KR100343350B1 - Supertwist liquid crystal display - Google Patents

Abstract

The present invention relates to a super twisted liquid crystal display having excellent properties when the nematic liquid crystal mixture contains one or more compounds of the following formula:

(3)

(Wherein, R ¹ , R ² , , p, r and s are as defined in claim 1).

Description

[0001] SUPERWIST LIQUID CRYSTAL DISPLAY [0002]

The SLCD defined at the outset is described, for example, in EP 0 131 216 B1; DE 34 23 993 A1; EP 0 098 070 A2; M. M. Schadt and F. F. Leenhouts, 17th Freiburg Congress on Liquid Crystals (Apr. K. K. Kawasaki, SID 87 Digest 391 (20.6); M. Shat and F. Linfts, SID 87 Digest 372 (20.1); K. K. Katoh, " Japanese Journal of Applied Physics, Vol. 26, No. 11, L 1784-L 1786 (1987); F. Lin Hoots, Allen, Appl. Phys. Lett. 50 (21), 1468 (1987). a. half. HA van Sprang and H. G. HG Koopman, J. Appl. Phys. 62 (5), 1734 (1987); tea. second. TJ Scheffer and J. < RTI ID = 0.0 > J. Nehring, Appl. Phys. Lett. 45 (10), 1021 (1984); Shat and F. Lin Hootz, Appl. Phys. Lett. 50 (5), 236 (1987); blood. EP Raynes, Mol. Cryst. Liq. Cryst. Letters Vol. 4 (1), pages 1-8 (1986). As used herein, the term SLCD includes any highly twisted display device having a twist angle value of 160 ° to 360 °, such as a Waters display device (CM Waters) LCD (DE-A 35 03 259), SBE-LCD (T.J. Schaefer and J.B.), Proc. Soc. Inf. Disp. (New York) (1985) (3rd International Display Conference, Kobe, Japan) 50 (1987), 236, DST-LCD (EP-A 0 246 (1984) 1021), OMI-LCD (M. Schat and F. Linfoot, Appl. Phys. Lett. 842) or BW-STN-LCD (K. Kawasaki, SID 87 Digest 391 (20.6)).

This type of SLCD has excellent gradients of the electro-optic characteristic lines and hence better contrast values, and significantly lower contrast angular dependencies compared to standard TN displays. Particularly at relatively low temperatures, there is a great interest in SLCDs having very short reaction times. To obtain a short reaction time, the viscosity of the liquid crystal mixture was used, in particular, while using a normally unidirectional additive having a relatively high vapor pressure. However, the reaction time obtained was not suitable for all applications.

To obtain a clear electro-optical characteristic line, a liquid crystal composition should have a relatively large K ₃ / K ₁ value and a relatively small Δε / ε ₁ value.

In addition to optimizing contrast and response types,

1. Wide d / p window

2. High long-term chemical stability

3. High electrical resistance

4. It consists of a mixture of low frequency dependence on extreme voltage.

The combination of parameters obtained is still very inadequate, especially in high-multiplex STN (1/400). This is because, in some cases, various conditions are adversely affected by the material parameters.

Therefore, there is a great demand for a SLCD having a very short reaction time and at the same time a wide working temperature range, high characteristic line slope, excellent angular dependence of contrast and low extreme voltage meeting the aforementioned conditions.

DE 35 09 170 discloses compounds of the general formula:

[Chemical Formula 1]

(2)

Chemiker Zeitung 104 (1980), 269-271 describes a compound of formula (3) having a long-chain alkyl radical (m + n> 9). However, the compound of formula (III) has only a steric phase which is unfavorable for use in a nematic liquid crystal mixture. Surprisingly, by reducing the chain length, the nematic phase range and smectic phase degradation were obtained at the same time.

The present invention relates to a super twisted liquid crystal display (SLCD) having a very short reaction time and an excellent steepness and angle dependency, and a novel nematic liquid crystal mixture used therefor.

It is an object of the present invention to provide an SLCD which does not have the above-mentioned disadvantages, or which is only at a lower level and which has a very good slope.

It has now been found that this object can be achieved by using a nematic liquid crystal mixture comprising a 1,2-dicyclohexylethylene derivative of the formula (3).

(3)

(Wherein,

R ¹ is an alkyl, alkoxy or alkenyl radical having 1 to 10 carbon atoms which is unsubstituted or monosubstituted with CN or CF ₂ or mono-substituted with at least halogen and wherein at least one CH ₂ group in the radical is substituted with -O- It can be,

R ² is (CH ₂ ) _n -CH═CH-R ^a or (CH ₂ ) _n -CH═CH ₂ and, when r = 1,

R ^a is straight chain alkyl having 1 to 6 carbon atoms,

n is from 0 to 6,

p and r are each independently of the other 0 or 1, and

s is 1 or 2).

The compound of formula 3 significantly increases the slope of the STN mixture without increasing the reaction time.

Therefore,

Two planar-parallel outer plates forming a cell with the frame,

- a positive dielectric anisotropic nematic liquid crystal mixture present in the cell,

An electrode layer having an alignment layer worn inside the outer plate,

An SLCD containing an angle of twist between the longitudinal axis of the molecules of the outer plate surface and the outer plate of about 1 to 30 and a twist angle from the alignment layer to the alignment layer of the liquid crystal mixture in the cell having a value of -100 to 600 As a result,

The nematic liquid crystal mixture

a) from 20 to 90% by weight of liquid crystal component A consisting of at least one compound having a dielectric anisotropy greater than +1.5;

b) from 10 to 65% by weight of liquid crystal component B consisting of at least one compound having a dielectric anisotropy of -1.5 to +1.5;

c) 0 to 20% by weight of a liquid crystal component D consisting of at least one compound having a dielectric anisotropy of less than -1.5, and

d) an optically active component C in an amount of between about 0.2 and 1.3, the ratio between the layer thickness (plane-parallel outer plate spacing) and the neutral pitch of the chiral nematic liquid crystal mixture,

Characterized in that component B comprises at least one compound of formula (3)

(3)

(Wherein,

R ¹ is an alkyl, alkoxy or alkenyl radical having 1 to 10 carbon atoms which is unsubstituted or monosubstituted with CN or CF ₂ or mono-substituted with at least halogen and wherein at least one CH ₂ group in the radical is substituted with -O- It can be,

R ² is (CH ₂ ) _n -CH═CH-R ^a or (CH ₂ ) _n -CH═CH ₂ and, when r = 1,

R ^a is straight chain alkyl having 1 to 6 carbon atoms,

n is from 0 to 6,

p and r are each independently of the other 0 or 1, and

s is 1 or 2).

The invention also relates to corresponding liquid crystal mixtures for use in SLCD.

Preferred compounds of formula 3 are the specific compounds of subformulae 3a to 3k (L ¹ and L ² = H or F; n = 0 to 6; O = 0 to 6; alkyl = C _1-6 )

[Chemical Formula 3]

(3b)

[Chemical Formula 3c]

(3d)

[Formula 3e]

(3f)

[Formula 3g]

[Chemical Formula 3h]

[Chemical formula 3j]

[Chemical Formula 3k]

A preferred novel mixture consists of a compound of the following formula:

≪ EMI ID =

[Formula 3m]

(3n)

≪ EMI ID =

[Chemical Formula 3p]

[Formula 3q]

[Chemical Formula 3]

[Chemical Formula 3s]

(Wherein R < ^a > is preferably straight chain alkyl and n is 0 to 6). R ^b and R ^{b '} are each independently of the other preferably H or methyl, and further ethyl, propyl, butyl, pentyl or hexyl within the general formulas 3c-3j. O is 0-6.

In the compounds of formula (III), R < ¹ > is preferably alkyl, alkoxy, CN or halogenated alkyl or alkenyl radicals. The halogen is preferably F. Specifically, when p = 1, R ¹ is F, Cl, OCF ₃ , OCF ₂ H, CF ₃ , OCH ₂ CF ₃ , OCHFCF ₃ , OC ₂ F ₅ , C ₂ F ₅ , OC ₂ F ₄ H or OCHF ₂ < / _RTI > and the ring A ^* or to be.

Particularly preferred are compounds wherein R ¹ and / or R ² is an alkenyl radical, the double bond is in the 1- or 3-position and has a trans-structure.

If R < ¹ > is an alkyl radical and / or an alkoxy radical, it may be straight-chain or branched. Straight chain is preferred and has 2, 3, 4, 5, 6 or 7 carbon atoms and is thus preferably ethyl, propyl, butyl pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, Heptoxy, and additionally methyl, octyl, nonyl, decyl, methoxy, octoxy, nonoxy or decoxy.

The oxalkyl is preferably a straight chain 2-oxapropyl (= methoxymethyl), 2- (= enoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 2-, 3-, 4-, or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxacetyl, 2-, 3-, 4-, 5-, 6- or 7- 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, or 2-, 3-, 4-, 5-, 6-, 7-, Lt; / RTI >

If ten thousand and one R ¹ is CH ₂ group is an alkyl radical substituted by -CH = CH-, which may be straight or branched or straight chain. It is preferably straight-chain and has 2 to 10 carbon atoms. Thus, it is specifically exemplified by vinyl, prop-1- or -2-ethyl, but-1-, 2- or -3ethyl, pent-1-, Hept-1-yl, 2-, 3-, 4-, 5- or 6-enyl, oct-1, -1-, 2-. 3-, 4-, -5-, -6- or -7-enyl, non-1-, 2-, 3-, -8-enyl, or des-l-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.

If R < ¹ > is an alkyl radical in which one CH ₂ is replaced by -O- and one is -CO-, they are preferably adjacent. They thus contain one acyloxy group -CO-O- or one oxycarbonyl group -O-CO-. They are preferably straight-chain and have 2 to 6 carbon atoms.

Thus, specifically, the above are specifically exemplified by acetoxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetoxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, Propoxycarbonyl, butoxycarbonyl, propoxycarbonyl, propoxycarbonyl, propoxycarbonyl, propoxycarbonyl, propoxycarbonyl, propoxycarbonyl, propoxycarbonyl, Ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, propoxycarbonylmethyl, , 2- (propoxycarbonyl) ethyl, 3- (methoxycarbonyl) propyl, 3- (ethoxycarbonyl) propyl or 4- (methoxycarbonyl) butyl.

If R ¹ is an alkaryl radical in which one CH ₂ group is unsubstituted or substituted with a substituted -CH = CH- and the adjacent CH ₂ group is replaced by CO or CO-O or O-CO, it may be linear or branched . It is preferably straight-chain and has from 4 to 13 carbon atoms. Thus, specifically, it is specifically exemplified by acryloyloxymethyl, 2-acryloyloxyethyl, 3-acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl, 6-acryloyloxy Hexyl, 7-acryloyloxyheptyl, 8-acryloyloxyoctyl, 9-acryloyloxynonyl, 10-acryloyloxydecyl, methacryloyloxymethyl, 2- methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl, 8-methacryloyl Lt; RTI ID = 0.0 > 9-methacryloyloxynonyl. ≪ / RTI >

If ten thousand and one R ¹ is CN or CF ₃ mono-substituted alkyl or alkenyl radical, this radical is preferably straight-chain ω - position is substituted by CN or CF _3.

If R < ¹ > is an alkyl or alkenyl radical which is at least monosubstituted by halogen, then this radical is preferably straight-chain and the halogen is preferably F or Cl. In the case of multiple substitution, the halogen is preferably F. The radicals obtained also contain perfluorinated radicals. In the case of single substitution, fluorine or chlorine substitution can be made at any desired position, but is preferably the omega - position.

Compounds of formula (III) containing branching group R < ¹ > are important because they are often more soluble in conventional liquid crystal based materials and are particularly important as such chiral dopes if they are optically active.

Branched groups of this type generally do not have one or more chain branches. Preferred branched radicals are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl Methylpentyl, 2-ethylhexyl, 2-propylpentyl, isopropoxy, 2-methylpropoxy, 2-methylbutoxy, Ethylhexoxy, 1-methylhexoxy and 1-methylheptoxy.

It is an alkyl radical substituted ten thousand and one R ¹ has more than one CH ₂ group with -O- and / or -CO-O-, straight chain, which may be straight or branched. A branched chain is preferred and has 3 to 12 carbon atoms. Thus, specifically, the above are specifically exemplified by biscarboxymethyl, 2,2-biscarboxyethyl, 3,3-biscarboxypropyl, 4,4-biscarboxybutyl, 5,5-biscarboxypentyl, (Methoxycarbonyl) methyl, 2,2-bis (methoxycarb) naphthyl, 7,7-bis carboxyheptyl, 8,8-bis carboxy octyl, (Methoxycarbonyl) ethyl, 3,3-bis (methoxycarbonyl) propyl, 4,4-bis (methoxycarbonyl) butyl, (Ethoxycarbonyl) methyl, 2,2-bis (ethoxycarbonyl) heptyl, 7,7-bis (methoxycarbonyl) heptyl, (Ethoxycarbonyl) ethyl, 3,3-bis (ethoxycarbonyl) propyl, 4,4-bis (ethoxycarbonyl) butyl and 5,5-bis (ethoxycarbonyl)

Compounds of formula (III) containing a flap R ² suitable for multi-condensation reactions are suitable for the preparation of liquid crystal line concentrates.

Formula (3) includes the above compound and optical counterparts and mixtures thereof.

Of the compounds of formula (III) and sub-formulas thereof, it is preferred that one or more radicals present therein are indicated as being preferred.

In the compound of formula (3), stereoisomers wherein the cyclic cyclohexane ring [cis] is trans-1,4-disubstituted are preferred.

Compounds of formula 3 can be prepared by known methods as described in literature (for example in standard work such as Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart) Accurate under reaction conditions suitable for the reaction.

The novel compounds are prepared, for example, as described in DE 35 09 170 A1:

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

The novel compounds can also be prepared as follows; Variations which are not described in detail here but are known per se can be used herein.

[Reaction Scheme 4]

[Reaction Scheme 5]

[R ^b and R ^{b '} : H or alkyl having 1 to 6 carbon atoms; r: 0 or 1]

[Reaction Scheme 6]

The present invention also relates to compounds of formula (3), (3e) and to a process for the preparation of the novel intermediates of formula (4).

[Chemical Formula 4]

(Wherein R ^b is H or alkyl having 1 to 6 carbon atoms, and alkyl is C ₁ -C ₆ -alkyl)

[Reaction Scheme 7]

[R ^b and R ^{b '} : H or alkyl]

The new liquid crystal mixture preferably has the following composition:

- Component A preferably comprises the compounds of formulas (5) and (6).

[Chemical Formula 5]

[Chemical Formula 6]

Wherein R is alkyl having 1 to 12 carbon atoms and one or two non-adjacent CH ₂ groups are replaced with -O-, -CH = CH-, -CO-, -OCO- or -COO- However, And Are each, independently of one another, or ego,

L < ^1-6 > are each, independently of one another, H or F,

Z ¹ is -COO-, -CH ₂ CH ₂ - or a single bond,

Z ² is -CH ₂ CH ₂ -, -COO, -C≡24

C- or a single bond,

And, -OCHF- or a single bond, - Q is -CF ₂ -, -CHF-, -OCF ₂

Y is F or Cl,

a is 1 or 2, and

b is 0 or 1).

Preferred compounds of formula 5 correspond to sub-formulas 5a to 5d:

[Chemical Formula 5a]

[Chemical Formula 5b]

[Chemical Formula 5c]

[Chemical Formula 5d]

Wherein R, L < ¹ > and L < ⁵ > are as defined above.

Preferred compounds of formula 6 correspond to sub-formulas 6a to 6t:

[Chemical Formula 6a]

[Formula 6b]

[Chemical Formula 6c]

[Chemical formula 6d]

[Formula 6e]

(6f)

[Chemical Formula 6g]

[Chemical Formula 6h]

[Formula 6i]

[Chemical formula 6j]

[Chemical Formula 6k]

≪ EMI ID =

[Formula 6m]

[Chemical Formula 6n]

≪ EMI ID =

[Chemical Formula 6p]

[Chemical Formula 6q]

[Chemical Formula 6r]

[Chemical Formula 6s]

[Chemical Formula 6t]

In addition to one or more compounds of formula (3), preferred mixtures comprise one, two or three or more compounds of formula (5a, 5b, 5c, 5d, 6d, 6h, 6i, 6l, 6m or 6s, preferably one or more of formula To four compounds of formula 3 and one to three compounds of formulas 5b and 5c.

For example, individual compounds of formulas (5) and (6) or sub-formulas thereof or alternate compounds which may be used in the novel SLCD are known or can be similarly prepared as known compounds.

In a particularly preferred embodiment, component A further comprises a compound of formula (7a-7e): < EMI ID =

[Formula 7a]

[Formula 7b]

[Formula 7c]

[Formula 7d]

[Formula 7e]

Wherein R is an alkyl group having 1 to 12 carbon atoms and one or two non-adjacent CH ₂ groups are substituted with -O-, -CH = CH-, -CO-, -OCO- or -COO- However,

Q ¹ is or ego,

Z ³ is , -CH ₂ CH ₂ - and, -CO-CO-, -O-CO- or a single bond, and

silver or to be.

The mixture preferably comprises 5 to 50% of a compound of formula (7a). Compounds of formula (7a), in particular those of formulas (5e), (5f), (5g), (5h), (5i) and (5k), wherein Z ¹ is -CH ₂ CH ₂ -, -COO- or a single bond, are preferred.

[Chemical Formula 5e]

[Chemical Formula 5f]

[Chemical Formula 5g]

[Chemical Formula 5h]

(5i)

[Chemical Formula 5j]

[Chemical Formula 5k]

Component A preferably comprises at least one compound of formula (5k) and, if desired, at least one compound of formula (5j).

The novel mixture preferably comprises at least one polar compound having a high transparency point selected from the group consisting of compounds of formulas 5l to 5p:

≪ EMI ID =

[Formula 5m]

[Chemical Formula 5n]

≪ EMI ID =

[Chemical Formula 5p]

In compounds 5l to 5p, the 1,4-phenylene ring may also be pendantly substituted with one or two fluorine atoms. Preferred compounds of this type are compounds of formulas 5q to 5t:

[Chemical Formula 5q]

[Chemical Formula 5r]

[Chemical Formula 5s]

[Chemical Formula 5t]

In the novel mixture, the magnification of the compound 5l to 5p is preferably about 2 to 25%. Preferred liquid crystal mixtures preferably comprise from 10 to 40% of at least one compound from group B.

The compounds from group B are excellent in their low rotational viscosity ( r ₁ ) values of <150 mPa · s and their high transparency (> 120 ° C.).

- Component B comprises at least one compound selected from the group consisting of compounds of formulas 8a to 8i:

[Chemical Formula 8a]

[Formula 8b]

[Chemical Formula 8c]

[Chemical Formula 8d]

[Chemical Formula 8e]

[Chemical Formula 8f]

[Chemical Formula 8g]

[Chemical Formula 8h]

[Formula 8i]

(Wherein R ^{1 '} and R ^2' are as defined for R).

- Component B further comprises at least one compound selected from the group consisting of compounds of formulas 8j to 8x:

[Chemical Formula 8j]

[Chemical Formula 8k]

&Lt; EMI ID =

[Formula 8m]

[Formula 8n]

&Lt; EMI ID =

[Chemical Formula 8p]

[Formula 8q]

&Lt; EMI ID =

[Chemical Formula 8s]

[Chemical Formula 8t]

[Chemical Formula 8u]

[Chemical Formula 8v]

[Formula 8w]

[Formula 8x]

Wherein R ^{1 '} and R ^2' are as defined for R and the 1,4-phenylene group at 8j to 8s, 8w and 8x may also be monosubstituted or multisubstituted independently of one another by fluorine, .

- Component B further comprises at least one compound selected from the group consisting of compounds of formulas 8y to 8ad:

[Formula y]

(Z)

[Chemical Formula 8aa]

[Chemical Formula 8ab]

[Chemical Formula 8ac]

[Chemical Formula 8ad]

Wherein R ^{1 '} and R ^2' are as defined for R and the 1,4-phenylene group at 8y to 8ad may also be monosubstituted or multisubstituted independently of one another by fluorine.

- Component B comprises at least one compound selected from the group consisting of compounds 8ae to 8af:

[Chemical Formula 8ae]

[Chemical Formula 8af]

_Wherein C _r H _{2r + 1} is a straight chain alkyl group having up to 9 carbon atoms.

In addition to components A, B and C, the liquid crystal mixture additionally comprises at least one compound selected from the group consisting of compounds of formulas 6 and 8, as defined for R ^{1 '} and R ^2'

[Chemical Formula 6]

[Chemical Formula 8]

Preferred liquid crystal mixtures comprise at least one component selected from the group consisting of compounds of the formula:

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

Wherein Y is F or Cl, L &lt; ¹ &gt; is H or F, and R is as defined above.

The liquid crystal mixture also contains an optically active component C in an amount such that the ratio between the layer thickness (plane-parallel outer plate spacing) and the neutral pitch of the chiral nematic liquid crystal mixture is at least 0.2. In the case of this component, a number of chiral dopes are available to the person skilled in the art, to some extent, such as cholesteryl nonanoate, S811 (Merck, Darmstadt, FRG) and CB 15 . The choice of dope is not important in itself.

