirring, aluminum chloride was added. 0.275g? 'Dry diethyl ether 2
．． 5 was added together with all. Furthermore, the 4- obtained in step 1)
(3-trifluoromethylheptanoyl)anisole 0
．． A solution of 48 g dissolved in a 2.5 mN diethyl ether solution was added, and the mixture was heated under reflux for 30 minutes. After the reaction was completed, 6N sulfuric acid (5sj) was added, and the mixture was extracted with diethyl ether. After drying the obtained ether layer over anhydrous sodium sulfate, the solvent was distilled off to obtain 0.46 g of 4-(quatrifluoromethylheptyl)anisole.

Step 3) Production of (-)-4-(3-)trifluoromethylheptyl)phenol 0.46 g of 4-(3-trifluoromethylheptyl)anisole obtained in Step 2) and 15 servings of acetic acid, A mixed solution of 2.8 ml of 47% hydrobromic acid was reacted by heating under reflux for 13 hours. After the reaction was completed, 50 mL of ice water was added,
Extraction was performed with diethyl ether, and the resulting ether layer was washed three times with an aqueous sodium bicarbonate solution. After drying over anhydrous sodium sulfate, the solvent was distilled off and purification was performed by distillation under reduced pressure to obtain the target product, 4-(3-trifluoromethylhebutyl).
0.24g of phenol was obtained.

(Yield 56%) (bp, 140-150°C 10.036s Hg) Specific optical rotation [α]2' -4,,5° (C3,11,CHCj'
z) [α] shi:, -7.8°(C3,11,CHCj'
3) Example 2 ITO (Indium Tin) as transparent material
A polyimide resin precursor (manufactured by Toshi Co., Ltd., 5p-sio) was formed on a glass substrate with a film formed thereon by spinner coating, and then baked at 300°C for 60 minutes to form a polyimide film. . Next, this coating was subjected to an orientation treatment by rubbing, and cells were created in such a manner that the coating was perpendicular to the rubbing treatment axis (cell spacing: 8 #Lm).

A nematic liquid crystal composition (Rixon GR-
63: Injected with biphenyl liquid crystal mixture (manufactured by Chisso Corp.),
When a TN (twisted nematic) cell was observed using a polarizing microscope, it was observed that a reverse domain (striped pattern) was present.

A TN cell was prepared in the same manner as above using a liquid crystal mixture in which the optically active substance of Example 1 of the present invention (1 part by weight) was added to the Rixon GR-63 (99 parts by weight),
When this was observed using a polarizing microscope, no reverse domain was observed and it was found to be a nematic phase with good uniformity.

From this, it was confirmed that the optically active substance of the present invention is effective in preventing reverse domains.

Example 3 The following exemplified compounds were mixed in the following parts by weight to prepare liquid crystal composition C.
It was created.

Exemplary compound no.

Structural Formula Further, the following exemplified compounds were mixed with the liquid crystal composition C in the weight parts shown below to prepare a liquid crystal composition.

Exemplary Compound No., Parts by Weight Liquid Crystal Composition C97 Next, two glass plates with a thickness of 0.71 were prepared, an ITO film was formed on each glass plate, a voltage application electrode was created, and a voltage application electrode was formed on each glass plate. 5iOz was vapor-deposited to form an insulating layer.

Silane coupling agent (manufactured by Shin-Etsu Chemical, K
BM-602) A 0.2% isopropyl alcohol solution was applied for 15 seconds using a spinner with a rotation speed of 2000 r, p, m, to perform surface treatment. After this, at 120°C for 20
A heating drying process was performed for a minute.

Furthermore, a polyimide resin precursor [manufactured by Toshi ■, 5P-510] was applied on a glass plate with an ITO film that had been surface treated.
Rotate 1.5% dimethylacetamide solution at 2000 r.
, p, m spinner for 15 seconds. After film formation,
A heating condensation firing process was performed at 300°C for 60 minutes. The thickness of the coating film at this time was about 250.

After firing, the film was rubbed with acetate flocked cloth, then washed with isopropyl alcohol, and alumina pieces with an average particle size of 2 μm were sprinkled on one glass plate, and each rubbed shaft was Make sure they are parallel to each other.

Glass plates were glued together using an adhesive sealant (manufactured by Chisso ■, Rixon Bond) and dried by heating at 100° C. for 60 minutes to create a cell. The cell thickness of this cell was measured using a Berek phase plate and was found to be about 2 l.

A ferroelectric liquid crystal element was prepared by injecting the mixed liquid crystal composition into this cell in an isotropic liquid state and slowly cooling it from the tokichi phase to 25°C at a rate of 20°C/h.

The uniform alignment within this liquid crystal element was excellent, and a monodomain state was obtained.

Example 4 Liquid crystal composition A was prepared by mixing the following parts by weight of the liquid crystal compounds exemplified below.

<Liquid crystal composition A> Exemplary compound no.

30 parts by weight υ 70 parts by weight 5 parts by weight of the optically active substance of Example 1 was added to this liquid crystal composition A to obtain a liquid crystal composition B.

Liquid crystal composition B exhibited an S■C'' phase, and its spontaneous polarization was 1.7 times that of liquid crystal composition A.

In addition, using a liquid crystal element prepared in the same manner as in Example 3 using the liquid crystal composition A and liquid crystal composition B, optical properties under crossed Nicols were measured by applying a peak-to-peak voltage of 20 V. The response speed was measured by detecting a typical response (change in amount of transmitted light from 0 to 90%). As a result, the response time of liquid crystal composition B was 10 m at 95°C under the condition of applying ±5 V.
5ec, which was about 60% of that of liquid crystal composition A.

Example 5 Production of (+)-4-(3-trifluoromethylnonyl)phenol In Example 1, instead of (+)-3-)-lifluoromethylhebutanoic acid, (-)-3-) (−)-4-(3-)-Lifluoromethylnonyl)phenol was obtained by performing the same steps except using lifluoromethylnonanoic acid.

(bp, 187℃10.33msHg) [α]+20.3", [αkoni:5+52.9'"(C
2,75,CHCj':+) (bp, 182℃10.40vsHg) [α]28
+ 2.4°, [α]2:5+7.1° (C1,5
1, CHCl'3) [Effects of the Invention] As explained above, according to the present invention, not only is it useful as an optically active intermediate, but it also exhibits high stability and large spontaneous polarization when induced into a liquid crystalline compound. It is possible to provide an optically active substance that provides

Furthermore, by using a liquid crystal composition containing the optically active substance of the present invention in a liquid crystal element, it is possible to obtain large spontaneous polarization, high-speed response, and good display characteristics.

Claims (2)

[Claims] (1) The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, R is an alkyl group having 1 to 12 carbon atoms, and Q is -
H, -OH or -COOH, P represents 1 or 2,
C^* indicates an asymmetric carbon atom) An optically active substance represented by: (2) The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (In the formula, R is an alkyl group having 1 to 12 carbon atoms, and Q is -
H, -OH or -COOH, P represents 1 or 2,
C^* indicates an asymmetric carbon atom) A liquid crystal composition comprising at least one optically active substance represented by: