WO1998020006A1 - Fluoroalkylated dioxane derivatives, liquid crystal compositions, and liquid-crystal display elements - Google Patents

Abstract

Liquid-crystal compounds which have remarkably large Δε values and high specific resistance values and are excellent in compatibility with existing liquid-crystal compounds and suitable particularly for the low-voltage driving of TFT-type liquid-crystal display elements; and liquid-crystal compositions containing the same. The above compounds are dioxane derivatives represented by general formula (1): wherein n0 is an integer of 2 to 10; n1 and n2 are each independently an integer of 0 to 2; and n3 and n4 are each independently 0 or 1, with n1, n3 and n4 satisfying the relationships: n3≥n4 and n1 + n3 + n4≤2; Q1 and Q2 are each independently hydrogen, fluoro or chloro; Za, Zb and Zc are each independently a single bond, -CH2CH2-, -CH2CH2CH2CH2-, -COO- or -CF2O-; A1 and A2 are each independently selected from among the groups (a) to (i), and Y is hydrogen, halogeno or C1-C5 haloalkyl.

Description

 Specification

 Dioxane derivative having fluoroalkyl group, liquid crystal composition and liquid crystal display device

 The present invention relates to a liquid crystal compound and a liquid crystal composition, and more particularly, to a liquid crystal composition, particularly a dioxane derivative having a fluoroalkyl group, which is a liquid crystal compound suitable as a component of a liquid crystal composition for TFT, and a liquid crystal composition containing the same. And a liquid crystal display device formed using the liquid crystal composition.

Background art

 Liquid crystal display devices utilize the optical anisotropy and dielectric anisotropy of liquid crystal materials. Depending on the display method, TN type (twisted nematic type), DS type (dynamic scattering type), GH There are various types of liquid crystal materials, such as liquid crystal type (guest-host type), DAP type (alignment phase change type), and STN type (super twisted nematic type). The properties of liquid crystal materials suitable for each use are different. In recent years, in particular, liquid crystal display devices with higher display quality have been demanded, and in order to meet the demand, demand for active matrix display devices represented by TFT (thin film transistor type) is increasing. The liquid crystal material used in any display element must be stable to moisture, air, heat, light, etc., exhibit a liquid crystal phase over as wide a temperature range as possible around room temperature, have low viscosity, Good compatibility with liquid crystal compounds (hereinafter referred to as compounds having a liquid crystal phase and compounds that do not impair the liquid crystal phase even when mixed with other liquid crystals) and liquid crystal compositions, and have a large dielectric anisotropy value It must have (Δ ε), optimal optical (refractive index) anisotropy value (Δ η) and high resistivity. However, at present, no single compound satisfies all of these conditions, and at present the liquid crystal composition obtained by mixing several liquid crystal compounds is used.

Recently, low-voltage drivability has been particularly required for TFTF-type liquid crystal display devices.To meet this demand, liquid crystal compounds with Δ Δ larger than the conventional liquid crystal materials used for TFT-type liquid crystal display devices have been developed. And liquid crystal compositions have become necessary. For this reason, a liquid crystal material having a high resistivity and a large value of ε has been actively developed. Conventionally, a fluorine-based liquid crystal material having a high specific resistance value, for example, the following formula (10) The compounds shown in (1) are generally known (Japanese Patent Publication No. 01-04496). -

The compound (10) is used mainly as a component of a liquid crystal composition for TFTs because it has a higher specific resistance value than a liquid crystal compound having a cyano group, but its external ε is 8. 7 and cannot be used as a liquid crystal material for low-voltage driving represented by the currently required 2.5 V driving.

 The above-mentioned extrapolation Δε is determined by dissolving compound (10) in a mother liquid crystal having a nematic phase, Δp of the composition thus obtained, Δp of the mother liquid crystal, and mixing of the compound in the composition. Although it is a calculated value obtained from the ratio, it substantially reflects the value of the compound (10) (in the following description, the value of △ e for the compound is used in the same meaning as described above).

 A trifluorophenyl derivative represented by the following formula (11) is known as a compound having a Δ £ larger than that of the compound (10) (Japanese Patent Application Laid-Open No. H02-233366).

The compound (1 1) has a value of 11.7, which is larger than that of the compound (10). However, for the same reason as described above, a material that can meet the demand for a lower voltage in the market is used. Absent.

Further, a trifluoromethylphenyl derivative represented by the formula (12) and a trifluoromethoxyphenyl derivative represented by the formula (13) are known (Japanese Patent Application Laid-Open No. H04-506636).

However, these compounds also have insufficient △ ε (for example, Δε of compound (13) is 8.7 (I DY (Television Technical Report) 95)), and for the same reason as above. We cannot meet the demand for low voltage in the factory.

 In the above compound (13), there is also known a three-ring compound represented by the following formula (14) in which two fluorine atoms are substituted at the lateral position of the central benzene ring (IDΥ (Television Technical Report) 9 Five) .

This compound (14) has a Δ £ of 13.0, which is 4.3 larger than that of the above compound (13). However, for the same reason as above, it is necessary to reduce the market voltage. It is not a material that can meet the demands.

 A dioxane derivative represented by the following formula (15) is also known as a compound exhibiting a larger Δ £. (Japanese Unexamined Patent Publication (Kokai) No. 02-2333626).

According to the measurement by the present inventors, this compound (15) exhibits a large value of about 15 as a result, but by using this compound, the driving voltage of the TFT-type liquid crystal display element can be brought to a required level. However, it is still insufficient to reduce the amount to a lower value, and the appearance of a compound having a larger Δε is expected. As a dioxane derivative similar to the above compound (15), a dioxane derivative having a fluoroalkyl group as shown in the formula (1) (6) is also known (US Pat. No. 5494946). 06), but the Δε of this compound does not exceed that of the compound (15).

Disclosure of the invention

 An object of the present invention is to solve the above-mentioned drawbacks of the prior art, to obtain a significantly large Δε, a high specific resistance value, electrical and chemical stability, and compatibility with existing liquid crystal compounds. Another object of the present invention is to provide a liquid crystal compound which is suitable for driving a TFT type liquid crystal display element at a low voltage, a liquid crystal composition containing the same, and a liquid crystal display element using the same.

The present inventors have conducted intensive studies in order to achieve the above object. As a result, the present inventors have found that the molecule has a combination of a fluor □ alkyl group and a 1,3-dioxane-1,2,5-diyl group, Benzene, cyclohexane or silinane ring which may be substituted by a fluorine or chlorine atom via a covalent bond, — CH ₂ CH ₂ — or CH ₂ CH ₂ CH ₂ CH ₂ — The dioxane derivative has a large structure, has good compatibility with existing liquid crystal compounds, and shows high specific resistance. They found it to be the best material and completed the invention.

 That is, the configuration of the present invention is as follows.

 (1) General formula (1)

(Wherein η 0 is an integer of 2 to 10, η 1 and η 2 are each independently an integer of 0 to 2, and η 3 and η 4 are each independently 0 or 1. , Η 3 ≥n 4 and n 1 + η 3 + η 4≤2, Q and Q ₂ each independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Za, Zb and Z c each independently represent a single atom A bond, — CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —COO— or one CF ₂₀ —, wherein ring A 1 and ring A 2 are each independently a group represented by formulas (a) to ( i)

Y represents a hydrogen atom, a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms, and when the halogen atom is a fluorine atom, nl = n2 = n4 = 0, n 3 21 and Zb are two single bonds and ring A 1 is not a group represented by the formula (b), and the halogenated alkyl group is one or more non-adjacent groups in the group. The methylene group may be replaced by an oxygen atom or a sulfur atom. Each element constituting the compound may include those selected from their isotopes. A dioxane derivative represented by the formula:

 (2) The dioxane derivative according to (1), wherein nl2n3 = n4 = 0.

(3) The dioxane derivative according to (1), wherein nl + n3 + n4 = 1. (4) The dioxane derivative according to (1), wherein nl + n3 + n4 = 2. -

(5) The dioxane derivative according to (1), wherein n2 ≠ 0 and ring A1 is a group represented by formula (a).

 (6) The dioxane derivative according to (1), wherein n 2 = 0 and n 3 = 1.

 (7) The dioxane derivative according to (1), wherein n 2 = 0, n 3 = 1, and ring A1 is a group selected from the group consisting of formulas (c) to (g).

 (8) (1) A liquid crystal composition comprising at least one kind of the dioxane derivative according to any one of (7).

 (9) As a first component, at least one dioxane derivative according to any of (1) to (7) is contained, and as a second component, the general formulas (2), (3) and (4)

(In each formula, R ₃ , Yi, L], L ₂ , and Z ₂ may be the same or different from each other in each formula, and R ₃ is an alkyl group having 1 to 10 carbon atoms, In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or one CH 2 CH—, and an arbitrary hydrogen atom may be substituted with a fluorine atom. off Tsu atom, a chlorine atom, OCF _3, 〇_CF _{2 H, CF 3, CF 2} H, CFH 2, OCF 2 CF 2 H or OCF ₂ CFHCF _3, L, and L ₂ hydrogen atoms each independently may Is a fluorine atom, and Z ₂ is each independently — CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, —COO—, —CF ₂ 0—, — OCF ₂ —, — CH-CH— Or simple -O 98/20006 is indicated. Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted by a fluorine atom, and ring C is trans-1,1, 4-cyclohexylene or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom. In the compounds of each formula, each element constituting them may include those selected from their isotopes. ) A liquid crystal composition comprising at least one compound selected from the group consisting of:

 (10) As a first component, at least one dioxane derivative according to any one of (1) to (7) is contained, and as a second component, a general formula (5) and Ζ or (6)

(In each formula, R ₄ and R ₅ each independently represent an alkyl group having 1 to 10 carbon atoms. In the alkyl group, non-adjacent ^ or more methylene groups are an oxygen atom or one CH 2 CH And any hydrogen atom may be replaced by a fluorine atom, Y ₂ is one CN group or one C≡C—CN, and ring E is trans-1,4-cyclohexyl. Methoxyhexylene, 1,4-phenylene, 1,3-dioxane-1,2,5-diyl or pyrimidine-1,2,5-diyl, ring G is trans-1,4-cyclohexylene, hydrogen atom 1,4-Phenylene or pyrimidine-2,5-diyl which may be substituted by a fluorine atom, ring H is trans and 4-cyclohexylene or 1,4-phenylene, Z ₃ is CH ₂ CH ₂ - one COO- or a single bond, L _3, L ₄ and L ₅ represents a hydrogen atom or a fluorine atom each independently, b, c Oyo d is each independently 0 or 。. In the compounds of the formulas, each element constituting them may include those selected from their isotopes.) A liquid crystal composition comprising at least one of the following. (11) As the first component, at least one dioxane derivative according to any of (1) to (7) is contained, and as the second component, the general formulas (2), (3) and (4) )