The novel liquid crystal mixture preferably comprises at least one compound selected from group B1 consisting of the compounds of formulas 13a to 13d and /

[Chemical Formula 13a]

[Chemical Formula 13b]

[Chemical Formula 13c]

[Chemical Formula 13d]

Wherein R ^{1 '} and R ^2' are each independently of the other as defined for R and Z is -CH ₂ CH ₂ -, -CO-O-, -O-CO- or a single bond, and

silver or to be),

And at least one compound selected from group B2 consisting of the compounds of formulas (13e) to (13g) and / or comprises:

[Chemical Formula 13e]

[13f]

[Chemical Formula 13g]

(Wherein,

R is as defined above,

Z ⁰ is -CH ₂ CH ₂ - or a single bond,

Q ⁰ is or ego,

Wherein r is from 1 to 9,

X is CN or F,

L &lt; ¹ &gt; is H or F)

And at least one compound selected from the group B3 consisting of the compounds of the following formulas 13h, 13i and 13j:

[Chemical Formula 13h]

[Formula 13i]

[Chemical Formula 13j]

Wherein R ^{1 '} and R ^2' are, independently of each other, as defined for R,

Y is F or Cl, and silver or to be).

In a particularly preferred embodiment, the novel mixture comprises from about 5 to 35%, in particular from 10 to 20%, liquid crystal tolane compounds. This makes it possible to significantly reduce the reaction time using a smaller layer thickness (about 5-6 mu m). Particular preference is given to mixtures comprising at least one compound selected from the group T consisting of the compounds of the formulas 14a to 14c:

[Chemical Formula 14a]

[Chemical Formula 14b]

[Chemical Formula 14c]

(Wherein,

Q ² is or ego,

silver or , And preferably ego,

t is 0 or 1

L &lt; ^1-6 &gt; are each, independently of one another, H or F,

And, -OCHF- or a single bond, - Q is -CF ₂ -, -CHF-, -OCF ₂

Y is F or Cl,

R ^{1 '} and R ^2' are each independently of one another as defined for R)

The magnification of the compound from the T group is preferably 5 to 30%, especially 5 to 20%.

Component B preferably comprises one or more compounds of formulas 15 to 17:

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

Wherein R ^{1 '} and R ^2' are each independently of the other as defined for R and R ^{1 '} is preferably alkyl having 1 to 4 carbon atoms, especially 1 to 2 carbon atoms, and R ^2''it is an alkoxy group having preferably 1 to 4 carbon atoms, particularly 1 to 2 of carbon atoms).

The magnification of the compound from the group B1 is preferably 10 to 50%, particularly 15 to 40%.

A particularly preferred compound of formula 13c is a compound of sub-formulas 13k and 13l:

[Chemical Formula 13k]

&Lt; EMI ID =

(Wherein, R ^{3 'is} _{CH 3 - (CH 2) o} -O-, CH 3 - (CH 2) p -, trans _{-H- (CH 2) q -CH =} CH- (CH 2 CH 2) _b -CH ₂ O- or trans _{-H- (CH 2) q -CH =} CH- (CH 2 CH 2) b -, CH 3 - (CH 2) o -O-CH 2 - , and

R ^{4 '} is CH ₃ - (CH ₂ ) _p -

o is 1, 2, 3 or 4,

q is 0, 1, 2 or 3,

b is 0 or 1, and

p is 1, 2, 3 or 4).

Particularly preferred are those compounds of formula (13c) wherein one of the radicals R ^{3 '} or R ^4' is O- (CH ₂ ) _o -CH ₃ or CH ₂ -O- (CH ₂ ) _o -CH ₂ -.

Also preferred are compounds of the sub-formulas:

[Formula 13m]

Wherein R ^{3 '} and R ^4' are each independently of the other as defined above.

The magnification of the compound of formula (13c) having the sub-formula is preferably about 5 to 45%, particularly preferably about 10 to 35%. Particularly preferred compounds of formula (13d) have the following sub-formulas:

[Chemical Formula 13n]

Wherein R ^* is CH ₃ - (CH ₂ ) _o -O- or trans-H- (CH ₂ ) _q -CH═CH- (CH ₂ CH ₂ ) _b -CH ₂ O-, and R ^{2 '} Is CH ₃ - (CH ₂ ) _p -, and in the above

o is 1, 2, 3 or 4,

q is 0, 1, 2 or 3,

b is 0 or 1, and

p is 1, 2, 3 or 4).

The magnification of the compound or the compound of the formula (13d) is preferably about 5 to 40%, particularly preferably about 10 to 35%.

The mixture preferably comprises a compound of formula &lt; RTI ID = 0.0 &gt; 13c, &lt; / RTI &gt;

&Lt; EMI ID =

In a particularly preferred embodiment, the mixture simultaneously comprises the compounds of formulas 13c and 13d, wherein the total magnification of the components from group B1 is as observed.

If the compound of formula 13a and / or 13c is present, then R ² and R ³ are preferably each independently of the others n-alkyl having 1 to 7 carbon atoms or (trans) -n- Alkenyl. Z is preferably a single bond.

In the equation,

silver or ego,

Also preferred are novel mixtures comprising at least one compound of formula (13d) wherein R ^{1 '} and R ^2' have the preferred meanings given above, particularly preferably those having 1 to 7 carbon atoms.

In all cases, the overall magnification of the components from group B1 is as observed.

The magnification of the compound from the B2 group is preferably about 5 to 45%, especially 5 to 20%. The magnification (preferred range) for 13d to 13g is as follows:

13e: about 5 to 30%, preferably about 5 to 15%

The sum of 13d and 13g: about 5 to 25%, preferably about 10 to 20%.

Preferred compounds from group B2 are shown below:

[Chemical Formula 13p]

[Formula 13q]

[Chemical Formula 13r]

[Chemical Formula 13s]

[Chemical Formula 13t]

R 'is preferably n-alkyl having 1 to 7 carbon atoms or (trans) -n-alkenyl having 3 to 7 carbon atoms. R ^{1 '} preferably has the preferred meanings given above for R or is fluorine. L ¹ is preferably fluorine. x is 1-15.

The novel mixture preferably contains at least one compound selected from the group consisting of 13r, 13s and 13t in a total magnification of about 5 to 35%.

In a particularly preferred embodiment, the novel mixture further comprises, besides 13r, 13s and 13t (R = F), for example, a terminal fluorinated compound selected from the group consisting of:

[Chemical Formula 18]

[Chemical Formula 19]

Further comprising a polar hetero ring compound selected from the group consisting of:

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

Wherein R ^{1 '} is preferably n-alkyl having 1 to 7 carbon atoms or (trans) -n-alkenyl having 3 to 7 carbon atoms, a is 1 or 2, b is 0 Or 1, X ⁰ is F, Cl, CF ₃ , -OCF ₃ or -OCHF ₃ , and L ¹ is H or F.

The total magnification of all terminal fluorinated compounds is preferably about 5 to 65%, especially about 15 to 40%.

The magnification of the compound from group B3 is preferably about 5 to 30%, particularly preferably about 10 to 20%. R ^{2 '} is preferably n-alkyl or n-alkoxy, each having from 1 to 9 carbon atoms.

However, similar compounds containing alkenyl or alkenyloxy groups can also be used. Compounds of formula 13h are preferred.

The novel mixture preferably comprises a compound from formula (3) and a compound from at least one of the groups B1, B2 and B3. The mixture preferably comprises at least one compound from group B1 or at least one compound from group B2 and / or group B3.

The magnification of the compound of component C is preferably 0 to 20%, especially 0 to 10%.

