JP2003277359A - Liquid crystalline 3,4-substituted pyrrole - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stable liquid crystalline compound having large dielectric constant anisotropy, regulated optical anisotropy and high compatibility, and to provide a liquid crystal display device using a liquid crystal composition containing the compound and drivable at low voltage. <P>SOLUTION: The compound is shown by formula (1) (wherein, Ra is H, a halogen atom, -CN, an alkyl or the like; A<SP>1</SP>, A<SP>2</SP>and A<SP>3</SP>are each 1,4- cyclohexylene, decahydro-2,6-naphthylene, 1,4-phenylene, 2,6-naphthylene or the like; Z<SP>1</SP>, Z<SP>2</SP>and Z<SP>3</SP>are each a single bond, alkylene or the like; Y<SP>1</SP>is F or -CF<SB>3</SB>; and m and n are each 0 or 1). A composition containing this compound, and the liquid crystal display device containing the composition are also provided, respectively. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystal compound. More specifically, a liquid crystal compound suitable as a component of a liquid crystal composition for TN mode, STN mode, TFT mode, or OCB mode, a liquid crystal composition containing the same, and a liquid crystal composition containing the same The present invention relates to a liquid crystal display device.

The term "liquid crystal compound" is used as a generic term for a compound which exhibits a liquid crystal phase and a compound which does not exhibit a liquid crystal phase but is useful as a component of a liquid crystal composition. A liquid crystal compound, a liquid crystal composition and a liquid crystal display device may be referred to as a compound, a composition and a device, respectively. The compounds represented by the formulas (1) to (12) are respectively converted from the compound (1) to the compound (12).
It may be written as. In formulas (2) to (12), structural units such as B, D, and E surrounded by hexagons are rings B,
Ring D, ring E and the like are shown.

[0003]

2. Description of the Related Art Liquid crystal display devices have twisted nematic (TN), dynamic scattering (DS), guest host (GH), orientation phase change (DAP), super twisted nematic (STN), and voltage controlled compound depending on the display method. Refraction (VCB, ECB or T
B), in-plane switching (IPS), vertical alignment (VA), multi-domain vertical alignment (MVA), optical compensation bend (OCB) and other modes. The properties of the composition required for the device depend on these modes. In any mode, the composition needs to be stable to moisture, air, heat, light and the like.

In recent years, there has been a demand for an element having a low driving voltage and a high contrast. To lower the drive voltage,
The dielectric anisotropy (Δε) of the composition may be increased (M.
F.Leslie, Mol. Cryst. Liq. Cryst., 1970, 12, 5
7). A composition having a small optical anisotropy (Δn) is suitable for the VA, MVA and IPS modes. Some modes require a composition with large optical anisotropy

[0005]

[Patent Document 1] JP-A-5-346563

[Patent Document 2] Japanese Patent Laid-Open No. 2000-226584

[Patent Document 3] European Patent Application Publication No. 421408

[Patent Document 4] European Patent Application Publication No. 886179

[Non-Patent Document 1] J. Leroy et al., Tetrahedron Let
t., 35 , 8605 (1994).

[Non-Patent Document 2] J. Leroy et al., J. Fluorine Che
m., 25 , 255 (1984).

[0006]

The object of the present invention is to provide a stable liquid crystal compound having a large dielectric anisotropy, a controlled optical anisotropy and an excellent compatibility with other liquid crystal compounds, It is to provide a liquid crystal composition containing this compound. Another object of the present invention is to provide a liquid crystal display device that can be driven at a low voltage by using this composition.

[0007]

In order to achieve the above object, the constitution of the present invention is as described in items 1 to 26. 1. A compound represented by formula (1). In the formula (1), Ra is hydrogen, halogen, —CN, or alkyl having 1 to 20 carbon atoms, and in this alkyl, any —CH ₂ — is —O—, —S—, —CH═.
CH -, - C≡C-, or -SiH ₂ - may be replaced by, and any hydrogen may be replaced by halogen.

"Any -CH in alkyl_Two-Is-
O-, -CH = CH-, etc. "
The meaning of the phrase is shown by an example. C_FourH₉At-CH_Two−
A part of a group in which is replaced by -O- or -CH = CH-
Is C_ThreeH₇O-, CH_Three-O- (CH_Two)₂-, CH_Three
-O-CH_Two-O-, H_TwoC = CH- (CH_Two)_Three-,
CH_Three-CH = CH- (CH_Two)₂-, CH_Three-CH =
CH-CH_Two-O-. Thus any word is
Means "at least one". Consider the stability of the compound
Considering that CH is adjacent to oxygen_Three-OO-CH
_Two-Rather than CH _Three-O-CH_Two-O- is preferred
Yes.

Preferred Ra is hydrogen, halogen, cyano, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy, alkylsilyl, and alkylsilylalkyl. Also preferred are those groups in which at least one hydrogen has been replaced by halogen. Preferred halogens are fluorine and chlorine. These groups are preferably linear rather than branched. The preferred carbon number is 1-10. The configuration of -CH = CH- is preferably trans rather than cis. Particularly preferred Ra is fluorine, alkyl, alkoxy, and alkenyl.

A ¹ , A ² and A ³ are independently 1,4
- cyclohexylene, decahydro-2,6-naphthylene, 1,4-phenylene or 2,6-naphthylene,, any hydrogen in these rings may be replaced by halogen, arbitrary -CH ₂ - , -O-, -S
-, - CH = CH -, - CO-, or -SiH ₂ - may be replaced by, and any -CH = can -N =
May be replaced with.

Preferred A ¹ , A ² or A ³ are 1,4
-Cyclohexylene, 1,4-cyclohexynylene,
1,3-dioxane-2,5-diyl, decahydro-
2,6-naphthylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4
-Phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,
3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-2,
5-diyl, 2,6-naphthylene, 1-fluoro-2,
6-naphthylene, and 1,3-difluoro-2,6-
It is naphthylene. 1,4-cyclohexylene and 1,3
The conformation of -dioxane-2,5-diyl is preferably trans rather than cis.

Z ¹ , Z ² and Z ³ are independently a single bond or alkylene having 1 to 4 carbon atoms, and in the alkylene, any —CH ₂ — is —O—, —S—, —CH═CH.
-, - C≡C -, - CO- , or -SiH ₂ - may be replaced by, and any hydrogen may be replaced by halogen.

Preferred Z¹, Z^TwoOr Z^ThreeIs-(CH
_Two)_Two-, -CH_TwoO-, -OCH _Two-, -CF_TwoO
-, -OCF_Two-, -CH_TwoSiH_Two-, -SiH_TwoC
H_Two-, -COO-, -OCO-, -CH_TwoCO-,-
COCH_Two-, -CH = CH-, -CF = CF-, -C
≡ C-,-(CH_Two)_Four-,-(CH_Two)_TwoCF_TwoO
-, And -OCF_Two(CH_Two)_Two− -CH =
The configuration of CH- and -CF = CF- is higher than that of cis.
Lance is preferred.

Y ¹ and Y ² are independently fluorine or trifluoromethyl (--CF ₃ ). m and n are independently 0 or 1. A compound in which m and n are 0 has 2 rings. The compound in which m is 0 and n is 1 has 3 rings. The compound in which m and n are 1 has 4 rings.
Since there is no big difference in the properties of the compounds, compound (1)
^It may be composed of isotopes such as ² H (deuterium) and ¹³ C.