(In each formula, R ₃ , Yi> L), L ₂ , and Z ₂ may be the same or different from each other in each formula, and R ₃ is an alkyl group having 1 to 10 carbon atoms, In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or one CH 2 CH—, and an arbitrary hydrogen atom may be substituted with a fluorine atom. The full Tsu atom and a chlorine _{atom, 0CF 3, 0CF 2 H,} CF 3, CF 2 H, CFH 2, 0CF 2 CF 2 H or OCF ₂ CFHCF _3, L, and L ₂ are each independently hydrogen atom Is a fluorine atom, Z and Z ₂ are each independently CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, C 1 —, — CF ₂ 0—, — 0CF ₂ —, — CH = CH— or indicates a single bond. Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-1,2,5-diyl or a hydrogen atom in which a hydrogen atom may be substituted by a fluorine atom 1,4-phenylene, Ring C is trans-1 1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom. In the compounds of each formula, each element constituting them may include those selected from their isotopes. ) Containing at least one compound selected from the group consisting of: and a third component represented by the general formula (7), (8) or (9)

R _f • Z.-K † -R ₇ (8)

(In each formula, R ₆ , RTI, J and K may be the same or different from each other in each formula, and R ₆ and R ₇ are each independently an alkyl group having 1 to 10 carbon atoms. In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or —CH = CH, and any hydrogen atom may be substituted with a fluorine atom. J and K are each independently, xylene trans one 1, 4 Shikuro, pyrimidine one 2, 5 - 1 Jiiru or hydrogen atoms may be substituted by fluorine atoms, 4 - phenylene, Z ₄ and Z _{And 5} , each independently represents one C≡C—, one C〇0—, —CH ₂ CH ₂ —, —CH = CH— or a single bond. May include those selected from their isotopes.) At least one compound selected from the group consisting of The liquid crystal composition characterized by containing class.

 (12) As a first component, at least one dioxane derivative according to any one of (1) to (7) is contained, and as the second component, the general formula (5) and

Contains at least one compound selected from (6) and at least one compound selected from the group consisting of the general formulas (7), (8) and (9) as a third component A liquid crystal composition comprising:

(13) As a first component, at least one dioxane derivative according to any one of (1) to (7) is contained, and as a part of the second component, the general formulas (2) and (3) And at least one compound selected from the group consisting of (4), and as the other part of the second component, selected from the above general formulas (5) and Z or (6). A liquid crystal composition comprising at least one compound selected from the group consisting of the general formulas (7), (8) and (9) as a third component. object.

 (14) The liquid crystal composition according to any one of (8) to (13), further comprising an optically active compound.

 (15) (8) Liquid non-element composed using the liquid crystal composition according to any one of (14)

BEST MODE FOR CARRYING OUT THE INVENTION

The liquid crystal compound represented by the general formula (1) of the present invention, that is, the dioxane derivative having a fluoroalkyl group, has a combination of a fluoroalkyl group and a 1,3-dioxane-2,5-diyl group in a molecule, and A fluorine or chlorine atom is substituted through a covalent bond at the 2-position of the ring, i. (: ^ 1 ₂ (? ^ — Or-(1 "1 ₂ (: ^ 1 ₂ (1" 1 ₂ (: 9 ₂ It has a structure in which the core part is composed of two to four rings including a dioxane ring, to which a benzene ring, a cyclohexane ring or a silinane ring may be bonded. (For example, the compound No. 52 described later has a value of 19), and has high compatibility with existing liquid crystal compounds and high resistivity.

 Therefore, when such a liquid crystal compound of the present invention is used as a component of a liquid crystal composition, a liquid crystal composition particularly useful for lowering the voltage of a TFT type liquid crystal display device can be provided.

 In the above general formula (1), n 0 is an integer related to the determination of the chain length (the number of carbon atoms) of the fluoroalkyl group, and the value is 2 to 10 from the viewpoint of the balance between the viscosity required for the compound and the clearing point. Suitable, preferably 2-7, more preferably 2-5.

Z a, Zb and Z c of the linking group are as described above, and each is independently a single bond, one CH ₂ CH ₂ —, — CH ₂ CH ₂ CH ₂ CH ₂ —, one C〇 0— or one Indicates CF ₂ -1. n2 is an integer for determining the chain length (the number of carbon atoms) of the linking group provided between the 2-position of the dioxane ring and the other ring, and 0 to 2 is suitable. Depending on if the value is 0, Ru 1 or 2 der each linking group is a single bond, - CH ₂ CH ₂ - or a _{CH 2 CH 2 CH 2 C h} 2 - become.

Of the above linking groups, a single bond has a relatively high clearing point, a relatively low viscosity, And electrically stable compounds — CH ₂ CH ₂ — and — CH ₂ C'H ₂ CH ₂ C

H 2-is a chemically and electrically stable compound having excellent compatibility with other liquid crystal compounds or liquid crystal compositions, and -C 00-is a compound having a high clearing point and showing a large △ ε. The compound, —CF ₂₀ —, has a low viscosity, a relatively large hardness, and can provide a chemically and electrically stable compound, respectively.

 Nl is an integer of 0 to 2; n3 and n4 are each independently 0 or 1; n3≥n4 and n1 + n3 + n4≤2. As a specific example of a combination satisfying such conditions, nl, 113 and 114 are all 0, 111 and 114 are both 0, 113 is 1, n1 is 1, and n3 and n4 are both 0 and n 1 + n 3 + n 4 is 2 (11 1 and 11 3 are both 1 and n 4 is 0, n 1 is 2 and n 3 and n 4 are both 0).

Compounds corresponding to these combinations in order are represented by the following formulas (1-1a), (1b) to (ld), (11e) and (1f) to (lh). Can be shown.

F- (CH ₂ ) _n0

(1-h) (In each formula, n 0, n 2, Z a, Zb, Z c, ring A 1, ring _{A 2, Q !, Q 2,} - Y represents the same meaning as before SL, n 5 is 1 or It is 2.)

 Among the above compounds, those represented by the formula (1-1a) are low in viscosity, have excellent compatibility with other liquid crystal compounds or liquid crystal compositions, and have a large Δε. The compound represented by b) has a large Δη and a large εε, and n 2 n 0 in the compounds represented by the formulas (1 c), (1−d) and (1—e). Has a large △ ε, has a relatively low viscosity and a high specific resistance.

 In the above formula (111), those in which n 2 = 0 have a particularly high clearing point and have a lower viscosity than those represented by the above formulas (111-b) to (1—d). is there.

 Further, the four-ring compounds represented by the formulas (1 to f) to (1 to h) have a high clearing point and a large Δε.

の in the terminal substituent represents a hydrogen atom, a halogen atom or a halogenated alkyl group having 1 to 5 carbon atoms as described above, and the halogenated alkyl group is one or more methylene groups which are not adjacent to each other in the group. May be replaced by an oxygen atom or a sulfur atom. Among them, compounds in which the halogen atom is a fluorine atom have a relatively large Δε, have low viscosity, and have excellent compatibility with other liquid crystal compounds or liquid crystal compositions. The compound halogenated alkyl group is CF ₃ are those having a very large delta epsilon, is also a compound which is 〇_CF ₃ is a low viscosity.

The above-mentioned halogen atom is a chlorine atom, and the halogenated alkyl group in which one or more non-adjacent methylene groups in the group are replaced with an oxygen atom. ₂ ? ₂ 11 or 0〇? ₂ 〇? 《[Ji? _The compound represented by ₃ has a large Δη and a high transparent point, and the compound replaced by the same oxygen atom is OCH ₂ CF ₂ H ゃ OCH ₂ CF ₃ has a high clear point. Very low viscosity.

Preferred examples of the alkyl group or halogenated alkyl group in which one or more non-adjacent methylene groups in the group are replaced by an oxygen atom, further include a difluoromethyl group and a difluorochloro group. Methyl group, 2,2,2-Trifluoroethyl group, 1,2,2,2-Tetrafluoroethoxy group, 2-Fluoroethyl group, 3-Fluoropropyl group, 4-Fluorobutyl group, Difluoromethoxy group, Difluorochloromethoxy group Group, pentachlorofluoroethoxy group and heparofluoropro Poxy groups and the like can be mentioned. '-Ring A 1 and ring A 2 each independently represent a group selected from the group consisting of formulas (a) to (i) as described above, and the group is a 1,4-phenylene group Those having a fluorine atom or a chlorine atom introduced as a side substituent may be used.

 The introduction of these fluorine or chlorine atoms results in a compound having a large viscosity as the number increases, and a compound having a low viscosity and a high clearing point as the number of hydrogen atoms increases. Can be.

 By the way, comparing the groups represented by the formulas (b), (c) and (e), (e) shows the largest Δε, and (b) shows the compound with the lowest viscosity and high clearing point. It is known to give.

The group of the silinane ring represented by the formula (h) or (i) can give a compound having excellent compatibility with other liquid crystal compounds and liquid crystal compositions at a low temperature. As described above, the compounds of the present invention each have a fluoroalkyl group and a dioxane ring in combination. Among them, a covalent bond at the 2-position of the dioxane ring, one CH ₂ CH ₂ — or —CH ₂ CH ₂ CH _{2 A} benzene ring, cyclohexane ring or silinane ring, which may be substituted by a fluorine or chlorine atom via CH ₂ —, is bonded, and the core consists of 2 to 4 rings including a dioxane ring. It is preferable in that it has a specifically large Δε.

 Among the benzene rings which may be substituted by the fluorine or chlorine atom, 3-fluoro 1,4-phenylene group has a relatively large △ ε, exhibits a high liquid crystal phase temperature range and low viscosity. And a compound having good compatibility, and a 3,5-difluorophenylene group having a very large Δε and a very good compatibility can be obtained.

 The liquid crystal compound represented by the general formula (1) of the present invention may include those in which each element in the formula is selected from their isotopes. That is, there is no particular change in the liquid crystal characteristics as compared with the case where the isotope is not contained even when such isotopes are contained, and a similar effect can be obtained.

The compound of the present invention is particularly suitable as a component of a liquid crystal composition for TFT. \ Other applications, for example, for ΤΝ, guest host mode, polymer dispersed liquid crystal display device , For dynamic scattering mode, for STN, for in-plane switching, for OCB mode or as a component of R-OCB mode liquid crystal composition. Also suitable as a compound for a liquid crystal.

 The liquid crystal composition provided by the present invention comprises at least one liquid crystal compound represented by the general formula (1) as a first component.

 It is necessary that the content be 0.1 to 9.9% by weight based on the weight of the liquid crystal composition in order to exhibit excellent characteristics, preferably 1 to 50% by weight, more preferably. 3 to 20% by weight.