In a particularly preferred embodiment, the novel mixture preferably contains about 5 to 20% of at least one compound having a dielectric anisotropy (component C) of not more than -2. Compounds of this type are, for example, derivatives of 2,3-dicyanohydroquinone or derivatives thereof as described in DE-A 32 32 707 or DE-A 34 07 013 Cyclohexane derivatives containing structural units of formula &lt; RTI ID = 0.0 &gt; (I) &lt; / RTI &gt;

However, compounds containing structural units 2,3-difluoro-1,4-phenylene, for example DE-A 38 07 801, 38 07 861, 38 07 863, 38 07 864 or 38 07 908 Lt; / RTI &gt; are preferred. Particular preference is given to tolans containing the above structural units as described in International Patent Application PCT / DE 88/00133, in particular the compounds of the formulas:

(25)

(26)

Wherein R ⁵ and R ⁶ are each independently of the other preferably n-alkyl having 1 to 7 carbon atoms or n-alkenyl having 3 to 7 carbon atoms and Z ⁰ is -CH ₂ CH ₂ - or a single bond).

Particularly preferred are phenylcyclohexylcarboxylates of the formula:

(27)

(28)

- Component C comprises at least one compound selected from the group consisting of:

[Chemical Formula 29]

(30)

(31)

(32)

(33)

Wherein R ^{1 '} and R ^2' are as defined for R and b is 0 or 1.

- Component B comprises at least one compound selected from the group consisting of the following Formulas 34 to 36:

(34)

(35)

(36)

Wherein alkyl and alkoxy are alkyl or alkoxy radicals having from 1 to 7 carbon atoms.

Component C specifically increases the slope of the property line.

In a particularly preferred embodiment, the mixture comprises about 5 to 35%, particularly preferably about 10 to 20%, liquid crystal tolane compounds. This allows for a much shorter reaction time using a smaller layer thickness (about 5-6 mu m). Particularly preferred tallanes are shown below:

[Chemical Formula 14d]

[Chemical Formula 14e]

Wherein R ^{1 *} is preferably n-alkyl or n-alkoxy having 1 to 7 carbon atoms, Z ⁰ is -CH ₂ CH ₂ - or a single bond,

silver or , And preferably And Q ³ is or ego,

Wherein X ⁰ is F, Cl or OCF ₃ ,

R ^{2 *} is n-alkyl or n-alkoxy each having 1 to 7 carbon atoms or n-alkenyl or n-alkenyloxy having 3 to 7 carbon atoms each.

Component A preferably comprises one or more compounds of the formula:

[Chemical Formula 14f]

(Wherein R &lt; ⁷ &gt; is or ego,

x is an integer of 1 to 15,

L &lt; ^3-6 &gt; are each, independently of one another, H or F, and

X 'is F, Cl or OCF ₃ .

More particularly preferred embodiments are described below:

- Component C comprises at least one compound containing a 1-cyano-trans-1,4-cyclohexyl group or a 2,3-difluoro-1,4-phenylene group;

- two or more compounds of formula 7c or 7e;

- the compounds of formulas 7c and 7e;

At least one compound from the group consisting of:

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

Wherein alkyl is a straight chain alkyl radical having 2 to 7 carbon atoms and L &lt; ¹ &gt; is H or F;

At least one compound wherein R is a trans-alkenyl group or a trans-alkenyloxy group;

- one or more compounds selected from the group:

(43)

(44)

[Chemical Formula 45]

(46)

(Wherein R ^{1 '} and R ^2' have the preferred meanings described for the compound of component B). In the above-mentioned compounds, the 1,4-phenylene group may also be substituted with fluorine. The magnification of these compounds in the liquid crystal mixture is 0 to 25%, preferably 5 to 15%.

In a more preferred embodiment, the mixture comprises:

- at least one, especially 1, 2, 3 or 4 compounds selected from compounds of formulas 6d, 6b, 6i and 6p;

- at least two compounds selected from compounds of formula (5e, 5i or 5j);

One or more compounds of formula 13d;

At least one compound of formula 14a or 14b;

At least one compound of the formula:

(47)

(48)

(Wherein R is as defined for formula (6)).

Specifically, when the layer thickness is used for thick SLCDs, the new mixture exhibits a significantly shorter total reaction time (= t _on + t _off ).

The short overall response time is an important criterion in the SLCD used in laptops to enable the display of cursor movement, especially without interference.

The liquid crystal mixture used in the SLCD according to the present invention is hereditary with Δ∈ ≥1. Δε is ≥3 the liquid crystal mixture is particularly preferred and is even more especially preferred is a liquid crystal composition which Δε is ≥5.

The liquid crystal mixture according to the present invention has a good extreme voltage V ₁₀ / Lt; / RTI &gt; Optical path variation d. If a value of Δ n is given, the value of the layer thickness d is determined by the optical anisotropy Δ n. Particularly high d. At the value of [ Delta] n, the use of a liquid crystal mixture according to the invention having a relatively high optical anisotropy value is generally preferred since the d value can be set relatively small accordingly, which leads to a better reaction time value . However, the liquid crystal display according to the present invention containing a liquid crystal mixture according to the present invention having a relatively small ? N value is also characterized by favorable reaction time values. The liquid crystal mixture according to the present invention is also characterized by having an advantageous slope of the electrooptical characteristic line and can be operated at a high far flex ratio. Besides, the liquid crystal mixture according to the present invention has high stability, good electrical resistance and frequency dependency of extreme voltage. The liquid crystal display device according to the present invention has a wide operating temperature range and excellent contrast dependency.

The polarity of the liquid crystal display device according to the present invention, the electrode substrate plate and the specific alignment (indicator) of the adjacent liquid crystal molecules are each set to a value of 160 ° to 720 °, Corresponds to a conventional structure for this type of display device. The term &quot; structure &quot; as used herein is broadly used and also includes all derivative and deformation of super twisted cells, in particular matrix display elements, and display elements containing additional magnets. The surface inclination angles in the two outer plates may be the same or different. It is preferable that the inclination angle is the same.

However, an essential difference of the display device according to the present invention with respect to what has heretofore been used conventionally based on a twisted nematic cell is the selection of the liquid crystal component of the liquid crystal layer.

The liquid crystal mixtures which can be used according to the invention are prepared in a well known manner. Generally, a desired amount of the component used in a lesser amount is dissolved in the component constituting the main component at a reasonable elevated temperature. It is also possible to mix and then mix a solution of the components in an organic solvent, for example acetone, chloroform or methanol, and then remove the solvent again, for example by kind.

The heritability can also additionally contain additives known to those skilled in the art and described in the literature. For example, 0-15% multicolor dyes may be added.

The following examples are intended to illustrate the present invention without limiting it.

The following abbreviations are used:

S-N smectic-nematic phase transition temperature

N-I nematic-isotropic phase transition temperature

c.p. Transparent point

visc. Viscosity (mPa.s)

After turning _{on the} t _on switch,

Time to get 90%

t _off After turning on the switch,

Time to get 10%

V ₉₀ / V ₁₀ Clarity

t _ave (Average reaction time)

SLDC operates in multiplex mode (drain ratio) 1: 240, bias 1:16, operating voltage 10 volts, thus t _on = t _off .

For now and in the future, all temperatures are displayed in ° C. % Is weight%. The reaction time and viscosity values are for 20 ° C.