2. Ra is alkyl having 1 to 20 carbons, and in this alkyl, any —CH ₂ — is —O.
-, - S -, - CH = CH-, or may be replaced by -C≡C-, and any hydrogen may be replaced by ^{halogen; A} 1, A ² and ^{A 3} are independently 1,4-cyclohexylene, 1,3-dioxane-2,
5-diyl or 1,4-phenylene in which any hydrogen may be replaced by halogen; Z ¹ and Z ² are independently a single bond, — (CH ₂ ) ₂ —, —COO—, —O.
_{CO -, - CH 2 O -} , - OCH 2 -, - CF 2 O-,
_{-OCF 2 -, - CH = CH} -, - CF = CF -, - C
_{≡C -, - (CH 2)} 4 -, - (CH 2) 2 -CF 2 O
- _{(CH 2) 2} - - a and, ^{Z 3} is a single _bond, - or _{-OCF 2, (CH 2) 2} -, - OCO -, - CH 2 CO
-, - CH = CH -, - CF = CF -, - C≡C-, or - _{(CH 2) 4} - A compound according to claim 1 is.

3. Item 1 or 2 in which m and n are 0
The compound according to. 4. Item 3. The compound according to item 1 or 2, wherein m is 0 and n is 1. 5. Item 3. The compound according to Item 1 or 2, wherein m and n are 1. 6. Item 3. The compound according to item 1 or 2, wherein Z ³ is — (CH ₂ ) ₂ —. 7. Item ^3. The compound according to Item 1 or 2, wherein Z ³ is a single bond. 8. Item 1 in which all of Z ¹ , Z ² and Z ³ are single bonds
Or the compound according to 2.

9. Item 1 wherein A ¹ , A ² and A ³ are independently 1,4-cyclohexylene or 1,4-phenylene in which arbitrary hydrogen may be replaced by halogen.
Or the compound according to 2. 10. A ¹ and A ³ are 1,4-cyclohexylene, Z ¹ and Z ³ are single bonds, m is 1, and
The compound according to Item 1 or 2, wherein n is 0. 11. Item 3. The compound according to item 1 or 2, wherein at least one of Z ¹ and Z ² is —CF ₂ O—.

12. At least one base selected from the group consisting of sodium hydride, potassium hydride, lithium hydride, sodium hydroxide, and potassium hydroxide.
By the reaction of 3,4-difluoropyrrole with an organic halide at a temperature of 0 ° C. or higher and 200 ° C. or lower,
Alternatively, a method for producing a liquid crystalline 3,4-difluoropyrrole derivative or a liquid crystalline 3,4-bis (trifluoromethyl) pyrrole derivative by reacting 3,4-bis (trifluoromethyl) pyrrole with an organic halide.

13. Item 1 to 11 containing at least one liquid crystal compound, at least 2
A composition of ingredients. 14. As the first component, at least one compound according to any one of items 1 to 11 is contained, and as the second component, selected from the group of compounds represented by formulas (2), (3) and (4). A composition containing at least one compound as defined above. In the formula, R ¹ is alkyl having 1 to 10 carbon atoms, and in this alkyl, any —CH ₂ — is —O— or —CH.
═CH— and any hydrogen may be replaced by fluorine; X ¹ is fluorine, chlorine,
_{-OCF 3, -OCHF 2, -CF 3} , -CHF 2, -C
_{H 2 F, -OCF 2 CHF 2} , or -OCF ₂ CHF
CF ₃ ; L ¹ and L ² are independently hydrogen or fluorine; Z ⁴ and Z ⁵ are independently — (CH ₂ ) _{2
-, - (CH 2) 4} -, - COO -, - CF 2 O -, - O
CF ₂ —, —CH═CH—, or a single bond; ring B
And ring D is independently 1,4-cyclohexylene, 1,
3-dioxane-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine, ring E is 1,4-cyclohexylene or in which any hydrogen is replaced by fluorine. Good 1,4-phenylene.

15. Formulas (1b-1-1) and (1b-1
-2) and at least one compound selected from the group of compounds represented by (1b-2-1), the compound represented by formula (3-2-1):
And at least one compound selected from the group of compounds represented by (3-3-1), and formula (3-23-1)
And a composition containing at least one compound selected from the group of compounds represented by (3-24-1). In the formula, Ra is hydrogen, halogen, —CN, or carbon number 1
Alkyl of 20, any _-CH 2 - in the alkyl may, -O -, - S -, - CH = CH -, - C
≡C-, or -SiH _2- may be substituted.
And any hydrogen may be replaced by a halogen;
R ¹ is alkyl having 1 to 10 carbons, and in this alkyl, any —CH ₂ — is —O— or —CH═CH.
May be replaced by-and any hydrogen may be replaced by fluorine.

16. As the first component, at least one compound according to any one of items 1 to 11 is contained, and as the second component, a compound selected from the group of compounds represented by formulas (5) and (6). A composition containing at least one. In the formula, R ² and R ³ are independently alkyl having 1 to 10 carbon atoms, and in this alkyl, any —CH ₂ — may be replaced by —O— or —CH═CH—,
And any hydrogen may be replaced by fluorine; X
² is -CN or -C≡C-CN; ring G is 1,4
-Cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5
-Diyl; ring J is 1,4-cyclohexylene, 1,4-phenylene in which any hydrogen may be replaced by fluorine, or pyrimidine-2,5-diyl; ring K is 1,4- in there cyclohexylene or 1,4-phenylene; ^{Z 6} is _{- (CH 2) 2 -,} - COO -, - C
_{F 2 O -, - OCF 2} -, or a single ^{bond; L} 3,
L ⁴ and L ⁵ are independently hydrogen or fluorine;
b, c and d are independently 0 or 1.

17. As a first component, at least one compound according to any one of items 1 to 11 is contained, and as a second component, selected from the group of compounds represented by formulas (7), (8) and (9). A composition containing at least one compound as defined above. In the formula, R ⁴ and R ⁵ are independently alkyl having 1 to 10 carbon atoms, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—,
And any hydrogen may be replaced by fluorine; ring M and ring P are independently 1,4-cyclohexylene or 1,4-phenylene; L ⁶ and L ⁷ are independently hydrogen or fluorine. Yes, at least 1 of L ⁶ and L ⁷
Is fluorine; Z ⁷ and Z ⁸ are independently-(CH
₂ ) _2- , -COO- or a single bond.

18. As a first component, at least one compound according to any one of items 1 to 11 is contained, and as a second component, from the group of compounds represented by the formulas (2), (3) and (4). A composition comprising at least one compound selected and, as a third component, at least one compound selected from the group of compounds represented by formulas (10), (11) and (12). In the formula, R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons, and in this alkyl, any —CH ₂ — may be replaced by —O— or —CH═CH—,
And any hydrogen may be replaced by fluorine; ring Q, ring T and ring U are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or any hydrogen is replaced by fluorine. 1,4-phenylene may be also present; Z ⁹ and Z ¹⁰ are independently -C≡C-, -CO.
_{O -, - (CH 2)} 2 -, - CH = CH-, or a single bond.

19. A compound containing at least one compound according to any one of items 1 to 11 as a first component, and a compound selected from the group of compounds represented by the formulas (5) and (6) as a second component. Containing at least one
As the third component, the above formulas (10), (11) and (1
A composition containing at least one compound selected from the group of compounds represented by 2).

20. As a first component, at least one compound according to any one of items 1 to 11 is contained, and as a second component, from the group of compounds represented by the formulas (7), (8) and (9). At least one compound selected is contained, and as the third component, at least one compound selected from the group of compounds represented by the formulas (10), (11) and (12) is contained. Composition.