 The liquid crystal composition of the present invention may be composed of only the above-mentioned first component. In addition to this, the second component is selected from the group consisting of the general formulas (2), (3) and (4) referred to above. A mixture of at least one compound (hereinafter, referred to as a second component A) and at least one compound selected from the group consisting of general formulas (5) and / or (6) (hereinafter, referred to as a second component B) Or a mixture of at least one compound selected from the group consisting of general formulas (7), (8) and (9) as a third component, and an optically active component as another component. Known compounds can also be mixed for the purpose of adjusting the compounds, the threshold voltage, the liquid crystal phase temperature range, Δε, Δη, the viscosity and the like.

Among the above-mentioned component II, preferred examples of the compound included in the general formula (2) include the following formulas (2-1) to (2-9), and preferred examples of the compound included in the general formula (3) Preferred examples of the compounds contained in (3-1) to (3-69) and the general formula (4) include the compounds represented by the formulas (4-1) to (4-24).

CO CD CO

CM CM C CVJ C CVJ

o) (26-

L ΐ

690 difficult 6 <UY1 <I 9000Ζ / 86 OAV r / idJGd

9

Five

) (ε

) (2εε- 6 I

9000 86 OAV 0 z

9000Ζ / 86 OAV ϊ ζ

9000 86 ΟΛ \ zz

9000Z / 86 OM.

ί '2

(

(

9000Z / 86 OAV (In each formula, R ₃ and Y have the same meaning as described above. Further, each element constituting the compound of each formula may include those selected from their isotopes.)

 The compounds represented by these general formulas (2) to (4) have a positive Δε, are excellent in thermal stability and chemical stability, and have a high voltage holding ratio (a large specific resistance value). This is an indispensable compound when preparing liquid crystal compositions for TFTs that require high reliability.

 When preparing a liquid crystal composition for TFT, the amount of the compound used is preferably in the range of 1 to 99% by weight based on the total weight of the liquid crystal composition, but is preferably 10 to 97% by weight. More preferably, it is 40 to 95% by weight. In that case, compounds represented by formulas (7) to (9) may be contained.

 The compounds represented by the above general formulas (2) to (4) can also be used for preparing a liquid crystal composition for STN display mode or TN display mode.

Next, among the second component B, preferred examples of the compound contained in the general formula (5) include the following formulas (5-1) to (5-40); Preferred examples include the compounds represented by the formulas (6-1) to (6-3).

690 / one OAV

£ (s

(Five

) (525-

(In each formula, R ₄ , R ₅ , and Y ₂ have the same meanings as described above. Further, each element constituting the compound of each formula may include those selected from their isotopes.)

 The compounds represented by the general formulas (5) and (6) have a large Δε and a large Δε, and are particularly used for the purpose of reducing the threshold voltage of the liquid crystal composition. In addition, for the purpose of widening the nematic range of the liquid crystal composition, such as adjusting Δη and increasing the clearing point, to improve the steepness of the threshold voltage of the liquid crystal composition for STN display mode and 方式 display mode. Is also used, particularly when preparing a liquid crystal composition for an STN display mode or a ΤΝ display mode.

 This compound can reduce the threshold and voltage of the liquid crystal composition as the amount of the compound is increased, but increases the viscosity. Therefore, as long as the viscosity of the liquid crystal composition satisfies the required characteristics, it is more advantageous to use a large amount of the liquid crystal composition for low voltage driving.

Under these circumstances, the liquid crystal composition for the SΤ ま た は display method or Τ Ν display method was prepared. In the case of producing the liquid crystal composition, the amount used is suitably in the range of 0.1 to 99% by 9% by weight based on the total weight of the liquid crystal composition, preferably 10 to 97% by weight, more preferably 40 to 97% by weight. It is 95% by weight.

Among the third components, the following formulas (7-1) to (7-11) are preferred examples of the compound contained in the general formula (7), and the following formulas (7-11) are preferred examples of the compound contained in the general formula (8). Preferred examples of the compounds included in (8_1) to (8-18) and the general formula (9) include the compounds represented by the formulas (9-1) to (9-16).

ΐ ε

690tO / Z.6dT / XDd 9000Ζ / 86ΟΛ ζ ε

(138- (In each formula, R ₆ and R ₇ have the same meaning as described above. Further, each element constituting the compound of each formula may include those selected from their isotopes.)

 The compounds represented by the general formulas (7) to (9) are compounds having a small absolute value of Δε and close to zero, and among them, the compound represented by the general formula (7) mainly adjusts the viscosity of the liquid crystal composition. Alternatively, the compounds of the general formulas (8) and (9) are used for the purpose of adjusting Δη and for expanding the nematic range of the liquid crystal composition such as increasing the clearing point, and for adjusting Δη.

 This compound increases the threshold voltage of the liquid crystal composition as the amount used increases, but decreases the viscosity. Therefore, as long as the threshold voltage of the liquid crystal composition satisfies the required characteristics, the larger the amount used, the better.

 Under these circumstances, when preparing a liquid crystal composition for a TFT, the above-mentioned amount is suitably at most 40% by weight, preferably at most 35% by weight, based on the total weight of the liquid crystal composition. On the other hand, when preparing a liquid crystal composition for the STN display method or the ΤΝ display method, the amount used is preferably 70% by weight or less, more preferably 60% by weight, based on the total weight of the liquid crystal composition. It is as follows.

 Next, among the other components, the optically active compound is generally used in a special case, for example, OCB (0 Ptica 1 iy and omp ensated birefringence). It is added for the purpose of inducing the helical structure of the composition to adjust the required torsion angle, and thereby preventing reverse twist.

This optically active compound is a compound widely selected from known compounds as long as the above object is achieved, preferably an optically active compound represented by the following formulas (Op-1) to (〇p-8). Can be mentioned.

By adding these optically active compounds, the liquid crystal composition is twisted ω pitch

(p i t ch) length is adjusted. The pitch length of this twist is in the range of 40 to 200 μm if the liquid crystal composition is for TFT or TN, in the range of 6 to 20 μm for STN, and the bistable TN (Bist ab le TN) If it is for the mode, it is preferable to adjust each in the range of 5 to 4 zm.

 At this time, two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the pitch length.

 The liquid crystal composition provided according to the present invention is generally prepared by a method known per se, for example, a method in which various components are mutually dissolved at a high temperature.

 If a dichroic dye such as a merocyanine-based, styryl-based, azo-based, azomethine-based, azoxy-based, quinophthalone-based, anthraquinone-based, or tedrazine-based dye is added during the preparation, a guest-host (GH) mode can be obtained. It can also be used as a liquid crystal composition. The liquid crystal composition according to the present invention is typified by NCAP prepared by encapsulating a nematic liquid crystal in a microcapsule, and a polymer-network liquid crystal display device (PNLCD) prepared by forming a three-dimensional network polymer in the liquid crystal. It can also be used as a liquid crystal composition for birefringence control (ECB) mode and dynamic scattering (DS) mode, including those for polymer dispersed liquid crystal display devices (PDLCD).

 Thus, the nematic liquid crystal composition of the present invention is prepared, and the following composition examples 1 to 26 can be shown as examples.

 In each of the composition examples, the compounds are indicated according to the rules shown in Table 1 below, and the groups shown in the columns of the left terminal group, the bonding group, the ring structure, and the right terminal group are shown in the symbol columns. The hydrogen atom on trans-1,4-cyclohexylene and the trans, trans-bicyclohexane-1,4'-diyl group is replaced by an isotope deuterium atom. When the above groups are represented by the formulas (60) and (61), respectively, the hydrogen atoms J 1, J 2, J 3, J 4, J 5, J 6, J 7 And any of J 8 are replaced by only those selected from the corresponding deuterium atoms 1 D, 2 D, 3 D, 4 D, 5 D, 6 D, 7 D and 8 D. H [1D, ~ 8D].

The compound No. attached to the compound of the present invention is the same as that shown in Examples described later. Yes, the content of the compound means% by weight unless otherwise specified. '-In addition, the characteristic data of the composition examples are T _NI (nematic isotropic liquid transition temperature or clearing point), V (viscosity: measurement temperature 20.0 ° C), Δη (refractive index anisotropy). : Measurement temperature 25.0), Δε (Dielectric anisotropy value: Measurement temperature 25.0 ° C), V _th (Threshold voltage: Measurement temperature 25. (TC) and P (Pitch: The measurement temperature was 25 ° C).

-98/20006

 table 1

-Composition Example 1 "A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F, F) B (F) — F (No. 5 2) 1 0.0%

1 V 2 -BEB (F, F) —C 5.0% 3 HB—C 15.0%

1-BTB-35.0%

2-BTB- 1 1 0.0%

3 -HH- 4 1 1.0% 3-HHB-1 1 1.0% 3 -HHB-39.0%

3 -H 2 BTB- 2 4.0%

3 -H 2 BTB- 3 4.0% 3 -H 2 BTB- 4 4.0%

3-HB (F) TB-26.0% 3-HB (F) TB-36.0% The characteristics of this composition were determined, and the results were as follows.

 7? = 2 0.1 mPa as

 N = 0. 1 6 0

 £ 1 = 7.6

V, _h = 1.76 V

 In addition, 100 parts of the above primary composition was added with 8 parts of the optically active compound represented by the formula (Op-4) described above to obtain a secondary composition. The properties of the secondary composition were determined as follows. Met.

 P = 1 0.5 zm

Composition example 2

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F) -CF 3 (No. 7) 5.0%

F 2 -GHB (F) -OCF 3 (No. 9 5) 5.0%

 3 -HB-C 0%

3 -H [I D, 2 D, 3 D] B— C 0% 3 -HB (F) — C 0%

2-BTB- 10%

3-HH- 40%

3 -HH-VFF 0%

2 -H [I D, 2 D, 3 D] HB-C 0% 3 -HHB-C 0%

3 -HB (F) TB— 20% 3 -H2 BTB- 20%

3 -H 2 BTB- 30% 3 -H 2 BTB- 40% When the characteristics of this composition were determined, it was as follows _c

 7? = 2 1.2 mPa as 455 382 866 559 Δn = 0.15 3

 Δ ε 1 = 7.8

V _th = _2.26 V

Composition example 3

 A liquid crystal composition having the following compound content was prepared.

 F 5-GB-OCF 3 (No. 1 3) 5.0%

F 3 -HGB (F, F) -CF 3 (No. 1 3 7) 2.0%

30 1 -BEB (F)-C 1 3.0%

401 -BEB (F) -C 1 3.0%

501 -BEB (F) One C 1 3.0%

2 -HHB (F)-C 1 5.0%

3 -HHB (F)-C 1 5.0%

4 o This

Composition

 Below

 5 -BB-C 50%

2-P y B-220%

3-P y B-220%

4-Py B- 2 2, 0%

6-Py B--53, 0% 6-Py B-06 3, 0% 6-Py B-07 3.0% 6-Py B 08 3.0%

3-Py BB-F 6.0%

4-PyBB-F 6.0%

5-Py BB-F 6.0% 3 -HHB- 16% 3 -HHB-3 8.0%

2 -H2 BTB- 2 4.0%

2 -H 2 BTB- 3 4.0%

2-H2 BTB- 45.0% 3 -H2 BTB- 25.0%

3-H2 BTB- 3 5.0%

3-H2 BTB- 4 5.0% The properties of this composition were determined and were as follows.