In the present application and in the following examples, the structure of the liquid crystal compound is indicated by the abbreviation of the first letter of the chemical formula, and the chemical formulas are shown in Tables 1 and 2 below. All radicals C _n H _{2n + 1} and C _m H _{2m + 1} are straight-chain alkyl radicals having n and m carbon atoms, respectively. The code in Table 2 is straightforward. In Table 1, only the abbreviations for the parent structure are given by the codes of the substituents R ¹ , R ² , L ² and L ² separated by -

In addition to one or more compounds of formula (3), preferred mixtures include one or more of the compounds mentioned in Tables 1 and 2.

[Table 1]

[Table 2]

The following examples are intended to illustrate the present invention without limiting it. So far and so,% is weight percent. All temperatures are given in ° C. mp represents a melting point, and cp represents a transparent point. C is a crystalline state, N is a nematic phase, S is a smectic phase, and I is an isotropic phase. The number between these symbols represents the transition temperature. Δ n represents optical anisotropy (589 n, 20 ° C.), and viscosity (㎟ / sec) was determined at 20 ° C.

The "work-up" is carried out, if necessary, by adding water and extracting the mixture with dichloromethane, diethyl ether, methyl quaternary-butyl ether or toluene, separating the organic phase, Means to purify the product by distillation under reduced pressure or by crystallization and / or chromatography. The following abbreviations are used:

DAST diethylaminosulfur trifluoride

DMEU 1,3-dimethyl-2-imidazolidinone

POT potassium tert-butoxide

THF tetrahydrofuran

pTsOH p-toluenesulfonic acid

Example 1

Step 1.1

In a nitrogen atmosphere, 0.4 mol of trans-4-n-ethylcyclohexylmethyltriphenylphosphonium iodide and 0.4 mol of 4- [trans-4- (trans-4-propylcyclohexyl) cyclohexanecarbaldehyde were dissolved in THF 1140 ml and 0.4 mol of potassium tert-butoxide is added with stirring at room temperature. The mixture is stirred at room temperature overnight, water and dilute hydrochloric acid are added and the mixture is subjected to usual treatment.

Step 1.2

0.275 mol of the compound of the formula I is dissolved in 400 ml of toluene under a nitrogen atmosphere and the mixture is refluxed with 0.072 mol of sodium benzene sulphinate and 110 ml of 1N hydrochloric acid. The mixture is subsequently applied to a conventional treatment.

Compounds of the following general formula are prepared analogously:

Example 2

Step 2.1

162 mmol of trans-4-n-ethylcyclohexylethyltriphenylphosphonium bromide and 162 mmol of trans-4- (4-methylphenyl) cyclohexanecarbaldehyde were dissolved in 500 ml of THF in a nitrogen atmosphere, 162 mmol of butoxide are added with stirring at room temperature. The mixture is stirred for 2 hours, water is added and the mixture is subjected to usual treatment.

Step 2.2

The isomerization is carried out analogously to Step 1.2.

C 43 S _B 89 N 156.6 I; Δ n = +0.103; ?? = 0.58

Compounds of the following general formula are prepared analogously:

Example 3

Step 3.1

In a nitrogen atmosphere, 0.21 mol of 1,4-cyclohexanedione and 0.53 mol of methoxytriphenylphosphonium chloride are dissolved in 200 ml of THF and 0.56 mol of potassium tert-butoxide is added with stirring at room temperature. The mixture is stirred for 2 hours, water and dilute hydrochloric acid are added, and the mixture is subjected to usual treatment.

Step 3.2

The product of step 3.1 is dissolved in 915 ml of THF, 230 ml of 2N HCl are added and the mixture is stirred with boiling for 2 hours. The mixture is subsequently applied to a conventional treatment.

Step 3.3

In a nitrogen atmosphere, 0.31 mol of trans-4-n-ethylcyclohexylmethyltriphenylphosphonium iodide is suspended in 520 ml of THF, and 0.31 mol of potassium tert-butoxide is added little by little. The mixture is stirred for 1 hour at 0 ° C, 0.13 ml of cyclohexane-1,4-dicarbaldehyde is added, and the mixture is stirred at room temperature for 1 hour. Water and diluted hydrochloric acid are added and the mixture is applied to conventional processing.

Isomerization is carried out analogously to step 1.2. C 98 S _B 190 N 235.7 I

Compounds of the following general formula are prepared analogously:

Example 4

Under a nitrogen atmosphere, 2.93 ml of methoxymethyltrimethyltriphenylphosphonium chloride and 2.93 mol of 4-cyclohexanonecarboxylate are dissolved in THF 4 1 and 2.93 mol of potassium tert-butoxide is added with stirring at room temperature. The mixture is stirred for 2 hours, water and dilute hydrochloric acid are added, and the mixture is subjected to usual treatment.

50.4 mmol of the compound of the formula II, 1.0 g of 10% HCl, 20 ml of THF and 50.4 mmol of acetaldehyde are stirred at room temperature for 0.75 h. Water and methyl tertiary-butyl ether are added and the mixture is subjected to conventional treatment.

Under a nitrogen atmosphere, 46.1 mmol of potassium tert-butoxide in 20 ml of THF is added dropwise to 46.1 mmol of methyltriphenylphosphonium bromide dissolved in 50 ml of THF at 0 ° C. The mixture is stirred for 10 minutes and then 46.1 mmol of the compound of formula III dissolved in 20 ml of THF is added dropwise to the solution. The mixture is warmed to room temperature, water and dilute HCl and methyl tertiary-butyl ether are added, and the mixture is applied to conventional processing.

65.8 mmol of bitride are introduced into 35 ml of toluene at 0 ° C, and 72.3 mmol of morpholine dissolved in 20 ml of toluene is added with stirring. The solution is added dropwise to 32.9 mmol of the compound of formula IV dissolved in 30 ml of toluene at -40 &lt; 0 &gt; C, and the mixture is stirred at -40 to -50 [deg.] C for 70 minutes. Water is added at -40 [deg.] C and 10% HCl is added at -10 [deg.] C. The mixture is then subjected to conventional treatment.

0.40 mol of potassium tertiary-butoxide was added to 0.04 mol of the compound of the general formula V, 0.04 mol of 4- [trans-4- (trans-4-propylcyclohexyl) cyclohexylmethyltriphenylphosphonium iodide and 1140 ml of THF Little by little; During this addition, the reaction temperature should not exceed 35 ° C. The mixture is stirred overnight at room temperature, hydrolyzed, dilute HCl is added, and the mixture is applied to conventional processing. C -2 S _B 188 N 222.2 I; [Delta] n = +0.888; ? = 1.03

Compounds of the following general formula are prepared analogously:

Mixture Example

Example M1

PCH-3 21.0% Transparency [0 ° C]: +86

PCH-5 15.0% ? N [589 nm; 20 ° C]: + 0.1428

PCH-302 23.0% STN 240 °

K6 5.0% d. [ Delta] n [ mu m]: 0.85

BCH-32 7.0% V _(10,0,20) [V]: 2.38

ECCP-31 5.0% V ₉₀ / V ₁₀ : 1.0305

ECCP-32 5.0% t _ave [ms]: 263

CPTP-301 5.0%

CPTP-302 4.0%

CPTP-303 4.0%

CVCP-3-1 6.0%

Example M2

PCH-3 21.0% Transparency [0 ° C]: +86

PCH-5 15.0% ? N [589 nm; 20 &lt; 0 &gt; C]: + 0.1416

PCH-302 23.0% STN 240 °

K6 6.0% d. [ Delta] n [ mu m]: 0.85

BCH-32 8.0% V _(10,0,20) [V]: 2.34

ECCP-31 4.0% V ₉₀ / V ₁₀ : 1.036

ECCP-32 4.0% t _ave [ms]: 248

CPTP-301 4.0%

CPTP-302 4.0%

CPTP-303 4.0%

CVCC-3-3 6.0%

Example M3

The following parameters:

Twist 240 °

MuX 1: 240

d · Δn [ μ m] 0.85 has the following characteristics:

Clear point: 90.1 DEG C,

Δ n [589 nm; 20 &lt; 0 &gt; C]: 0.1421

0.0 &gt; d / p &lt; / RTI &gt; of 0.53,

ME2N.F 2.0%

ME3N.F 3.0%

PCH-3 20.0%

PCH-5 6.0%

PTP-201 5.0%

BCH-32 8.0%

BCH-52 8.0%

CPTP-301 5.0%

CPTP-302 5.0%

CPTP-303 4.0%

PCH-302 6.0%

CCH-34 5.0%

CCH-35 5.0%

CVC-V1-2 6.0%

CVC-V1-3 6.0%

CVC-V1-4 6.0%

Has the following switching mode:

V ₁₀ 2.39 V

V ₉₀ / V ₁₀ 1.051

t _ave 217 ms

Example M4

An STN display as described in M3 has the following characteristics:

Clear point: 93.1 DEG C,

Δ n [589 nm; 20 &lt; 0 &gt; C]: 0.1408

0.0 &gt; d / p &lt; / RTI &gt; of 0.53,

ME2N.F 2.0%

K6 6.0%

K9 6.0%

PCH-3 18.0%

BCH-32 7.0%

BCH-52 7.0%

CPTP-301 5.0%

CPTP-302 4.0%

CPTP-303 4.0%

CCH-34 5.0%

CCH-35 4.0%

CVC-V1-2 10.0%

CVC-V1-3 10.0%

CVC-V1-4 10.0%

CBC-33 2.0%

Has the following switching mode:

V ₁₀ 2.496 V

V ₉₀ / V ₁₀ 1.048

t _ave 213 ms

Example M5

An STN display as described in M3 has the following characteristics:

Transparent point: 87.6 DEG C,

Δ n [589 nm; 20 &lt; 0 &gt; C]: 0.1397

0.0 &gt; d / p &lt; / RTI &gt; of 0.52,

ME2N.F 2.0%

K6 4.0%

K9 5.0%

PCH-3 22.0%

PTP-201 2.0%

BCH-32 5.0%

BCH-52 5.0%

CPTP-301 5.0%

CPTP-302 5.0%

CPTP-303 5.0%

CCH-34 5.0%

CCH-35 5.0%

CVC-V1-2 10.0%

CVC-V1-3 10.0%

CVC-V1-4 10.0%

Has the following switching mode:

V ₁₀ 2.44 V

V ₉₀ / V ₁₀ 1.039

t _ave 223 ms

Example M6

An STN display as described in M3 has the following characteristics:

Clear point: 86.4 DEG C,

Δ n [589 nm; 20 &lt; 0 &gt; C]: 0.1395

0.0 &gt; d / p &lt; / RTI &gt; of 0.52,

ME-2N.F 2.0%

K6 4.0%

K9 5.0%

PCH-3 22.0%

PTP-201 2.0%

BCH-32 5.0%

BCH-52 5.0%

CPTP-301 5.0%

CPTP-302 5.0%

CPTP-303 5.0%

CCH-34 5.0%

CCH-35 5.0%

CVC-V1-2 10.0%

CVC-V1-3 10.0%

CVC-V-3 10.0%

Has the following switching mode:

V ₁₀ 2.432 V

V ₉₀ / V ₁₀ 1.042

t _ave 215 ms

Example M7

An STN display as described in M3 has the following characteristics:

Clear point: 85.9 ° C,

Δ n [589 nm; 20 &lt; 0 &gt; C]: 0.1395

0.0 &gt; d / p &lt; / RTI &gt; of 0.52,

ME2N.F 2.0%

K6 4.0%

K9 5.0%

PCH-3 22.0%

PTP-201 2.0%

BCH-32 5.0%

BCH-52 5.0%

CPTP-301 5.0%

CPTP-302 5.0%

CPTP-303 5.0%

CCH-34 5.0%

CCH-35 5.0%

CVC-V1-2 10.0%

CVC-V1-3 10.0%

CVC-1V-V 10.0%

Has the following switching mode:

V ₁₀ 2.4 V

V ₉₀ / V ₁₀ 1.039

t _ave 209 ms

Examples M8 to M13

The composition of the liquid crystal medium and the properties of the STN displays produced using it (twist = 240 DEG) are shown in the table below:

[Table 3]

[Table 4]

Examples M14 to M17

The composition of the liquid crystal medium and the characteristics of the STN display produced using it (twist = 240 °) are shown in the following table:

[Table 5]

[Table 6]

Examples M18 to M25

The composition of the liquid crystal medium and the characteristics of the STN display produced using it (twist = 240 °) are shown in the following table:

[Table 7]

[Table 8]

Example M26

A liquid crystal medium comprising:

ME2N.F 2.0% ? N [589 nm; 20 &lt; 0 &gt; C]: 0.1390

K6 6.0% clear point [占 폚]: 84.6 占 폚

K9 5.0% V ₁₀ 2.265 V

PCH-3 18.0% V ₉₀ / V ₁₀ 1.045

PTP-102 4.0% t _ave [ms] 200

PTP-201 4.0%

BCH-32 7.0%

BCH-52 7.0%

CPTP-301 3.0%

CCH-34 8.0%

CCH-35 7.0%

CVCP-1V-1 4.0%

CVCP-V-1 7.0%

CVCP-V-1 5.0%

CVCP-V-3 8.0%

CVCP-V-4 5.0%

Comparative Example 1

STN display device as described in embodiment M3:

PCH-3 21.0% Transparency [° C]: +85

PCH-5 15.0% ? N [589 nm; 20 &lt; 0 &gt; C]: +0.1413

PCH-302 23.0% STN 240 °

K6 4.0% d. [ Delta] n [ mu m] 0.85

BCH-32 7.0% d / p 0.54

_{CCP-20CF 3 4.0% V (} 10,0,20) [V] 2.36

CCP-30CF ₃ 2.0% V ₉₀ / V ₁₀ 1.042

ECCP-31 5.0% t _ave [ms] 245

ECCP-32 5.0%

CPTP-301 5.0%

CPTP-302 5.0%

CPTP-303 4.0%

Comparative Example 2

STN display device as described in Embodiment 20:

ME2N.F 4.0% Transparency [° C]: +87.2

ME3N.F 3.0% ? N [589 nm]: 0.1365

PTP-20F 23.0% STN 240 °

BCH-32 6.0% d. [ Delta] N [ mu m] 0.85

CCH-34 3.0% V _(10,0,20) [V] 2.26

CCH-3-2V 29.0% V ₉₀ / V ₁₀ 1.038

PCH-1V-N 25.0% t _ave [ms] 208

PCH-3V-N 5.0%

BCH-3V-2 21.0%

Example M27

PCH-2 10.0% Transparency [° C]: 89

PCH-3 24.0% ? N [589 nm; 20 ° C]: + 0.1395

ME2N.F 2.0% Δε [1 kHz, 20 ℃]: 7.5

CVC-3V 5.0% d. [ Delta] n [ mu m]: 0.85

CVC-3-V1 4.0% d / p 0.53

CVCP-V-1 6.0% V _(10,0,20) 2.20

CVCP-1V-1 6.0% V ₉₀ / V ₁₀ [V]: 3.4%

CVCP-V-1 7.0%

PTP-102 4.0%

PTP-201 5.0%

CPTP-301 5.0%

BCH-32 8.0%

BCH-52 5.0%

CCH-34 9.0%

Claims (20)