21. As a first component, at least one compound according to any one of items 1 to 11 is contained, and as a second component, from the group of compounds represented by the formulas (2), (3) and (4). At least one compound selected from the group of compounds represented by the formulas (5) and (6) is contained as a third component.
As the fourth component, containing the above formulas (10) and (11).
And a composition containing at least one compound selected from the compound group represented by (12).

22. Item 22. The composition according to any one of items 13 to 21, further containing at least one optically active compound. 23. Any one of items 13 to 22
A liquid crystal display device containing the composition according to the item.

24. The compound according to claim 1 or 2, wherein Y ¹ and Y ² are fluorine. 25. The compound according to claim 1 or 2, wherein Y ¹ and Y ² are trifluoromethyl. 26. The compound according to claim 1 or 2, wherein Y ¹ is fluorine and Y ² is trifluoromethyl.

Preferred groups in the compounds (2) to (12) are as follows. Alkyl is preferably linear rather than branched. 1,4-cyclohexylene and 1,
Regarding the conformation of 3-dioxane-2,5-diyl, trans is preferable to cis. These compounds may be composed of isotopes such as ² H (deuterium) and ¹³ C because there is no great difference in the properties of the compounds. Incidentally, - the meaning of the phrase "optional -CH ₂ - in the alkyl may be replaced by -O- or -CH = CH-" was described in the section 1 of the configuration of the present invention. Although symbols such as R ¹ and ring B are used in a plurality of compounds, these R ¹ (or ring B) may be the same or different.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION First, the compound (1) of the present invention will be further described. The compound (1) is a 3,4-difluoropyrrole derivative or 3,4-difluoropyrrole derivative having a large dielectric anisotropy.
It is a bistrifluoromethylpyrrole derivative. The dielectric anisotropy of the compound (A) is calculated from the corresponding 3,4-difluorophenyl derivative (Mol. Cryst. Liq. Cryst., 1991, 20
Larger than that of (see 9, 1).

The effects of the types of the terminal group Ra, the rings A ^{1 to} A ³ and the bonding groups Z ^{1 to} Z ^{3 on} the characteristics of the compound (1) will be described. When compound (1) is added to the composition, this property is reflected in that of the composition. Ra of compound (1)
Is a linear alkyl, the temperature range of the liquid crystal phase is wide and the viscosity is low. When Ra is branched alkyl, it has good compatibility with other liquid crystal compounds. When Ra is an optically active alkyl, it can be used as a chiral dopant. In these groups, any —CH ₂ — is —O—, —S—, —CH═CH—,
Or when replaced by -C [identical to] C-, or when any hydrogen is replaced by halogen, the compounds have similar properties.

When the ring A ¹ , A ² or A ³ is 1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, the optical anisotropy is small and the viscosity is low. When the ring is decahydro-2,6-naphthylene, the optical anisotropy is small and the compatibility is good. When the ring is 1,4-phenylene or 1,4-phenylene in which arbitrary hydrogen is replaced by halogen, the optical anisotropy is large and the viscosity is low. When the ring is 2,6-naphthylene, the optical anisotropy is large and the range of the nematic phase is wide.

The linking group Z ¹ , Z ² or Z ³ is a single bond,
When CH = CH- and -CF = CF-, the viscosity is low. Linking group is - _{(CH 2) 2} - or - _{(CH 2) 4} -
When, the compatibility is good. When the bonding group is -C≡C-, the clearing point is high and the viscosity is low. When the bonding group Z ¹ or Z ² is —COO— or —CF ₂ O—, the dielectric anisotropy is particularly large.

When Y ¹ and Y ² are fluorine, the clearing point is high. When Y ¹ and Y ² are trifluoromethyl, the dielectric anisotropy is large. When Y ¹ is fluorine and Y ² is trifluoromethyl, the compound has intermediate properties. The bicyclic compound has a large dielectric anisotropy and the temperature range of the liquid crystal phase is wide on the low temperature side. The compound having three rings has a high clearing point. The 4-ring compound has a large dielectric anisotropy and a particularly high clearing point.

Preferred compound (1) is compound (1a-
1) to (1f-7).

[0036]

[0037]

[0038]

[0039] In the formula, Ra, Z ¹ , Z ² , and Z ³ are the same as those of item 1 in the constitution of the present invention.

The compound (1) is the 4th edition, Experimental Chemistry Course (Maruzen), Organic Synthesis (Organic Synthesi).
s, John Wiley & Sons, Inc), Organic Reactions, John Wiley & Sons, In
It can be synthesized by appropriately selecting and combining the methods described in c) or other literatures. 3,4-
Difluoropyrrole rings have been described in the literature (J. Leroy, Tetrahedron
It can be synthesized by the method described in Letters, 1994, 35 (46), 8605). The 3,4-bis (trifluoromethyl) pyrrole ring is described in the literature (J. Leroy et al, Synthesis, 1982, 4,3
It can be synthesized by the method described in 13). A linking group Z ¹ ,
An example of a method of generating Z ² or Z ³ will be described in items (I) to (IX). Before that, the scheme of the generation method is shown. In this scheme, MSG ¹ and MSG ² are organic chemical groups. One of these is an organic chemical group containing a 3,4-difluoropyrrole ring or a 3,4-bis (trifluoromethyl) pyrrole ring. The compounds (1-1) to (1-9) correspond to the compound (1).

[0041]

[0042]

[0043]

[0044]

(I) Generation of single bond It was synthesized with an aryl boric acid derivative (21) by a known method.
(22) with an aqueous carbonate solution and a catalyst such as tetrakis.
Striphenylphosphine palladium (Pd (PPh ₃)_Four)of
Compound (1-1) is combined by reacting in the presence of
To achieve. This compound (1-1) was synthesized by a known method.
Compound (23) with n-butyllithium (n-BuLi)
Zinc chloride, dichlorobistriphenylphosphine
Tin palladium (PdCl₂(PPh₃)₂) Like a catalyst, and
Compound (22) can be synthesized by sequentially acting.
I can do it.

(II) Formation of -COO- and -OCO- After butyllithium is caused to act on the compound (23) to induce a lithiated product, carbon dioxide is caused to act to obtain a carboxylic acid (24). This is dehydrated and condensed with an alcohol (25) or a phenol (25) synthesized by a known method to synthesize a compound (1-2) having —COO—. A compound having -OCO- can also be synthesized by this method.

(III) Formation of -CF ₂ O- and -OCF _2- Compound (1-2) is treated with a sulfurizing agent such as Lawesson's reagent to give compound (26). This compound was converted into hydrogen fluoride pyridine complex (M. Kuroboshi et al., Chem. Let.
t., 1992, 827) or diethylaminosulfur trifluoride (William H. Bunnelle et al., J. Org. Chem.
1990, 55, 768) to fluorinate the compound (1-3) having —CF ₂ O—. By this method -OC
F 2 _- can also be synthesized that compounds with.

(IV) Formation of -CH = CH- Compound (27) synthesized by a known method is added with potassium t-
A base such as butoxide (t-BuOK) is allowed to act to generate phosphorus ylide. On the other hand, the compound (23) is reacted with butyllithium to induce a lithiated product, and then a formamide such as N, N-dimethylformamide is reacted to obtain an aldehyde (28). This is reacted with phosphorus ylide to synthesize the compound (1-4). Depending on the reaction conditions, a cis isomer is produced, and thus it is isomerized to the trans isomer by a known method.

(V)-(CH ₂ ) ₂ -Production Compound (1-4) is catalytically hydrogenated in the presence of a catalyst such as palladium carbon (Pd-C) to give Compound (1-5). To synthesize.