T _NI = 9 0.6 ° C

 7? = 34. OmP a-s

 N = 0.1 0.15

 £ 1 = 5.9

V _th = 2.5 1 V

Composition Example 5

 A liquid crystal composition having the following compound content was prepared.

 F 2 -G 2 B (CD -CL (No. 20) 4.0%

3 -GB-C 1 0.0%

4-G B-C 1 0.0%

2-BEB— C 1 2.0% 3 -Py B (F)-F 6.0%

3 One HE B-04 8.0%

4-HEB-02 6.0%

5-HEB-01 6.0% 3 -HEB-02 5.0% 5 -HEB-02 4.0%

5 -HE B-55.0%

4 -HE B-5 5.0% 10-BEB-2 4.0% 3 -HHB- 1 6.0% 3 -HHEBB-C 3.0% 3 -HBEBB-C 3.0% 5 -HBEBB-C 3.0% The characteristics of this composition were determined, and the results were as follows.

T _N1 = 6 3.0 ° C

 77 = 37.7 mPas

 Δ n = 0.1 1 1 7

 Δ ε 1 = 1 0.7

V _th = 1.68 V

Composition Example 6

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F, F) B (F) -F (No. 5 2) 1 0.0%

F 2 -GHB (F) -OCF 3 (No. 95) 1 0.0%

F 2 -G 2 B (F) B (F) -F (No. 1 24) 1 0.0%

3 -HB-C 8.0%

7 -HB-C 3.0% 101 -HB-C 5.0% 3— HB (F) -C 5.0%

2—PyB-2 2.0%

3-Py B- 2 2.0%

4-PyB- 2 2.0%

101 -HH- 3 7.0%

2-BTB-01 7.0%

3-HHB- 1 2.0% 3 -HHB-F 4.0%

3—HHB-01 4.0% 3 -HHB- 3 3.0%

3 -H 2 BTB- 2 3.0% 3 -H 2 BTB- 3 3.0% 2-Py BH- 34.0% 3 -Py BH- 33.0%

3 -Py BB- 2 3.0% Composition Example 7

 A liquid crystal composition having the following compound content was prepared.

 F 5 -GBEB (F) -CL (No. 6 3) 5.0% F 2 -G 2HB (F) -OCF 2 CF 2H (No. 1 1 9) 4.0%

F 3 -HG 4 B (F, F) —F (No. 150) 4.0%

301 -BEB (F) -C 4.0% 501 -BEB (F) -C 4.0%

1 V2 -BEB (F, F) -C 1 0.0%

3 -HH-EMe 1 0.0%

3-HB— 02 1 8.0%

7 -HEB-F 2.0% 3 -HHE B-F 2.0%

5 -HHEB-F 2.009

3 -HBEB-F 4.0%

201 -HB E B (F) One 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-01 4.0%

3 -HHB- 3 1 3.0%

3-HEBEB-F 2.0% 3-HEBEB-1 2. Q% The properties of this composition were determined, and the results were as follows.

 8 7. 4. C

 77 = 38.5 mPas

Δη = 0.10 9 Δ ε 1 = 1 9.6

V, _h = 1.1 2V

Composition Example 8

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GHB B (F)-F (No. 1 5 2) 4.0%

5 -BEB (F) C 5.0%

V-HB-C 1 1.0%

5 -Py B-C 6.0%

4-B B-3 1 1.0%

3 -HH- 2 V 1 0.0%

5 -HH- V 1 1.0%

V-HHB- 1 7.0%

V 2 -HHB- 1 1 5.0%

3 -HHB- 1 5.0%

1 V 2 -HB B- 2 1 0.0%

3 -HHE BH- 35.0% The characteristics of this composition were measured, and the results were as follows.

 7? = 17.5 mPas

 Δ n = 0.1 1 1 7

 Δ ε 1 = 5.0

V, _h = 2.2 3V

Composition Example 9

 A liquid crystal composition having the following compound content was prepared.

F 4 -HHGB-CF 3 (No. 1 9 1) 5.0% 30 1 -BEB (F) 1 C 1 2.0% 50 1 -BE B (F)-C 4.0% 1 V 2- BEB (F, F) C 1 6.0% 3 -HB-02 1 0.0% 3 -HH- 4 3.0% 3 -HHB-F 3.0% 3 -HHB-1 8.0% 3 HHB-01 4.0% 3 -HBEB-F 4.0% 3 -HHEB-F 7.0% 5 -HHEB-F 7.0% 3 -H2 BTB- 2 4.0% 3 -H 2 BTB- 3 4.0% 3 -H 2 BTB-4 4.0% 3— HB (F ) TB-2 5.0% The properties of this composition were determined and were as follows.

T _N. = 1 0 0.1 ° C

 77 = 41.2 mPas

 N = 0. 1 4 2

 Δ ε 1 = 2 6.7

V _th = _1.36 V

Composition example 10

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F, F) B (F)-F (No. 5 2) 6.0% F 2 -GHB (F) -OCF 3 (No. 95) 6.0% F 3 -HGB ( F, F) -CF 3 (No. 1 3 7) 6.0%

2-BEB-C 1 2.0%

3-BEB-C 4.0%

4-BEB-C 6.0% 3 -HB-C 1 0.0%

3-HEB-04 1 2.0%

4-HEB-02 8.0%

5-HEB-01 8.0% 3 -HEB-02 6.0% 5 -HEB-02 5.0% 30 HHB—10% 3 -HHB-01 0% The properties of this composition were determined, and the results were as follows.

T _N. = 6 0.0 ° C

 7? = 35.5 mPas

 N = 0.1 0.1 8

 Δ £ 1 = 9.5

V _th = 1.5 3V

Composition example 1 1

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F) -CF 3 (No. 7) 4 0%

F 5 -GB-OCF 3 (No. 1 3) 30%

2 -BE B-C 1 0 0%

5 -BB-C 1 2 0%

1-BTB-30%

2 -BTB- 1 1 0 0%

1 0-B E B-2 1 0 0%

1 0-BEB- 5 1 2 0%

2 -HHB 1.4 0%

3 -HHB F 40% 3 -HHB 170% 3 -HHB 01 400% 3 -HHB 313,0% The properties of this composition were determined, and the results were as follows.

 7? = 19.8 mPas

Δη = 0.1 4 6 Δ ε 1 = 5.8

V _lh = 2.0 1 V

Composition example 1 2

 A liquid crystal composition having the following compound content was prepared.

 F 3-GB (F, F) B (F)-F (No. 5 2) 2.0%

F 2 -G 2 B (F) B (F)-F (No. 1 24) 2.0%

F 3 -HGB (F, F) -CF 3 (No. 1 3 7) 2.0%

1 V2 -BEB (F, F) 1 C 8.0%

3 -HB-C 4.0% V 2 V-HB-C 1 4.0%

V 2 V-HH- 3 19.0%

3 -HB-02 4.0%

3 -HHB- 1 1 0.0%

3 -HHB- 3 1 5.0% 3 -HB (F) TB- 2 4.0%

3 -HB (F) TB- 3 4.0%

3 -H 2 BTB- 2 4.0%

3 -H2 BTB- 3 4.0%

3 -H 2 BTB- 4 4.0% The characteristics of this composition were measured, and the results were as follows.

 77 = 2 0.9 mPa as

 Δ n = 0.12 9

 Δ ε 1 = 7.8

V, _h = 2.25V

Composition example 1 3

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F, F) B (F)-F (No. 5 2) 5.0%

F 3 -GB (F) -CF 3 (No. 7) 5.0% 5 -BTB (F) TB- 3 1 0.0% V 2 -HB-TC 1 0.0% 3 -HB-TC 1 0.0% 5 -HB-C 7.0% 5 -BB-C 3 . 0%

2-BTB- 1 1 0.0%

2-BTB-01 5.0%

3-HH- 4 5.0%

3 -HHB- 1 1 0.0% 3 -HHB- 3 1 1.0% 3 -H2 BTB- 2 3.0% 3 -H2 BTB- 3 3.0%

3 -HB (F) TB-23.0% The properties of this composition were determined, and were as follows.

T _N. = 92.0 ° C

 7? = 1 8.3 mP as

 Δn = 0.1 9 8

 Δ ε 1 = 6.6

V _th = 2.3 1 V

Composition example 1 4

 A liquid crystal composition having the following compound content was prepared.

 F 3-GB (F, F) B (F) F (No 5 2) 3.0%

F 3 -GB (F) -CF 3 (No 7) 3.0%

F 5 -GB-OCF 3 (No. 1 3) 3.0%

F 2 -GHB (F) -OCF 3 (No. 9 5) 3.0%

1 V 2-B E B (F, F)-C 6.0%

3 -HB-C 6.0%

2-BTB-1 1 0.0%

5 -HH-VFF 30.0% 1 -BHH-VFF 8.0% 1 One BHH-2 VFF 1 1.0% 3 -H 2 BTB- 2 5.0% 3 -H 2 BTB- 3 4.0% 3 -H 2 BTB- 4 4 . 0% 3 -HHB- 1 4. was determined characteristics 0% this composition, Atsuta _c as follows

 77 = 16.1 mPas

 Δη = 0.12 2

 Δ ε 1 = 5.8

V, _h = 2.39 V

Composition example 15

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F, F) B (F) One F (No. 5 2) 60% F 5 -GBEB (F) -CL (No. 63) 60% 2 -HB-C 50% 3 -HB-02 1 5 0%

2-BTB- 130%

3-HHB- 180% 3 -HHB-F 4.0%

3 -HHB-01 5, 0% 3—HHB— 3 1 4, 0% 3 -HHE B-F 4.0% 5 -HHEB-F 4.0%

2—HHB (F)-F 7.0%

3 -HHB (F) — F 7.0% 5 -HHB (F) — F 7.0%

3—HHB (F, F) — F 5.0% The properties of this composition were determined as follows. '―

 7? = 25.7mP as

 Δ n = 0.0.097

 Δ ε 1 = 4.5

Composition Example 1 6

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F, F) B (F) -F (No. 5 2) 5.0% F 2 -GHB (F) -OCF 3 (No. 95) 4.0%

F 2-G 2 B (F) B (F)-F (No. 1 24) 4.0%

2 -HHB (F)-F 1 7.0%

3 -HHB (F)-F 1 7.0% 5 -HHB (F)-F 1 6.0% 2 -H2HB (F) -F 1 0.0%

3 -H2HB (F) -F 5.0%

5 -H2HB (F) -F 1 0.0%

2 -HBB (F) 1 F 6.0%

3-HBB (F) -F 6.0% The properties of this composition were determined, and the results were as follows.