- two planar parallel plates forming a cell with the frame, - a positive dielectric anisotropic nematic liquid crystal mixture present in the cell, An electrode layer having an alignment layer superimposed on the inside of the outer plate, - an inclination angle between the longitudinal axis of the molecules of the outer plate surface and the outer plate of about 1 to 30, and - a super twisted liquid crystal display having a twist angle of from 100 to 600 占 from the alignment layer of the liquid crystal mixture in the cell to the alignment layer, Wherein the nematic liquid crystal mixture comprises: a) from 20 to 90% by weight of liquid crystal component A consisting of at least one compound having a dielectric anisotropy greater than +1.5; b) from 10 to 65% by weight of liquid crystal component B consisting of at least one compound having a dielectric anisotropy of -1.5 to +1.5; c) between 0 and 20% by weight of a liquid crystal component D consisting of at least one compound having a dielectric anisotropy of less than -1.5, and d) between the layer thickness (plane-parallel outer plate spacing) and the neutral pitch of the chiral nematic liquid crystal mixture Of an optically active component C in an amount of about 0.2 to 1.3, and component B comprises one or more compounds of formula (3): (3) (Wherein, silver or ego, R ¹ is an alkyl, alkoxy or alkenyl radical having 1 to 10 carbon atoms which is unsubstituted or monosubstituted with CN or CF ₂ or at least monosubstituted with halogen and wherein at least one CH ₂ group in the radical is substituted with -O- It can be, R ² is (CH ₂ ) _n -CH═CH-R ^a or (CH ₂ ) _n -CH═CH ₂ , and when r = 1, R ^a is straight chain alkyl having 1 to 6 carbon atoms, n is from 0 to 6, r is 0, 1 or 2, and s is 1 or 2). The method according to claim 1, A super twisted liquid crystal display device characterized in that component A comprises compounds of the following formulas (5) and (6): Formula 5 6 Wherein R is an alkyl group having 1 to 12 carbon atoms and one or two non-adjacent CH ₂ groups are replaced by -O-, -CH = CH-, -CO-, -OCO- or -COO- Lt; / RTI &gt; And Are each, independently of one another, or ego, L &lt; ^1-6 &gt; are each, independently of one another, H or F, Z ¹ is -COO-, -CH ₂ CH ₂ - or a single bond, Z ² is -CH ₂ CH ₂ -, -COO-, -C≡C- or a single bond, And, -CHF-, -OCF2-, -OCFH- or a single bond, - Q is -CF ₂ Y is F or Cl, a is 1 or 2, and b is 0 or 1). 3. The method according to claim 1 or 2, A super twisted liquid crystal display device characterized in that the component A comprises at least one compound of the following general formulas (5a) to (5d): 5a 5b Formula 5c 5d (Wherein R, L &lt; ¹ &gt; and L &lt; ⁵ &gt; are as defined in claim 2). 3. The method according to claim 1 or 2 , A super twisted liquid crystal display device characterized in that the component B comprises at least one compound represented by the following formula: Wherein R ^{1 '} and R ^2' are each independently of each other alkyl, alkoxy, alkenyl or alkenyloxy having 1 to 12 carbon atoms, And Z &lt; ² &gt; are as defined in claim 2). 3. The method according to claim 1 or 2 , Wherein the liquid crystal mixture comprises at least one compound of the following formula (13k): &lt; EMI ID = 13k (Wherein, R ^{3 'is} _{CH 3 - (CH 2) o} -O-, CH 3 - (CH 2) p -, trans _{-H- (CH 2) q -CH =} CH- (CH 2 CH 2) _b -CH ₂ O- or trans _{-H- (CH 2) q -CH =} CH- (CH 2 CH 2) b -, or _{CH 3 - (CH 2) o} -O-CH 2 - , and R ^{4 '} is CH ₃ - (CH ₂ ) _p - o is 1, 2, 3 or 4, q is 0, 1, 2 or 3, b is 0 or 1, and p is 1, 2, 3 or 4). 3. The method according to claim 1 or 2 , Wherein the component C comprises at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 29 to 33: Formula 29 Formula 30 31 (32) Formula 33 Wherein R ^{1 '} and R ^2' are as defined for R and b is 0 or 1. 3. The method according to claim 1 or 2 , Wherein the component B comprises at least one compound selected from the group consisting of compounds represented by the following Formulas 34 to 36: (34) (35) Formula 36 Wherein the alkyl and alkoxy radicals contain no more than 7 carbon atoms. 3. The method according to claim 1 or 2 , A super twisted liquid crystal display device characterized in that component A comprises at least one compound of the following formula (14f) 14f (Wherein, R ⁷ is or ego, x is an integer of 1 to 15, L &lt; ^3-6 &gt; are each, independently of one another, H or F, and X 'is F, Cl or OCF ₃ . The method according to claim 1, A super twisted liquid crystal display device characterized in that the component B comprises at least one compound of the following formula 3j and / or 3k: 3j 3k Wherein R ^b and R ^{b '} are each independently of the other H or alkyl having 1 to 6 carbon atoms, And R &lt; ^b & gt ^; is alternatively alkoxy having 1 to 6 carbon atoms, and &lt; RTI ID = 0.0 & r is 0 or 1). A liquid crystal mixture having the composition defined in any one of claims 1 to 3 . A compound of the general formula: (Wherein R ¹ and R ² are as defined in claim 1). Compounds of formula 3b: 3b (Wherein R, R ¹ are as defined in claim 1, wherein the alkyl is an alkyl radical having 1 to 6 carbon atoms). A compound of formula 3c: Formula 3c Wherein R ² and n are as defined in claim 1 and R ^b is H or alkyl having 1 to 6 carbon atoms. A compound of the formula (3d) (3d) R ^b and R ^{b '} are each independently H or alkyl having 1 to 6 carbon atoms, and n and o are each independently 0 to 6). A compound of the formula (3e) 3e Wherein R ² and n are as defined in claim 1 and R ^b is H or alkyl having 1 to 6 carbon atoms. A compound of formula (3f): Formula 3f Wherein R ² and n are as defined in claim 1 and R ^b is H or alkyl having 1 to 6 carbon atoms. A compound of the formula 3g: 3g Wherein R ¹ and n are as defined in claim 1 and R ^b is H or alkyl having 1 to 6 carbon atoms and L ¹ and L ² are H or F. A compound of formula (3h): 3h R ^b and R ^{b '} are each independently H or alkyl having 1 to 6 carbon atoms, and n and o are each independently 0 to 6). A compound of the general formula: Wherein R &lt; ¹ &gt;, R &lt; ² &gt; and Lt; / RTI &gt; are as defined in claim 1). A compound of the general formula: Wherein alkyl is C _1-6 -alkyl and R ^b is H or alkyl having 1 to 6 carbon atoms.