Production of (VI)-(CH ₂ ) ₄ — Using the compound (29) in place of the compound (27) to produce —CH═CH— according to the method (IV), and further catalytically hydrogenating the compound (29). 1-6) are synthesized.

(VII) Formation of -C≡C- In the presence of a catalyst of dichloropalladium and copper halide,
2-Methyl-3-butyn-2-ol is allowed to act on compound (23), and then deprotected under basic conditions to obtain compound (30). Compound (1-7) is synthesized by reacting compound (30) with compound (22) in the presence of a catalyst of dichloropalladium and copper halide.

(VIII) -CF = CF-Production Compound (23) is reacted with butyllithium to induce a lithiated product, and then tetrafluoroethylene is reacted to obtain compound (31). Lithiated compounds derived from the action of n-butyllithium on compound (22) and compound (3
Compound (1-8) is synthesized by reacting with 1).

(IX) -CH ₂ O- or -OCH _2- forming compound (28) is reacted with a reducing agent such as sodium borohydride (NaBH ₄ ) to obtain compound (32). This is converted to compound (33) with a halogenating agent such as hydrobromic acid. Compound (33) is reacted with compound (25) in the presence of potassium carbonate or the like to synthesize compound (1-9).

Next, the composition of the present invention will be further described.
The amount of compound used (percentage) is% by weight based on the total weight of the composition. This composition may contain only a plurality of compounds selected from the compound (1). A preferred composition contains at least one compound selected from the compound (1) in a proportion of 0.1 to 99%. This composition comprises at least one compound selected from the group of compounds (2), (3) and (4) as the second component, or compound (5).
And at least one compound selected from the group (6) may be contained. To reduce the dielectric anisotropy,
At least one compound selected from the group of compounds (7), (8) and (9) may be added. In order to adjust the threshold voltage, temperature range of liquid crystal phase, optical anisotropy, dielectric anisotropy, viscosity, etc., the compounds (10), (1
At least one compound selected from the groups of 1) and (12) may be further added to the composition. Other compounds may be added for the purpose of adjusting the physical properties of the obtained composition.

The compounds (2), (3) and (4) have positive dielectric anisotropy and are excellent in thermal stability and chemical stability. Used for. In this composition, the amount of these compounds used is 1 to 99%. It is preferably 10 to 97%, more preferably 40 to 95%. For the purpose of adjusting the temperature range of the liquid crystal phase, optical anisotropy, dielectric anisotropy, viscosity, or threshold voltage, the compound (10), (11) or (1
2) may be further added to the composition.

Since the compounds (5) and (6) have a large dielectric anisotropy, they are mainly used in compositions for STN and TN modes. These compounds are used for the purpose of broadening the temperature range of the liquid crystal phase of the composition, adjusting the optical anisotropy and viscosity, lowering the threshold voltage, improving the steepness of the threshold voltage, etc. . In the composition for STN or TN mode, the amount of compound (5) or (6) used is in the range of 0.1 to 99.9%. Preferably 10
˜97%, more preferably 40 to 95%. In order to adjust the temperature range of the liquid crystal phase, optical anisotropy, dielectric anisotropy, viscosity, or threshold voltage, the compound (10), (1
1) or (12) may be further added.

The compounds (7), (8) and (9) are used in a composition having a negative dielectric anisotropy. It is preferable to add at least one compound selected from the compounds (7), (8) and (9) to the composition for VA mode or the like. Increasing the amount of these compounds used decreases the threshold voltage of the composition but increases the viscosity. Therefore, as long as the required value of the threshold voltage is satisfied, a small amount used is preferable. Since the dielectric anisotropy of these compounds is negative and their absolute value is small, the amount used is 40%.
The above is preferable. It is more preferably 50 to 95%.
These compounds may be added to the composition having a positive value of dielectric anisotropy for the purpose of adjusting the elastic constant and the voltage transmittance curve. The amount used at this time is preferably 30% or less.

Compounds (10), (11) and (12)
The absolute value of the dielectric anisotropy of is small. The compound (10) is mainly used for the purpose of adjusting optical anisotropy or viscosity. The compounds (11) and (12) are used for the purpose of increasing the clearing point to widen the temperature range of the liquid crystal phase or adjusting the optical anisotropy. Increasing the amount of compounds (10), (11) and (12) used will increase the threshold voltage of the composition and decrease the viscosity. Therefore, a large amount may be used as long as the required threshold voltage of the composition is satisfied. In the composition for TFT mode, the amount of these compounds used is preferably 40% or less, more preferably 3% or less.
It is 5% or less. The amount of these compounds used in the composition for STN or TN mode is preferably 70%.
Or less, more preferably 60% or less.

Preferred compounds (2) to (12) are compounds (2-1) to (2-9) and compound (3-), respectively.
1) to (3-97), compounds (4-1) to (4-3)
3), compounds (5-1) to (5-56), compound (6-
1) to (6-3), compounds (7-1) to (7-3), compounds (8-1) to (8-5), compounds (9-1) to (9).
-3), compounds (10-1) to (10-11), compounds (11-1) to (11-18), and compound (12-
1) to (12-6). In these compounds,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X ¹ , and X ² are the same as those described in the constitution of the present invention.

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[0090]

The compositions of the present invention are prepared by known methods. For example, the component compounds are mixed and heated to dissolve each other. The properties may be adjusted by adding suitable additives to the composition. Such additives are well known to those skilled in the art. A chiral dopant or the like is added for the purpose of inducing a helical structure of liquid crystal to give a necessary twist angle and preventing reverse twist. Examples of chiral dopants are the optically active compounds (Op-1) to (Op-12) shown above.

A chiral dopant is added to the composition to adjust the pitch of twist. The twist pitch is preferably in the range of 40 to 200 μm for the TFT and TN modes and in the range of 6 to 20 μm for the STN mode. Bistable TN
1.5-4μ for (Bistable TN) mode
A range of m is preferred. At least two chiral dopants may be added for the purpose of adjusting the temperature dependence of pitch.

The composition for GH mode may be prepared by adding a dichroic dye such as merocyanine type, styryl type, azo type, azomethine type, azoxy type, quinophthalone type, anthraquinone type and tetrazine type.

The composition of the present invention comprises NCAP prepared by encapsulating nematic liquid crystal in a microcapsule, polymer dispersed liquid crystal display device (PDLCD) in which a three-dimensional network polymer is formed in the liquid crystal, for example, polymer network liquid crystal display. It can be used for devices (PNLCD). Further, it can be used for a birefringence control (ECB) mode and a DS mode.

[0095]

The present invention will be described in more detail with reference to the following examples. C, N and I at the phase transition temperature of the compound
Represent a crystal, a nematic phase and an isotropic liquid phase, respectively. C ₁ and C ₂ mean crystals different from each other.
The unit of temperature is ° C. No. Numbers such as 6 correspond to the compounds listed in Example 4.