 77 = 28.8 mPas

 N = 0.0 8 6

 Δ ε 1 = 6.4

V, _h = 1.6 V

 Further, 0.3 part of the optically active compound represented by the formula (Op_8) described above was added to 100 parts of the primary composition to obtain a secondary composition, and the properties of the secondary composition were obtained. It was right.

P = 7 8 Composition Example 17 ′ A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F, F) B (F)-F (No. 5 2) 6.0%

7 -HB (F)-F 5.0% 5 -H 2 B (F) -F 5.0%

3 -HB-02 1 0.0%

3 -HH- 4 2.0%

3 -HH C5 D, 6 D, 7 D] 1 43.0%

2 -HHB (F) -F 1 0.0% 3 -HHB (F)-F 1 0.0%

5 -HH [5 D, 6 D, 7 D] B (F) F 1 0.0%

3 -H 2 HB (F)-F 5.0%

2 -HBB (F) -F 3.0%

3 -HBB (F)-F 3.0% 2 -H 2 B B (F)-F 5.0%

3 -H 2 B B (F) -F 6.0%

3 -HHB- 1 8.0%

3 -HHB-01 5.0%

3 -HHB-34.0% The characteristics of this composition were measured, and the results were as follows.

 Sword = 19.5 mPas

 Δ n = 0. 0 9 0

 Δ ε 1 = 4.4

V, _h = 2.38 V

Composition Example 1 8

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F) -CF 3 (No. 7) 4.0%

F 5 -GB-OCF 3 (No. 13) 4.0% F 3 -GHB B (F)-F (No. 1 5 2) 4.0% F 4 -HHGB-C F 3 (No. 1 9 1) 4.0% 7-HB (F, F)-F 3.0% 3 HB- 02 7.0%

2 -HHB (F) -F 1 0.0%

3 -HHB (F) -F 1 0.0% 5 HHB (F) -F 1 0.0%

2 -HBB (F)-F 9.0%

3 -HB B (F) — F 9.0%

2-HB B-F 4.0% 3 HBB-F 4.0% 5 -HB B-F 3.0%

3—HB B (F, F) —F 5.0% 5-HBB (F, F) —F 10.0% The properties of this composition were determined, and the results were as follows.

 77 = 25.1 mPas

 Δη = 0.1 4

 Δ £ 1 = 6.5

V, _h = 1.64 V

Composition Example 1 9

 A liquid crystal composition having the following compound content was prepared.

 F 2 -G 4 B (F) — F (No. 2 2) 3.0% F 2 -GHB (F) -OCF 3 (No. 95) 3.0% F 3 -HGB (F, F) -CF 3 (No. 1 3 7) 3.0% F 3 -HG 4 B (F, F)-F (No. 1 5 0) 3.0% 7 -HB (F, F) 1 F 3. 0%

3 -H 2HB (F, F)-F 1 2.0%

4 -H 2 HB (F, F) — F 1 0.0% 5 -H2HB (F, F) —F 1 h. 0%

3 -HHB (F, F) — F 5.0%

4 -HHB (F, F) — F 5.0%

3-HH 2 B (F, F)-F 1 5.0%

5 -HH2 B (F, F) -F 1 0.0% 3 -HBB (F, F)-F 1 2.0% 3-HBCF 20B (F, F) 1 F 6.0% The properties were determined as follows.

T _N1 = 68.5 ° C

 7? = 27.4 mPas

 Δ n = 0.079

 Δ ε 1 = 8.8

V, _h = 1.53V

Composition Example 20

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F, F) B (F)-F (No. 52) 5.0%

F 2-G2HB (F) -OCF 2CF2H (No. 1 1 9) 5.0%

F 5 -GBEB (F) One CI (No 63) 3.0% F 3-GHB B (F) — F (No 1 52) 3.0% 7 -HB (F, F)-F 5.0% 3 -H2HB (F, F)-F 1 2.0%

3 -HHB (F, F) — F 1 0.0%

4 -HHB (F, F)-F 5.0% 3 -HBB (F, F)-F 1 0.0%

3 -HHE B (F, F)-F 1 0.0%

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) -F10% 3-HHBB (F, F) -F30% The properties of this composition were determined, and the results were as follows.

T _N1 = 75.7 ° C

 7? = 4 0.3 mPa a-s

 Δ n = 0.08 1

 Δ ε 1 = 1 3.1

V, _h = 1.39 V

Composition example 2 1

 A liquid crystal composition having the following compound content was prepared.

 F 2 -G 2 B (CD -CL (No. 20) 40% F 2 -GHB (F) -OCF 3 (No. 95) 70% F 3 -HGB (F, F) -CF 3 ( No. 1 3 7) 0%

3-HB-CL 100% 5 -HB-CL 40%

101 -HH- 550%

2 -HBB (F) -F 8 0%

3 -HBB (F) — F 80%

4-HHB-CL 80%

5-HHB-CL 8, 0%

3 -H2HB (F) -CL 4.0% 3 -HB B (F, F)-F 1 0.0% 5 -H2 BB (F, F) 1 F 9.0% 3 -HB (F) VB -24.0% 3 -HB (F) VB- 34.0% The characteristics of this composition were determined as follows.

T _N ] = 8 0.5 ° C

 77 = 23.8 mP as

Δ n = 0.122 Δ ε 1 = 6.1

V _th = 1.76 V

 Composition Example 22

 A liquid crystal composition having the following compound content was prepared.

 F 3-GB (F, F) B (F)-F (No. 52) 4.0%

F 3 -GB (F) -CF 3 (No. 7) 4.0% F 5-GB-OCF 3 (No. 1 3) 4.0% F 2 -G 2 B (F) B (F) F (No. 1 24) 4.0% F 3 -HGB (F, F) _CF 3 (No. 1 37) 4.0% 3 -HHB (F, F)-F 9.0%

3 -H 2 HB (F, F) — F 8.0%

4 -H 2 HB (F, F) —F 8.0%

5 -H2HB (F, F)-F 8.0% 3 -HBB (F, F)-F 2 1.0% 3 -H 2 B B (F, F)-F 1 0.0%

5 -HHBB (F, F) —F 3.0%

5 -HHEBB-F 2.0%

3 -HH2 BB (F, F)-F 3.0%

101-HBBH- 44.0% 1 O 1 -HBBH- 54.0% The properties of this composition were determined, and the results were as follows.

T _N. = 82.5. C

 77 = 39.5 mPa as

 Δ n = 0.104

 Δ ε 1 = 9.4

V _th = 1.50V

Composition Example 23

 A liquid crystal composition having the following compound content was prepared.

F 2-GHB (F) -OCF 3 (No. 95) 7.0% F 5 -GB-OCF 3 (No. 1 3) 5.0% F 2-G 2 B (F) B (F) F (thing N 0.1 2 4) 5.0% 5 HB-F 1 2.0%

6-HB-F 9.0%

7-HB-F 7.0%

3-HHB-OCF 3 7.0%

4-HHB-OCF 3 7.0%

5-HHB-OCF 3 5.0% 3 -HH 2 B-OCF 3 4.0% 5 -HH 2 B-OCF 3 4.0% 3 -HHB (F, F) -OCF 3 5.0% 3 -HBB (F) — F 1 0.0% 3 -HH 2 B (F) 1 F 3.0% 3 -HB (F) BH- 3 3.0% 5 -HB BH- 3 3.0%

3 -HHB (F, F) -OCF 2 H 4.0% The characteristics of this composition were measured, and the results were as follows.

 6 8.1. C

 7? = 19.0 mP as

 N = 0.08

 Ε1 = 4.7

Composition Example 24

 A liquid crystal composition having the following compound content was prepared.

F 2 -G 2 B (F) B (F) F (No. 1 2 4) 5.0% 5 -H 4 HB (F, F) -F 7.0% 5 -H 4 HB-OCF 3 1 5.0% 3 -H4 HB (F, F)-CF 3 8.0% 5 -H4 HB (F, F) — CF 3 10.0% 3 -HB-CL 6.0%

5 -HB-CL 4.0%

3 -H 2 B B (F) — F 1 0.0%

5 -HVHB (F, F)-F 5.0%

3 -HHB-OCF 3 5.0%

3 -H2HB-OCF 3 5.0% V-HHB (F)-F 5.0%

3 -HHB (F) — F 5.0%

5 -HHEB-OCF 3 2.0%

3 -HBEB (F, F)-F 5.0%

5 -HH-V 2 F 3.0% The properties of this composition were determined, and the results were as follows.

 7? = 28.4 mPa a s

 Δ n = 0.092

 Δ ε 1 = 8.4

V, _h = 1.62 V

Composition Example 2 5

 A liquid crystal composition having the following compound content was prepared.

 F 3 -GB (F) -CF 3 (No. 7) 5.0%

F 2 -G 2HB (F) -OCF 2 CF 2H (No. 1 1 9) 5.0%

F 3 -HGB (F, F) -CF 3 (No. 1 3 7) 5.0% F 3 -GHB B (F) — F (No. 1 5 2) 4.0%

2 -HHB (F) — F 2.0%

3 -HHB (F)-F 2.0% 5 -HHB (F)-F 2.0% 2 -HBB (F) -F 6.0% 3— HBB (F)-F 6.0%

3 -H 2 BB (F) -F 9.0% 3—HBB (F, F)-F 2 '5. ϋ%

5 -HBB (F, F)-F 19.0%

101-HBBH—45.0% 101-HBBH—55.0% The properties of this composition were determined and were as follows.

 7? = 4 0.8 mPas

 Δη = 0.125

 Δ ε 1 = 8.1

V, _h = 1.58 V

 Further, 100 parts of the above-mentioned primary composition was added with 25 parts of the optically active compound represented by the formula (Op-5) described above to obtain a secondary composition, and the properties of the secondary composition were obtained. It was right.

 P = Q 2 urn

Composition Example 2 6

 A liquid crystal composition having the following compound content was prepared.

 F 5 -GB-0CF 3 (No. 1 3) 2.0%

5 -HB-CL 1 0.0%

3 -HH- 4 7.0% 3 -HB-02 20.0%

3 -H2HB (F, F) —F 8.0%

3 -HHB (F, F)-F 8.0%

3 -HBB (F, F)-F 6.0%

2 -HHB (F)-F 5.0% 3 -HHB (F) -F 5.0%

5 -HHB (F) -F 5.0%

2-H2HB (F) — F 2.0%

3-H2HB (F)-F 1.0% 5 -H 2 HB (F) -F 2.0% 3— HHB B (F, F)-F 4.0% 3 -HBCF 20B-OCF 3 4.0% 5 -HBCF 2 OB (F, F) -CF 3 4.0%

3—HHB—13.0% 31 HHB-01 4.0% The compound represented by the general formula (1) according to the present invention has the formulas (11a) and (1—b) to (L-d), (1-e) and (1-f)-(l-h) are expanded to those known in the literature, for example, the fourth edition of Experimental Chemistry (Maruzen) , J. Org.Chem., _4_2_, 1821 (1977) and J. Chem.Soc.Perkin Tran s. 2, 204 1 (1899) It can be easily manufactured by making full use of the methods described in, for example.