Example 1 N- [2- [4- (4-propylcyclohexyl) cyclohexyl] ethyl] -3,4-difluoropyrrole (N
o. Synthesis of 6)

In a 50 mL three-necked flask, J. Leroy, Tetr
ahedron Letters, 1994, 35 (46), 8605, 3,4-difluoropyrrole (0.26 g;
2.5 mmol) in dimethyl sulfoxide (5 ml) was added with 30% potassium hydride (0.70 g; 5.2 mm).
ol) was added and the mixture was stirred at room temperature for 30 minutes. 1-
A solution of bromo-2- [4- [4-propylcyclohexyl] cyclohexyl] ethane (1.57 g; 5.0 mmol) in dimethyl sulfoxide (5 ml) was added, and the mixture was stirred at room temperature for 2 hours.
Stir for hours. After the reaction was stopped by adding water, diethyl ether was added. The organic layer was separated, and the aqueous layer was extracted with diethyl ether. The organic layers were combined, washed with brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to give the title compound (0.84 g; 2.5 mmol; yield 100%). This compound was a colorless crystal having a nematic phase. Phase transition temperature (° C.): C ₁ 36.3 C ₂ 63.7
N 79.6 I.D. ¹ H-NMR (CDCl ₃ ; δ p
pm): 6.23 (d, 2H), 3.68 (t, 2)
H), 1.74-1.66 (m, 8H), 1.56
(Q, 2H), 1.33 to 1.26 (m, 2H), 1.
41-1.09 (m, 4H), 1.03-0.79
(M, 13H).

Example 2 N- [2- (4-pentylcyclohexyl) ethyl]-
Synthesis of 3,4-difluoropyrrole (No. 2)

In a 50 ml three-necked flask, to a solution of 3,4-difluoropyrrole (0.26 g; 2.5 mmol) in dimethyl sulfoxide (10 ml) was added 30% potassium hydride (0.67 g, 5.0 mmol), and the mixture was allowed to stand at room temperature. 3
Stir for 0 minutes. Furthermore, 1-bromo-2- (4-pentylcyclohexyl) ethane (0.98 g; 3.8 mmo
A solution of 1) in dimethyl sulfoxide (3 ml) was added, and the mixture was stirred at room temperature for 2 hours. After water was added to stop the reaction, diethyl ether was added, the organic layer was separated, and the aqueous layer was extracted with diethyl ether. The organic layers were combined, washed with brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to give the title compound (0.37 g; 1.3 mmol; yield 65%). This compound was a colorless liquid at room temperature. Phase transition temperature (° C.): C 0.6 I.V. ¹ H-NMR (CDCl ₃ ; δ ppm): 6.23
(D, 2H), 3.68 (t, 2H), 1.74-1.
69 (m, 4H), 1.57 (q, 2H), 1.31-
1.19 (m, 6H), 1.17-1.11 (m, 4
H), 0.97-0.82 (m, 7H).

Example 3 N- [2- [4- (4-pentylcyclohexyl) cyclohexyl] ethyl] -3,4-difluoropyrrole (N
o. Synthesis of 6)

In a 50 mL three-necked flask, 30% potassium hydride (0.67 g; 5.0 mmol) was added to a solution of 3,4-difluoropyrrole (0.26 g; 2.5 mmol) in dimethylsulfoxide (5 ml), and the mixture was cooled to room temperature. At 3
Stir for 0 minutes. Furthermore, 1-bromo-2- [4- [4-pentylcyclohexyl] cyclohexyl] ethane (1.7
2 g; 5.0 mmol) of dimethyl sulfoxide (5 m
l) The solution was added and stirred at room temperature for 2 hours. After the reaction was stopped by adding water, diethyl ether was added. The organic layer was separated, and the aqueous layer was extracted with diethyl ether. The organic layers were combined, washed with brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to give the title compound (0.91
g; 2.5 mmol; yield 100%) was obtained. This compound was a colorless crystal having a nematic phase. Phase transition temperature (° C.): C 70.5 N 90.2 I.D. ¹ H-NMR (CDCl ₃ ; δ ppm): 6.23
(D, 2H), 3.68 (t, 2H), 1.75-1.
67 (m, 8H), 1.56 (q, 2H), 1.33-
1.18 (m, 6H), 1.16-1.07 (m, 4
H), 1.00-0.79 (m, 13H).

Example 4 Based on the description of Examples 1 to 3 and the detailed description of the invention,
The following compound No. 1-No. 110 is synthesized. The compounds obtained in Examples 1, 2 and 3 were also added.

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Uses of Representative Compositions of the Invention Examples 1-16
Summarized in. First, the compounds that are the components of the composition and their contents are shown. The compounds are represented by symbols for the left terminal group, the bonding group, the ring structure and the right terminal group according to the conventions in Table 1 shown below. However, the compound (1) does not have a right terminal group (-X). The numbers in parentheses correspond to the compounds shown in the table of Example 4. The compound content is% by weight. Next, the physical properties of the composition are shown. The method for measuring the physical property values is as follows.

Phase transition temperature of nematic-isotropic liquid (clearing point, NI; unit is ° C): The sample was placed on a hot plate equipped with a polarization microscope and heated at a rate of 1 ° C / min.
The temperature was measured when the sample started to change from a nematic phase to an isotropic liquid phase.

Viscosity (η; measurement temperature is 20.0 ° C .; unit is mPa · s): An E-type viscometer was used for viscosity measurement.

Optical anisotropy (Δn; measurement temperature 25.0)
(° C.): The optical anisotropy was measured using an Abbe refractometer with light having a wavelength of 589 nm.

Dielectric anisotropy (Δε; measurement temperature is 25.0)
C.): The gap between two glass substrates is 9 μm,
The sample was put in a liquid crystal cell having a twist angle of 80 °. A voltage of 10 V was applied to this cell, and the dielectric constant (ε∥) of the liquid crystal molecule in the long axis direction was measured. 0.5 V was applied and the dielectric constant (ε⊥) in the short axis direction of liquid crystal molecules was measured. The value of the dielectric anisotropy was calculated from the formula of ε∥-ε⊥.

Threshold voltage (Vth; measured temperature is 25.
0 ° C .; unit is Volt: The distance between two glass substrates is (0.5 / Δn) μm, and the twist angle is 8
0 °, normally white type
The sample was put in the liquid crystal display device of ype). Δn is a value of optical anisotropy measured by the above method. A rectangular wave having a frequency of 32 Hz was applied to this element. The voltage of the rectangular wave was increased, and the voltage value was measured when the transmittance of light passing through the device reached 90%.

When 0.8% by weight of the optically active compound (Op-4) was added to the composition of Use Example 1, the pitch of the composition was 10.8 μm. When 0.3% by weight of the optically active compound (Op-8) was added to the composition of Use Example 8, the pitch of the composition was 78.7 μm.

[0121]

[0122] Usage example 1         3-HBCb (F2) (No. 11) 5.0%         3-HCF2OBCb (F2) (No. 15) 10.0%         1V2-BEB (F, F) -C 5.0%         3-HB-C 15.0%         1-BTB-3 5.0%         2-BTB-1 5.0%         3-HH-4 11.0%         3-HHB-1 11.0%         3-HHB-3 9.0%         3-H2BTB-2 4.0%         3-H2BTB-3 4.0%         3-H2BTB-4 4.0%         3-HB (F) TB-2 6.0%         3-HB (F) TB-3 6.0%         NI = 91.3 (° C)         η = 22.2 (mPa · s)         Δn = 0.153         Δε = 8.0         Vth = 2.05 (V)

[0123] Usage example 2         3-HH2Cb (F2) (No. 6) 5.0%         3-HB (F) Cb (F2) (No. 12) 7.0%         2O1-BEB (F) -C 5.0%         3O1-BEB (F) -C 15.0%         4O1-BEB (F) -C 13.0%         5O1-BEB (F) -C 6.0%         2-HHB (F) -C 10.0%         3-HHB (F) -C 15.0%         3-HB (F) TB-2 4.0%         3-HB (F) TB-3 4.0%         3-HB (F) TB-4 4.0%         3-HHB-1 8.0%         3-HHB-O1 4.0%         NI = 88.7 (° C)         η = 83.1 (mPa · s)         Δn = 0.146         Δε = 30.6         Vth = 0.88 (V)

[0124] Usage example 3         5-H2Cb (F2) (No. 2) 2.0%         3-HB (F) 2Cb (F2) (No. 13) 2.0%         3-HHCb (F2) (No.5) 3.0%         3-HBCb (F2) (No. 11) 5.0%         5-PyB-F 4.0%         3-PyB (F) -F 2.0%         2-BB-C 5.0%         4-BB-C 4.0%         2-PyB-2 2.0%         3-PyB-2 2.0%         6-PyB-O5 3.0%         6-PyB-O6 3.0%         6-PyB-O7 3.0%         3-PyBB-F 6.0%         4-PyBB-F 6.0%         5-PyBB-F 6.0%         3-HHB-1 6.0%         3-HHB-3 8.0%         2-H2BTB-2 4.0%         2-H2BTB-3 4.0%         2-H2BTB-4 5.0%         3-H2BTB-2 5.0%         3-H2BTB-3 5.0%         3-H2BTB-4 5.0%         NI = 93.3 (° C)         η = 38.3 (mPa · s)         Δn = 0.195         Δε = 6.0         Vth = 2.30 (V)

[0125] Example of use 4         5-H2Cb (F2) (No. 2) 3.0%         3-HH2Cb (F2) (No. 6) 10.0%         3-HB (F, F) 2Cb (F2) (No. 14) 6.0%         3-HHCb (F2) (No. 5) 4.0%         3-HBCb (F2) (No. 11) 5.0%         3-HCF2OBCb (F2) (No. 15) 2.0%         3-GB-C 10.0%         2-BEB-C 6.0%         3-BEB-C 4.0%         3-PyB (F) -F 3.0%         3-HEB-O4 8.0%         4-HEB-O2 6.0%         5-HEB-O1 6.0%         3-HEB-O2 5.0%         5-HEB-5 5.0%         1O-BEB-2 2.0%         3-HHB-1 6.0%         3-HHEBB-C 3.0%         3-HBEBB-C 3.0%         5-HBEBB-C 3.0%         NI = 69.0 (° C)         η = 47.2 (mPa · s)         Δn = 0.115         Δε = 11.3         Vth = 1.31 (V)

[0126] Usage example 5         3-HH2Cb (F2) (No. 6) 6.0%         3-HB (F, F) 2Cb (F2) (No. 14) 9.0%         3-HHCb (F2) (No.5) 5.0%         2-BEB (F) -C 5.0%         3-BEB (F) -C 4.0%         4-BEB (F) -C 6.0%         1V2-BEB (F, F) -C 10.0%         3-HH-EMe 5.0%         3-HB-O2 9.0%         7-HEB-F 2.0%         3-HHEB-F 2.0%         5-HHEB-F 2.0%         3-HBEB-F 4.0%         2O1-HBEB (F) -C 2.0%         3-HB (F) EB (F) -C 2.0%         3-HBEB (F, F) -C 2.0%         3-HHB-F 4.0%         3-HHB-O1 4.0%         3-HHB-3 13.0%         3-HEBEB-F 2.0%         3-HEBEB-1 2.0%         NI = 78.6 (° C)         η = 42.6 (mPa · s)         Δn = 0.119         Δε = 25.6         Vth = 0.87 (V)

[0127] Usage example 6         3-HH2Cb (F2) (No. 6) 5.0%         3-HB (F) 2Cb (F2) (No. 13) 5.0%         5-BEB (F) -C 5.0%         V-HB-C 6.0%         5-PyB-C 6.0%         4-BB-3 11.0%         3-HH-2V 5.0%         5-HH-V 11.0%         V-HHB-1 7.0%         V2-HHB-1 15.0%         3-HHB-1 9.0%         1V2-HBB-2 10.0%         3-HHEBH-3 5.0%         NI = 88.3 (° C)         η = 20.6 (mPa · s)         Δn = 0.113         Δε = 5.2         Vth = 2.32 (V)

[0128] Usage example 7         3-HH2Cb (F2) (No. 6) 9.0%         3-HB (F) 2Cb (F2) (No. 13) 10.0%         3-HBCb (F2) (No. 11) 5.0%         5-HBCF2OB (F, F) -C 3.0%         3-HB (F, F) CF2OB (F, F) -C 3.0%         3-HB-C 9.0%         2-BTB-1 5.0%         5-HH-VFF 20.0%         1-BHH-VFF 8.0%         1-BHH-2VFF 11.0%         3-H2BTB-2 5.0%         3-H2BTB-3 4.0%         3-H2BTB-4 4.0%         3-HHB-1 4.0%         NI = 79.1 (° C)         η = 25.7 (mPa · s)         Δn = 0.119         Δε = 5.1         Vth = 2.48 (V)

[0129] Usage example 8         3-HH2Cb (F2) (No. 6) 5.0%         3-HHCb (F2) (No. 5) 10.0%         2-HHB (F) -F 7.0%         3-HHB (F) -F 17.0%         5-HHB (F) -F 16.0%         2-H2HB (F) -F 5.0%         3-H2HB (F) -F 5.0%         5-H2HB (F) -F 10.0%         2-HBB (F) -F 6.0%         3-HBB (F) -F 6.0%         5-HBB (F) -F 13.0%         NI = 97.6 (° C)         η = 28.9 (mPa · s)         Δn = 0.097         Δε = 5.4         Vth = 2.15 (V)

[0130] Usage example 9         3-HH2Cb (F2) (No. 6) 10.0%         3-HHCb (F2) (No. 5) 7.0%         3-HBCb (F2) (No. 11) 5.0%         3-HB (F) Cb (F2) (No. 12) 3.0%         3-HCF2OBCb (F2) (No.15) 5.0%         7-HB (F, F) -F 5.0%         3-H2HB (F, F) -F 5.0%         4-H2HB (F, F) -F 10.0%         3-HHB (F, F) -F 5.0%         4-HHB (F, F) -F 5.0%         3-HBB (F, F) -F 5.0%         3-HHEB (F, F) -F 10.0%         4-HHEB (F, F) -F 3.0%         5-HHEB (F, F) -F 3.0%         2-HBEB (F, F) -F 3.0%         3-HBEB (F, F) -F 5.0%         3-HGB (F, F) -F 5.0%         3-HHBB (F, F) -F 6.0%         NI = 70.1 (° C)         η = 39.3 (mPa · s)         Δn = 0.088         Δε = 13.1         Vth = 1.37 (V)

[0131] Usage example 10         3-HH2Cb (F2) (No. 6) 4.0%         3-HB (F) 2Cb (F2) (No. 13) 4.0%         3-HHCb (F2) (No.5) 5.0%         3-HCF2OBCb (F2) (No.15) 5.0%         5-H4HB (F, F) -F 7.0%         5-H4HB-OCF3 15.0%         3-H4HB (F, F) -CF3 4.0%         5-H4HB (F, F) -CF3 5.0%         3-HB-CL 6.0%         2-H2BB (F) -F 5.0%         3-H2BB (F) -F 5.0%         5-H2HB (F, F) -F 5.0%         3-HHB-OCF3 5.0%         3-H2HB-OCF3 5.0%         V-HHB (F) -F 5.0%         3-HHB (F) -F 5.0%         5-HHB (F) -F 5.0%         3-HBEB (F, F) -F 5.0%         NI = 67.6 (° C)         η = 29.8 (mPa · s)         Δn = 0.097         Δε = 8.5         Vth = 1.73 (V)