 In the above production, a 3-propanediol derivative corresponding to the compound group is required as one of the raw materials. First, a synthesis example of this compound is shown below.

 Synthesis of 1,3-propanediol derivatives for compounds represented by formulas (1-1a) to (1-d):

 Fluoroalkyl bromide (17) and getyl malonate (18) were allowed to act in the presence of lithium carbonate in an alcoholic solvent to give compound (19), which was then treated with lithium aluminum hydride ( (Hereinafter abbreviated as LAH) can be reacted in a non-protonic solvent such as tetrahydrofuran (hereinafter abbreviated as THF) to obtain the 1,3-propanediol derivative (20) for the title use.

Synthesis of 1,3-propanediol derivative for compound represented by formula (1-e): Compound (22) synthesized from fluoroalkyl bromide (17) and triphenylphosphine is converted to potassium t The compound is mixed with a base such as 1-butoxide in THF to produce an ylide, which is then reacted with cyclohexanedione monoethylene ketone (21) to obtain a compound (23), which is converted to Pd Hydrogenation is carried out in the presence of a (0) or Ni (0) catalyst, followed by addition of an acid for deprotection to obtain the cyclohexanone derivative (24). The compound (25) was obtained by adding the ethyl phosphonoacetate and sodium hydride to this mixture and conducting the Itti-Hea Horner reaction (see the 4th edition Experimental Chemistry Lecture (Maruzen) 19: 74-77). Hydrogenate this to ethyl ester After the derivative (26), a compound (27) is obtained by reacting lithium diisopropyl pyramide (hereinafter abbreviated as LDA) and methyl methyl carbonate in this order in a non-protonic solvent such as THF. By applying LAH to this, the 1,3-propanediol derivative (28) for the title use can be obtained.

Synthesis of 3-propanediol derivative using compound represented by formula (1—h): 1,3-propanediol described above except that cyclohexanedione monoethylene ketal (21) is replaced with compound (29) The 1,3-propanediol derivative (30) for the title use can be obtained in the same manner as the method for obtaining the derivative (28).

(C ₂ H ₅ 0) ₂ POCH ₂ C0 ₂ C ₂ H ₅ , NaH

 LDA, CICOOCH; OCH 3 LAH

OC ₂ H ₅

The compound of the present invention can be suitably obtained by using the thus obtained 1,3-propanediol derivative as one of the raw materials.

Preparation of the compound represented by the formula (1_a):

 (Compound of n220)

 It can be obtained by reacting a 1,3-propanediol derivative (20) with a benzaldehyde derivative (31) in the presence of an acid catalyst such as paratoluenesulfonic acid.

 (Compound with n 2 = 1)

 Using the benzaldehyde derivative (31), ethyl acetylethyl phosphonoacetate and sodium hydride, these were subjected to the Wittig-Hiehorner reaction described above to obtain the compound (32), which was hydrogenated to give the ethyl ester derivative. After making (33), a aldehyde derivative (34) is obtained by the action of a reducing agent such as diisobutylaluminum hydride (hereinafter abbreviated as DI BAL).

 Except that this compound is used in place of the benzaldehyde derivative (31), the reaction with the 1,3-propanediol derivative (20) is performed in the same manner as in the case of obtaining the compound of n 2 = 0, and the title compound is obtained. Obtainable.

 (Compound with n 2 = 2)

An aldehyde derivative (35) was obtained in the same manner as in the case of obtaining a compound with n 2 = 1, except that the aldehyde derivative (34) was used in place of the benzyl aldehyde derivative (31). The title compound can be obtained by reacting with the 1,3-propanediol derivative (20) in the same manner as in the case of obtaining the compound of n 2 = 0 except that the compound is used in place of the compound (31).

(20), Η ^÷

 (1-a) (η2 = 1)

(C ₂ H ₅ 0), POC¾C0 ₉ C-, H ₅ , NaH (34)>-

H

 (20), H

(1-a) (n2 = 2)

(Wherein Q, Q ₂ and Y have the same meanings as described above.) '· Production of compound represented by formula (1-1b):

 (Compound in which Zb is a single bond)

 A 1,3-propanediol derivative (20) was reacted with a benzaldehyde derivative (36) in the presence of an acid catalyst such as paratoluenesulfonic acid to obtain a phenyldioxane derivative (37), which was then treated with butyllithium. (Bu Li) is allowed to act at about −50 ° C. to obtain lithoide (38). The title compound can be obtained by subjecting it to a known method for synthesizing a homobiaryl compound, and there are usually two methods.

 One of them is a method described in J. Org. Chem., J_2, 1821 (1977), in which zinc chloride, Pd (0) and This is a method in which the bromobenzene derivative (39) acts sequentially in this order.

 The other one is a method described in J. Chem. Soc. Perkin Trans. 2, 2, 41 (1 89 9), and (i) converting iodide (38) to iodine. And (bor) a boronic acid derivative (40) obtained from the Grignard reagent prepared from the bromobenzene derivative (39) and a trialkyl borate, such as Pd (0) or the like. In this method, a coupling reaction is performed in the presence of a catalyst.

 (Compound in which Zb is -C〇〇—)

 The 4th edition Experimental Chemistry Course (Maruzen) Based on the method described in Vol. 22, page 16, the carboxylic acid derivative (41) was obtained by reacting the above thioide (38 with carbon dioxide). Based on the method described in Vol. 22, p. 46, the phenol derivative (42) was converted from 4-dimethylaminopyridine and 1,3-dicyclohexylcarbodiimide (hereinafter abbreviated as DCC). By acting in the coexistence, an ester (43) of the title compound can be obtained.

(2 ゎ is a compound represented by ₂₀ 0)

Bu i 1.Soc.Chim.Be 1 g., _8_, 293 (19778) Based on the method described in the above, the Lawson reagent is acted on the ester (43). This gives thione ester (44), which is then reacted with dimethylaminosulfur trifluoride (hereinafter abbreviated as DAST) in methylene chloride or glyme solvent, or One is based on the method described in Japanese Patent Application Laid-Open No. 6-263679, and is based on tetrabutylammonium dihydrogen trifluoride (hereinafter, abbreviated as TBAH 2 F 3) in methylene chloride or 1,2-dichloroethane. ) And N-Iodisuccinic acid imid (hereinafter abbreviated as NIS) to give the title compound.

 F- (CH2) no DAS

Y (1-b) (Zb: -CF ₂ 0-) (In the formula, Ch, Q ₂ and Y have the same meanings as described above.) '-Production of a compound represented by the formula (1-1C):

 (Compound in which Zb is a single bond)

 The above cyclohexanedione monoethylene ketone (21) is reacted with a bromobenzene derivative (39) and a Grignard reagent (45) prepared from magnesium to give a compound (46), which is converted into an acid. Dehydration, then hydrogenation to compound

After (47), deprotection is performed using an acid to obtain a cyclohexanone derivative (48). This is allowed to react with methoxymethyltriphenylphosphonium chloride and a ylide obtained from a base, followed by deprotection using an acid to obtain an aldehyde derivative (49). 1,3-propanediol derivative in the same manner as in the production of the compound (n 2 == 0) represented by the formula (1-a) except that this compound is used in place of the benzaldehyde derivative (31) By reacting with (20), the title compound can be obtained.

(Compound in which Z b is —CH ₂ CH ₂ —)

 The title compound can be obtained in the same manner as in the method for obtaining a compound in which Zb is a single bond, except that the compound (50) is used in place of the Grignard reagent compound (45).

(20), H ⁺

(lc) (Zb: single bond)

(In the formula, C, Q ₂ and Y have the same meaning as described above.)

Preparation of the compound represented by the formula (111):

 (n 3 = 1, compound in which ring A 1 is represented by formula (a))

 Except that the above aldehyde derivative (49) is replaced by a benzaldehyde derivative (31), the same procedure as in the production of the compound (n2 = 1) represented by the formula (1-1a) is used. Except that the aldehyde derivative (51) was obtained, and then this was used in place of the benzaldehyde derivative (31), the production of the compound (n 2 = 0) represented by the formula (11a) was the same as in the production of the compound (n 2 = 0). In the same manner, the title compound can be obtained by reacting with the 1,3-propanediol derivative (20).

 (Compound with n 3 = 2, ring A 1 force (a))

 Except that the aldehyde derivative (51) is used in place of the aldehyde derivative (49), n 3 = 1 and ring A1 is the same as the method for obtaining the compound represented by the formula (a). A compound can be obtained.

(Compounds wherein n 3 is 1 or 2, ring A 1 force (b), (c) or (e)) In the production of the compound represented by the formula (1-1 a), Y is a hydrogen atom, Q, A compound (52) in which Q ₂ is independently a hydrogen atom or a fluorine atom is synthesized, and then the compound is replaced with a phenyldioxane derivative (37). The title compound can be obtained in the same manner as in the production of the compound represented by (11b) (compound in which Zb is a single bond).

(C ₂ H ₅ 0) ₂ POCH ₂ C0 ₂ C ₂ H5, NaH Η ₂ DIBAL

 (49)

(1-d) (Zb: -CH ₂ CH _2- , ring Al: (a))

(51) (1-d) (Zb: -CH ₂ CH ₂ CH ₂ CH _2- , Ring Al: (a))

(1-d) (ring Al: (b), ( _C ), (e))

(Wherein, Q !, Q ₂ and Y have the same meaning as described above.)

Preparation of the compound represented by the formula (111):

 Except that the 1,3-propanediol derivative (28) is used in place of the 1,3-propanediol derivative (20), the title is the same as in the case of the production of the compound represented by the formula (1-1a). A compound can be obtained.

Preparation of the compound represented by the formula (1-1h):

 The title compound was prepared in the same manner as in the production of the compound represented by the formula (1-1a) except that the 1,3-propanediol derivative (30) was replaced with the 1,3-propanediol derivative (20). Can be obtained.

Production of the compound represented by the formula (111-f) or (1-g):

 It can be obtained by appropriately using the above-mentioned production methods of the compounds represented by the formulas (11a) to (1-e).

Production of compound having a silinane ring:

 A compound having a silanane ring typified by 11-sila or 4-sila14-cyclohexylene can be produced by applying the method described in JP-A-7770148.