[0132] Example of use 11         5-H2Cb (F2) (No. 2) 3.0%         3-HH2Cb (F2) (No. 6) 4.0%         3-HHCb (F2) (No.5) 3.0%         3-HCF2OBCb (F2) (No.15) 3.0%         7-HB (F) -F 4.0%         5-HB-CL 3.0%         3-HH-4 9.0%         3-HH-EMe 23.0%         3-HHEB (F, F) -F 10.0%         4-HHEB (F, F) -F 5.0%         3-HHEB-F 8.0%         5-HHEB-F 8.0%         4-HGB (F, F) -F 5.0%         5-HGB (F, F) -F 3.0%         3-H2GB (F, F) -F 5.0%         5-GHB (F, F) -F 4.0%         NI = 79.4 (° C)         η = 21.4 (mPa · s)         Δn = 0.067         Δε = 5.5         Vth = 1.50 (V)

[0133] Usage example 12         3-HH2Cb (F2) (No. 6) 15.0%         3-HHCb (F2) (No.5) 5.0%         5-H2HB (F, F) -F 5.0%         3-HBB (F, F) -F 15.0%         5-HBB (F, F) -F 30.0%         5-HBB (F) B-2 10.0%         5-HBB (F) B-3 10.0%         3-BB (F) B (F, F) -F 5.0%         5-B2B (F, F) B (F) -F 5.0%         NI = 105.9 (° C)         η = 53.6 (mPa · s)         Δn = 0.146         Δε = 10.5         Vth = 1.71 (V)

[0134] Example of use 13         3-HH2Cb (F2) (No. 6) 5.0%         3-HB (F) 2Cb (F2) (No. 13) 4.0%         3-HB (F, F) 2Cb (F2) (No.14) 5.0%         3-HHCb (F2) (No. 5) 4.0%         3-HCF2OBCb (F2) (No.15) 5.0%         3-BB (F, F) CF2OB (F, F) -F 30.0%         3-HH-4 4.0%         3-HHB (F, F) -F 5.0%         3-H2HB (F, F) -F 5.0%         3-HBB (F, F) -F 10.0%         2-HHBB (F, F) -F 3.0%         3-HHBB (F, F) -F 3.0%         3-HH2BB (F, F) -F 4.0%         3-HHB-1 6.0%         5-HBBH-1O1 7.0%         NI = 75.4 (° C)         η = 35.5 (mPa · s)         Δn = 0.116         Δε = 12.7         Vth = 1.33 (V)

[0135] Example of use 14         3-HHCb (F2) (No. 5) 8.0%         3-HEB-O4 20.0%         4-HEB-O2 20.0%         5-HEB-O1 20.0%         3-HEB-O2 18.0%         5-HEB-O2 14.0%         NI = 74.7 (° C)         η = 20.8 (mPa · s)         Δn = 0.091

[0136] Example of use 15         3-HB (F) 2Cb (F2) (No. 13) 6.0%         3-HH-2 5.0%         3-HH-4 6.0%         3-HH-O1 4.0%         3-HH-O3 5.0%         5-HH-O1 4.0%         3-HB (2F, 3F) -O2 6.0%         5-HB (2F, 3F) -O2 11.0%         3-HHB (2F, 3F) -O2 14.0%         5-HHB (2F, 3F) -O2 15.0%         3-HHB (2F, 3F) -2 24.0%         NI = 86.3 (° C)         Δn = 0.081         Δε = -3.9

[0137] Example of use 16         3-HB (F) 2Cb (F2) (No. 13) 5.0%         3-HH-5 5.0%         3-HH-4 5.0%         3-HH-O1 6.0%         3-HH-O3 6.0%         3-HB-O1 5.0%         3-HB-O2 5.0%         3-HB (2F, 3F) -O2 5.0%         5-HB (2F, 3F) -O2 10.0%         3-HHB (2F, 3F) -O2 12.0%         5-HHB (2F, 3F) -O2 13.0%         3-HHB (2F, 3F) -2 4.0%         2-HHB (2F, 3F) -1 4.0%         3-HHEH-3 5.0%         3-HHEH-5 5.0%         4-HHEH-3 5.0%         NI = 86.3 (° C)         Δn = 0.078         Δε = −3.2

[0138]

The liquid crystal compound of the present invention has a large dielectric anisotropy and a controlled optical anisotropy, has excellent compatibility with other liquid crystal compounds, and is chemically stable. Therefore, a liquid crystal display device capable of low voltage driving can be realized by a liquid crystal composition containing this compound as a component.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 19/34 C09K 19/34 19/40 19/40 19/42 19/42 G02F 1/13 500 G02F 1 / 13 500 F term (reference) 4C063 AA01 BB02 BB03 CC12 CC29 CC82 DD04 EE10 4C069 AC06 BB02 BB12 BC01 4H027 BB03 BB04 BC05 BD01 BD04 BD07 BD09 BD24 CB01 CC01 CC04 CD01 CD05 CN04 CM04 CN04 CM05 CM04 CM05 CM04 CM05 CR04 CR05 CS04 CT01 CT02 CT03 CT04 CT05 CU01 CU04 CU05 CW01 CW02 CX01 DB04 DC04 DE01 DE04 DF04 DH04

Claims (23)