 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

 In each example, C indicates a crystal, S indicates a smectic phase, N indicates a nematic phase, and I indicates an isotropic liquid phase.

Example 1

5-(3-Fluoropropyl) — 2— (4— (3,4-difluorophenyl) -3, 5-difluorophenyl)-1,3-dioxane (-n 0 = 3, nl = n 2 = n 4 = 0, η 3 = 1, ring Al = formula (e )), Production of a compound (No. 52)) in which Zb is a single bond, Ql is a fluorine atom, Q2 is a hydrogen atom, and Y is a fluorine atom

First stage

 Ethanol 3 3-Fluorobutyl mouth mopropane 23 1 g (1.64 mo 1), getyl malonate 26 3 g (1.64 mo 1) and potassium carbonate 2 26 g (1.64 mo 1) mo 1) was added and the mixture was refluxed for 10 hours. The reaction solution was filtered using celite, the solvent in the filtrate was distilled off, and the residue was extracted with hexane. The extract was washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain 223 g (l.01mo1) of diethyl 3-fluoropropylmalonate. Its yield from 3-fluorobutene mopropane was 61.6%.

Second stage

 THF11 was added to 7.6 g (1.52mo1) of LAH, and the mixture was cooled to 5 ° C. To this, a 100 ml THF solution of 223 g (1.01 mo 1) of dimethyl 2-fluoropropylmalonate was added dropwise so as not to exceed 20 ° C. After stirring at 10 ° C for 20 minutes, 5 Om1 of water was added dropwise so as not to exceed 20 ° C, and the mixture was stirred for 10 minutes, and 2N-NaOH 8 Oml was added dropwise. After the reaction solution was further stirred at room temperature for 30 minutes, 5 g of magnesium sulfate was added, and the mixture was filtered using celite. The solvent was distilled off to obtain 2- (3-fluoropropyl) -1,3-propanediol. 7 g (1.01 m01) were obtained. This reaction proceeded almost quantitatively.

Third stage

71 g (0.52 mol) of this substance and 96 g (0.68 mol) of 3,5-difluorobenzaldehyde were dissolved in 500 ml of toluene. Toluenesulfonic acid (hereinafter abbreviated as PTS) (17 g) was added, and the mixture was refluxed for 3 hours while being dehydrated using GeneStark. The reaction solution thus obtained was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over magnesium sulfate, and the solvent was distilled off. The residue was recrystallized twice using heptane, and 5— (3-fluoropropyl) —2- (3,5-difluorene phenyl) -11,3-dioxane 29 g (0.1 1 m 0 1 ). This one The yield from 3,5-difluorobenzaldehyde was 21.2%.

4th tier

 5.0 g (19.2 mmo 1) of the above product was dissolved in THF 5 Om 1 and cooled to 160 under a nitrogen atmosphere. To this solution, 1.5 mL of a 1.6 M solution of n-butyllithium in hexane (24.0 mmo 1) was added dropwise while keeping the solution temperature not exceeding 150 ° C. Stirred at temperature for 1 hour. Next, 48 mL (24.0 mmo 1) of a 5 M solution of zinc chloride in THF was added dropwise to the reaction solution while keeping the solution temperature not exceeding 150 ° C, and then added to room temperature. Warmed and stirred for 30 minutes. To this solution were added 0.5 g of tetrakistriphenylphosphine palladium and 4.63 g (2.0 mmol) of 1-promo 3,4-difluorobenzene, and the mixture was refluxed for 3 hours and 30 minutes. 100 ml of water was added to the obtained reaction solution, the product was extracted with toluene, and the extract was washed successively with 3N hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over magnesium sulfate. The solvent was distilled off. The residue was purified by column chromatography using heptane / ethyl acetate 5Z1 as a developing solvent, the solvent was distilled off, and the residue was recrystallized twice with heptane to give 5- (3-fluoropropyl 3.87 g (10.4 mm 01) of 2-) (4- (3,4-difluoroαphenyl) -1,3,5-difluorophenyl) -1,3-dioxane were obtained. The yield from 5- (3-fluoropropyl) -2- (3,5-difluorophenyl)-3-dioxane was 54.2%.

 1 H-NMR (CDC 13) δ (p pm):

7.39 to 7.02 (m, 5H), 5.40 (s, 1H), 4.72 (t, 1H), 4.37 to 4.13 (m, 5H) 3H), 3.69 to 3.44 (m, 2H), 2.28 to 12 (m, 4H).

 C— I 5 4.1 ° C

Based on the description in Example 1 and the column of the detailed description of the invention, the following compounds No. 1 to No. 217 can be produced. In addition, the compound obtained in Example 1 is shown again below. ZL

〇Μ

9 ·. Ν

17'ΟΜ

Otsu · 0Μ

Τ ·. Μ

6dr 9000Ζ / 86 ΟΛ \ fO / Z, / IDd

N r.

Ν οεο. 0 \

 ΓΟ sMr.

 6Γ.

:) Dimensions. . Dimension N O.

9 inch H O.

^ Dimensions ζ ·

e

 © 〇 ■

6 inch NO.

0.

8 L

tO / Z.6Jf / X3 <I 6 L

P0 / L6dT / ∑Dd 9000 86 OAV 0 8

9000Z / 86 OAVfO / Z.6af / X3d ΐ 8

6 ・ 0Ν

6 · Ν

Ζ6

90001/86 OAV

690tO / -6df / X3J 690, Meng OAV N: O. υ Ν Γ.

r.

 〇 〇 o

N r. Ν 0ΠΟ. o

ΝΙ ΪΟ.

CSO. Sa: S

1ΜΓ7Ο

ΰ Λΰά.

έ.

Dimension rN.

N. .

 N O.

 in

 〇 o

SMO.

K OZXO o

Ν ΓΟ

8ZJ

N0.

Cold O.

〇 oo

 Μ ΐ0,

Ν〇 as

οΝΐ

Example 2 (use example 1)

 Nematic liquid crystal composition containing a cyanophenylcyclohexane-based liquid crystal compound (hereinafter sometimes referred to as liquid crystal composition A 1):

 4— (4-Propylcyclohexyl) benzonitrile 2 4%

4- (4-pentylcyclohexyl) benzonitryl 36% 4— (4-heptylcyclohexyl) benzonitryl 25% 4— (4- (4-pentylcyclohexyl) phenylbenzonitryl 15 % Has the following properties:

Clearing point (T _N1 ): 71.7 ° C, cell thickness 8.8〃m Threshold voltage (V, _h ): 1.78 V, Δε: 11.0, Δη: 0 . Viscosity at 7 and 20 ° C (7?): 26.3 mPa's. '—85% by weight of this liquid crystal composition A 1 was obtained in Example 1 with 5— (3-fluoropropyl pill) -12- (4- (3,4-difluorophenyl) -1,3,5-difluorophenyl And 1,3-dioxane (compound N 0.52) were mixed at 15% by weight to prepare a liquid crystal composition B1. It exhibited a nematic phase even after standing at 120 ° C for 30 days, and its characteristics were as follows.

Clearing point (T _N1 ): 63.5 ° C, cell thickness 9.0〃m Threshold voltage (V _th ): 1.40ν, Δε: 12.2, Δη: 0.13 2, viscosity at 20 ° C (τ?): 36.8 mPa · s.

 The physical properties of the above compound No. 52 were calculated from the physical properties of the above liquid crystal compositions and the mixing ratios of the contained compounds by the external method, and the results were as follows.

Clearing point (T _NI ): 17.0 ° C, mm £: 19.0, mm n: 0.104, viscosity at 20 ° C (7?): 95.7 mPa · s .

 As described above, the liquid crystal compound of the present invention has an extremely large Δε, a high specific resistance value, is electrically and chemically stable, and has good compatibility with existing liquid crystal compounds. is there.

 Therefore, when the liquid crystal compound of the present invention is used as a component of a liquid crystal composition, low voltage driving of a liquid crystal display device, particularly, a TF F type liquid crystal display device can be achieved.

Industrial applicability

 The liquid crystal display device using the liquid crystal composition containing the liquid crystal compound of the present invention is used for watches, calculators, various measuring instruments, automobile panels, word processors, electronic notebooks, printers, convenience stores, televisions, and the like.

Claims

O 98/20006 Claims

 1. General formula (1)

(In the formula, n 0 is an integer of 2 to 10, n 1 and n 2 are each independently an integer of 0 to 2, and n 3 and n 4 are each independently 0 or 1. , N 3 ≥ n 4 and η 1 + η 3 + η 4 ≤ 2, Q and Q ₂ each independently represent a hydrogen atom, a fluorine atom or a chlorine atom, and Za, Zb and Zc each represent Independently represents a single bond, — CH ₂ CH ₂ —, — CH ₂ CH ₂ CH ₂ CH ₂ —, — CO〇— or —CF ₂₀ —, and ring A 1 and ring A 2 each independently represent a formula (A) to (i)

(d)

Wherein Y represents a hydrogen atom, a halogen atom or a halogenated alkenyl group having 1 to 5 carbon atoms, and nl = n 2 = n 4 = 0, n3 and Zb are two single bonds, and ring A1 is not a group represented by the formula (b), and the halogenated alkyl group is one or more non-adjacent methylenes in the group. The groups may be replaced by oxygen or sulfur atoms. Each element constituting the compound may include those selected from their isotopes. A dioxane derivative represented by the formula:

 2. Described in claim 1 where n 1 = n 3 -n 4 = 0!ジ dioxane derivatives.

3. The dioxane derivative according to claim 1, wherein n l + n 3 + n 4 = l.

4. The dioxane derivative according to claim 1, wherein n 1 + n 3 + n 4 = 2.

5. The dioxane derivative according to claim 1, wherein n 2 ≠ 0 and n 3 = 1.

6. The dioxane derivative according to claim 1, wherein n 2 = 0, n 3 = 1 and ring A 1 is a group represented by the formula (a).

 7. The dioxane derivative according to claim 1, wherein n 2 = 0, n 3 = 1, and ring A1 is a group selected from the group consisting of formulas (c;) to (g).

 8. A liquid crystal composition comprising at least one dioxane derivative according to any one of claims 1 to 7.

 9. As the first component, at least one dioxane derivative according to any one of claims 1 to 7 is contained, and as the second component, the general formulas (2), (3) and (4)

O 98/20006

(In each formula, R ₃ , Yi, L !, L ₂ , Z, and Z ₂ may be the same or different from each other, and R ₃ is an alkyl group having 1 to 10 carbon atoms. In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or one CH 2 CH—, and an arbitrary hydrogen atom may be substituted with a fluorine atom. Is a fluorine atom, a chlorine atom, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H, CFH ₂ , OCF ₂ CF ₂ H or 〇CF ₂ CFHCF ₃ , L, and L ₂ are each independently a hydrogen atom Or a fluorine atom, Z, and Z ₂ are each independently —CH ₂ CH ₂ —, one CH ₂ CH ₂ CH ₂ CH ₂ —, —COO—, —CF ₂ 0—, —〇CF ₂ —, — CH = CH— or a single bond Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or a hydrogen atom in which a hydrogen atom may be replaced by a fluorine atom or Two ren, C represents trans-1,4-cyclohexylene or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom In the compounds of each formula, each element constituting them is an isotope thereof. A liquid crystal composition characterized by containing at least one compound selected from the group consisting of:

 10. As the first component, at least one dioxane derivative according to any one of claims 1 to 7 is contained, and as the second component, the general formula (5) and / or (6)

(In each formula, R ₄ and R ₅ each independently represent an alkyl group having 1 to 10 carbon atoms. In the alkyl group, one or more non-adjacent methylene groups are an oxygen atom or one CH = It may be substituted with CH-, or any hydrogen atom may be substituted with a fluorine atom Y ₂ is one CN group or one C≡C—CN, and ring E is trans-1,4-synthesis Xylene, 1,4-phenylene, 1,3-dioxane-1,5-diyl or Is pyrimidine-1,2,5-diyl, ring G is trans-1,4-cyclohexylene, hydrogen atom may be substituted by fluorine atom 1,4-phenylene or pyrimidine — 2,5-diyl, ring H is trans-1,4-cyclohexylene or 1,4-phenylene, Z ₃ is one CH ₂ CH ₂ —, one COO— or a single bond, L ₃ , L ₄ and L ₅ are each independently It represents a hydrogen atom or a fluorine atom, and b, c and d are each independently 0 or 1. In the compounds of each formula, each element constituting them may include those selected from their isotopes. A liquid crystal composition comprising at least one compound selected from the group consisting of:

 1 1. As a first component, at least one dioxane derivative according to any one of claims 1 to 7 is contained, and as a second component, a general formula (2), (3) or (4)

(In each formula, R ₃ , Y, Li.L ₂ , Z, and Z ₂ may be the same or different between the formulas, and R ₃ is an alkyl group having 1 to 10 carbon atoms. In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or one CH 2 CH—, and an arbitrary hydrogen atom may be substituted with a fluorine atom. the full Tsu atom, chlorine _{atom, OCF 3, OCF 2 H,} CF 3, CF 2 H, CFH 2, OCF 2 Ji? ₂ ^ 1 or a hundred? ₂ 〇? 1 "1_Rei? _3, L, and L ₂ is each independently a hydrogen atom or a fluorine atom, Z and Z ₂ are each independently —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, — C OO—, — CF ₂ 0—, one OCF ₂ —, — CH2 CH— or single bond. Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-1,2,5-diyl or a hydrogen atom in which a hydrogen atom may be replaced by a fluorine atom, 1,4-phenylene, and Ring C is trans-1,1, 4- represents cyclohexylene or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom. In the compounds of each formula, each element constituting them may include those selected from their isotopes. ) Containing at least one compound selected from the group consisting of the following general formulas (7), (8) and (9):

R ₆ ~ ("l" ~ Z ₄ "(j" ~ Z ₅ — R ₇ (7)

R ₆ ~ l ")" Z ₄ ~ j ~ Z ₅ ~ (K ~ R ₇ (8)

(In each formula, R ₆ , RT.I, J and K may be the same or different between each formula, and R ₆ and R ₇ are each independently an alkyl group having 1 to 10 carbon atoms. In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or —CH = CH—, and any hydrogen atom may be substituted with a fluorine atom. , J and K are each independently trans-1,4-cyclohexylene, pyrimidine-1,25-diyl or 1,4-phenylene, in which a hydrogen atom may be replaced by a fluorine atom, Z 4 and Z ₅ each independently represents one C≡C—, one C〇〇one, one CH ₂ CH ₂ —, one CH = CH— or a single bond. The elements may include those selected from their isotopes.) The number of compounds selected from the group consisting of A liquid crystal composition comprising at least one of the following.

1 2. As the first component, dioxane g 9 according to any one of claims 1 to 7 Contains at least one derivative and as a second component-general formula (5) and / or (6)

(In each formula, R ₄ and R ₅ each independently represent an alkyl group having 1 to 10 carbon atoms. In the alkyl group, one or more methylene groups that are not adjacent to each other are an oxygen atom or one CH. == may be substituted with CH-, or any hydrogen atom may be substituted with a fluorine atom, Y ₂ is one CN group or one C≡C—CN, ring E is trans 1, 4 —Six mouth hexylene, 1,4-phenylene, 1,3-dioxane-1,5-diyl or pyrimidine-1,2,5-diyl, ring G is trans-1,4-cyclohexylene, hydrogen atom May be substituted with a fluorine atom 1,4-phenylene or pyrimidine 1,2,5-diyl, ring H is trans and 4-cyclohexylene or 1,4-phenylene, Z ₃ is CH ₂ CH ₂ —, one C〇0— or a single bond, L ₃ , L ₄ and L ₅ each independently represent a hydrogen atom or a fluorine atom, b, c and And d are each independently 0 or 1. In the compounds of each formula, each element constituting them may include those selected from their isotopes.) Contains at least one component, and as a third component, the general formulas (7), (8) and (9)

R, G Z ₅ ~ (K ~ R ₇ (8) "" K G R (9) (A in each formula, R "R ?, I, J and K may be the same or different from each other among each of the formulas, R _s and R ₇ are each independently an alkyl group having a carbon number of 1-1 0 In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or 1 CH 2 CH—, and any hydrogen atom may be substituted with a fluorine atom. I, J and K are each independently trans-1,4-cyclohexylene, pyrimidine-2,5-diyl or a hydrogen atom may be substituted with a fluorine atom, or 4-phenylene, Z ₄ and Z ₅ each independently represent a C—C—, —C00—, —CH ₂ CH ₂ —, —CH 2 CH— or a single bond. The elements may include those selected from their isotopes.) At least a compound selected from the group consisting of A liquid crystal composition characterized by containing one type.

 1 3. As the first component, at least one dioxane derivative according to any one of claims 1 to 7 is contained, and as a part of the second component, the general formulas (2), (3), and ( Four)

(In each formula, R ₃ , L, L ₂ , Z, and Z ₂ may be the same or different from each other in each formula, and R ₃ is an alkyl group having 1 to 10 carbon atoms, In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or 1 CH 2 CH—, and an arbitrary hydrogen atom may be substituted with a fluorine atom. Nitrogen atom, chlorine atom, OCF ₃ , OCF ₂ H, CF ₃ , CF ₂ H, CF'H ₂ , -OCF ₂ CF ₂ H or 0 CF ₂ CFHCF ₃ , L, and L ₂ are each independently A hydrogen atom or a fluorine atom, and Z ₂ are each independently —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, one C〇0—, one CF ₂₀ —, one CF ₂ —, Indicates one CH = CH— or a single bond. Ring B is trans-1,4-cyclohexylene, 1,3-dioxane-1,2,5-diyl or 1,4-phenylene in which a hydrogen atom may be substituted with a fluorine atom, and ring C is trans-1,1, 4-cyclohexylene or 1,4-phenylene in which a hydrogen atom may be replaced by a fluorine atom: diene. In the compounds of each formula, each element constituting them may include those selected from their isotopes. ) Containing at least one compound selected from the group consisting of the following general formulas (5) and / or (6):

(In each formula, R ₄ and R ₅ each independently represent an alkyl group having 1 to 10 carbon atoms. In the alkyl group, one or more non-adjacent methylene groups are an oxygen atom or one CH = Y ₂ may be substituted with a fluorine atom or CH ₂ may be substituted with CH—, Y ₂ may be a CN group or C 1 C—CN, and ring E may be a trans-1,4-cycloalkyl group. Hexylene, 1,4-phenylene, 1,3-dioxane-1,5-diyl or pyrimidine-1,2,5-diyl, ring G is trans-1,4-cyclohexylene, hydrogen atom is fluorine atom 1,4-Phenylene or pyrimidine-2,5-diyl, ring H is trans-1,4-cyclohexidylene or 1,4-phenylene, and Z ₃ is —CH ₂ CH ₂ — which may be substituted with one COO- or a covalent bond, L _3, L ₄ and L ₅ represents a hydrogen atom or a fluorine atom each independently, b, c And d is 0 or 1 each independently. In the compounds of the formula, each element constituting them may include those selected from the isotopes thereof.) Compound selected from the small Contains at least one kind, and as the third component, the general formulas (7), (8) and-(9)

R ₆ ~ fl Z ₄ ~ j | ~ Z ₅ —R ₇ (7)

R ₆ Z ₄ to Z ₅ HTK | ~ R ₇ (8)

(In each formula, R ₆ , RI, J and K may be the same or different from each other in each formula, and R ₆ and R ₇ are each independently an alkyl group having 1 to 10 carbon atoms, In the alkyl group, one or more non-adjacent methylene groups may be substituted with an oxygen atom or one CH = CH—, and any hydrogen atom may be substituted with a fluorine atom. J and K are each independently trans-one 1, 4-xylene to Shikuro, 1 pyrimidine one 2, 5 one Jiiru or hydrogen atoms may be substituted by fluorine atoms, 4-phenylene, Z ₄ and Zs Each independently represents a C—C—, —COO— CH ₂ CH ₂ —, — CH—CH—, or a single bond. The compound may include at least one compound selected from the group consisting of: A liquid crystal composition characterized by.

 1 4. The liquid crystal composition according to claim 8, further comprising an optically active compound.

 1 5. The liquid crystal composition according to claim 9, further comprising an optically active compound.

 1 6. The liquid crystal composition according to claim 10, further comprising an optically active compound.

17. The liquid crystal composition according to claim 11, further comprising an optically active compound.

1 8. The liquid crystal composition according to claim 2, further comprising an optically active compound.

 1 9. The liquid crystal composition according to claim 13, further comprising an optically active compound.

 20. A liquid crystal display device comprising the liquid crystal composition according to claim 8.

2 1. A liquid crystal display device comprising the liquid crystal composition according to claim 9.

2 2. A liquid crystal display device comprising the liquid crystal composition according to claim 10.

2 3. A liquid crystal display device comprising the liquid crystal composition according to claim 11.

2 4. A liquid crystal display device comprising the liquid crystal composition according to claim 12.

2 5. A liquid crystal display device comprising the liquid crystal composition according to claim 13.

2 6. A liquid crystal display device comprising the liquid crystal composition according to claim 14.

2 7. A liquid crystal display device comprising the liquid crystal composition according to claim 15.

2 8. A liquid crystal display device comprising the liquid crystal composition according to claim 16.

2 9. A liquid crystal display device comprising the liquid crystal composition according to claim 17.

30. A liquid crystal display device comprising the liquid crystal composition according to claim 18.

3 1. A liquid crystal display device comprising the liquid crystal composition according to claim 19.