[Claims] 1. A compound represented by formula (1). In the formula (1), Ra is hydrogen, halogen, —CN, or alkyl having 1 to 20 carbon atoms, and in this alkyl, any —CH ₂ — is —O—, —S—, —CH═.
CH -, - C≡C-, or -SiH ₂ - may be replaced by, and any hydrogen may be replaced by ^halogen; A 1, ^{A 2} and ^{A 3} are independently 1,4
- cyclohexylene, decahydro-2,6-naphthylene, 1,4-phenylene or 2,6-naphthylene,, any hydrogen in these rings may be replaced by halogen, arbitrary -CH ₂ - , -O-, -S
-, - CH = CH -, - CO-, or -SiH ₂ - may be replaced by, and any -CH = is -N
May be replaced with =; Z ¹ , Z ² and Z ³ are independently a single bond or alkylene having 1 to 4 carbon atoms;
In alkylene, any —CH ₂ — is —O—, —S
-, -CH = CH-, -C≡C-, -CO-, or-
SiH ₂ — and any hydrogen may be replaced by halogen; Y ¹ and Y ² are independently fluorine or trifluoromethyl; and m and n are independently 0 or It is 1. 2. Ra is alkyl having 1 to 20 carbon atoms, and in this alkyl, any --CH ₂ -is --O.
-, - S -, - CH = CH-, or may be replaced by -C≡C-, and any hydrogen may be replaced by ^{halogen; A} 1, A ² and ^{A 3} are independently 1,4-cyclohexylene, 1,3-dioxane-2,
5-diyl or 1,4-phenylene in which any hydrogen may be replaced by halogen; Z ¹ and Z ² are independently a single bond, — (CH ₂ ) ₂ —, —COO—, —O.
_{CO -, - CH 2 O -} , - OCH 2 -, - CF 2 O-,
_{-OCF 2 -, - CH = CH} -, - CF = CF -, - C
_{≡C -, - (CH 2)} 4 -, - (CH 2) 2 -CF 2 O
- _{(CH 2) 2} - - a and, ^{Z 3} is a single _bond, - or _{-OCF 2, (CH 2) 2} -, - OCO -, - CH 2 CO
-, - CH = CH -, - CF = CF -, - C≡C-, or - _{(CH 2) 4} - A compound according to claim 1 is. 3. The method according to claim 1, wherein m and n are 0.
The compound according to. 4. The compound according to claim 1 or 2, wherein m is 0 and n is 1. 5. The method according to claim 1 or 2, wherein m and n are 1.
The compound according to. 6. Z ¹ is — (CH ₂ ) ₂ —.
Or the compound according to 2. 7. The compound according to claim 1 or 2, wherein Z ³ is a single bond. 8. The compound according to claim 1 or 2, wherein all of Z ¹ , Z ² and Z ³ are single bonds. 9. A ¹ , A ² and A ³ are independently 1,4
A compound according to claim 1 or 2, which is -cyclohexylene or 1,4-phenylene in which optional hydrogen may be replaced by halogen. 10. A ¹ and A ³ are 1,4-cyclohexylene, Z ¹ and Z ³ are single bonds, and m is 1.
And n is 0. The compound of claim 1 or 2, wherein 11. At least one of Z ¹ and Z ² is —CF.
The compound according to claim 1, which is ₂ O-. 12. Sodium hydride, potassium hydride,
Reaction of 3,4-difluoropyrrole with an organic halide at a temperature of 0 ° C. or higher and 200 ° C. or lower, using at least one base selected from the group consisting of lithium hydride, sodium hydroxide, and potassium hydroxide. Or a method for producing a liquid crystalline 3,4-difluoropyrrole derivative or a liquid crystalline 3,4-bis (trifluoromethyl) pyrrole derivative by the reaction of 3,4-bis (trifluoromethyl) pyrrole with an organic halide . 13. At least one liquid crystal compound according to claim 1 is contained, and at least 2
A composition of ingredients. 14. A first component containing at least one compound according to any one of claims 1 to 11, and a second component represented by formulas (2), (3) and (4). A composition containing at least one compound selected from the group consisting of: In the formula, R ¹ is alkyl having 1 to 10 carbon atoms, and in this alkyl, any —CH ₂ — is —O— or —CH.
═CH— and any hydrogen may be replaced by fluorine; X ¹ is fluorine, chlorine,
_{-OCF 3, -OCHF 2, -CF 3} , -CHF 2, -C
_{H 2 F, -OCF 2 CHF 2} , or -OCF ₂ CHF
CF ₃ ; L ¹ and L ² are independently hydrogen or fluorine; Z ⁴ and Z ⁵ are independently — (CH ₂ ) _{2
-, - (CH 2) 4} -, - COO -, - CF 2 O -, - O
CF ₂ —, —CH═CH—, or a single bond; ring B
And ring D is independently 1,4-cyclohexylene, 1,
3-dioxane-2,5-diyl, or 1,4-phenylene in which any hydrogen may be replaced by fluorine, ring E is 1,4-cyclohexylene or in which any hydrogen is replaced by fluorine. Good 1,4-phenylene. 15. Formulas (1b-1-1) and (1b-1-).
2) and at least one compound selected from the group of compounds represented by (1b-2-1), selected from the group of compounds represented by formulas (3-2-1) and (3-3-1) At least one compound represented by the formulas (3-23-1) and (3-24-1). In the formula, Ra is hydrogen, halogen, —CN, or carbon number 1
Alkyl of 20, any _-CH 2 - in the alkyl may, -O -, - S -, - CH = CH -, - C
≡C-, or -SiH _2- may be substituted.
And any hydrogen may be replaced by a halogen;
R ¹ is alkyl having 1 to 10 carbons, and in this alkyl, any —CH ₂ — is —O— or —CH═CH.
May be replaced by-and any hydrogen may be replaced by fluorine. 16. A group of compounds represented by formulas (5) and (6), containing as a first component at least one compound according to any one of claims 1 to 11, and as a second component. A composition containing at least one compound selected from: In the formula, R ² and R ³ are independently alkyl having 1 to 10 carbon atoms, and in this alkyl, any —CH ₂ — may be replaced by —O— or —CH═CH—,
And any hydrogen may be replaced by fluorine; X
² is -CN or -C≡C-CN; ring G is 1,4
-Cyclohexylene, 1,4-phenylene, 1,3-dioxane-2,5-diyl, or pyrimidine-2,5
-Diyl; ring J is 1,4-cyclohexylene, 1,4-phenylene in which any hydrogen may be replaced by fluorine, or pyrimidine-2,5-diyl; ring K is 1,4- in there cyclohexylene or 1,4-phenylene; ^{Z 6} is _{- (CH 2) 2 -,} - COO -, - C
_{F 2 O -, - OCF 2} -, or a single ^{bond; L} 3,
L ⁴ and L ⁵ are independently hydrogen or fluorine;
b, c and d are independently 0 or 1. 17. A first component containing at least one compound according to any one of claims 1 to 11, and a second component represented by formulas (7), (8) and (9). A composition containing at least one compound selected from the group consisting of: In the formula, R ⁴ and R ⁵ are independently alkyl having 1 to 10 carbon atoms, and in this alkyl, arbitrary —CH ₂ — may be replaced by —O— or —CH═CH—,
And any hydrogen may be replaced by fluorine; ring M and ring P are independently 1,4-cyclohexylene or 1,4-phenylene; L ⁶ and L ⁷ are independently hydrogen or fluorine. Yes, at least 1 of L ⁶ and L ⁷
Is fluorine; Z ⁷ and Z ⁸ are independently-(CH
₂ ) _2- , -COO- or a single bond. 18. As a first component, at least one compound according to any one of claims 1 to 11 is contained, and as a second component, formulas (2) and (3) according to claim 14 are contained. And at least one compound selected from the group of compounds represented by (4), and as the third component, the compound represented by formula (10),
A composition containing at least one compound selected from the group of compounds represented by (11) and (12). In the formula, R ⁶ and R ⁷ are independently alkyl having 1 to 10 carbons, and in this alkyl, any —CH ₂ — may be replaced by —O— or —CH═CH—,
And any hydrogen may be replaced by fluorine; ring Q, ring T and ring U are independently 1,4-cyclohexylene, pyrimidine-2,5-diyl, or any hydrogen is replaced by fluorine. 1,4-phenylene may be also present; Z ⁹ and Z ¹⁰ are independently -C≡C-, -CO.
_{O -, - (CH 2)} 2 -, - CH = CH-, or a single bond. 19. A first component containing at least one compound according to any one of claims 1 to 11, and a second component comprising the formulas (5) and (6) according to claim 16. The compound containing at least one compound selected from the group consisting of compounds represented by the formulas (10), (11) and (12) according to claim 18 as a third component. A composition containing at least one compound according to claim 1. 20. As a first component, at least one compound according to any one of claims 1 to 11 is contained, and as a second component, formulas (7) and (8) according to claim 17 are contained. And at least one compound selected from the group of compounds represented by (9), and as the third component, compounds represented by formulas (10), (11) and (12) A composition comprising at least one compound selected from the group. 21. At least one compound according to any one of claims 1 to 11 is contained as a first component, and formulas (2) and (3) according to claim 14 are contained as a second component. And at least one compound selected from the group of compounds represented by (4), wherein the third component is selected from the group of compounds represented by formulas (5) and (6) according to claim 16. 19. A composition containing at least one compound selected from the group consisting of compounds represented by formulas (10), (11) and (12) according to claim 18, as a fourth component. object. 22. A composition according to any one of claims 13 to 21, further containing at least one optically active compound. 23. A liquid crystal display device containing the composition according to any one of claims 13 to 22.