DE2752975A1 - CRYSTALLINE LIQUID SUBSTANCES - Google Patents

Description

Title of the invention
Crystalline liquid substances
Field of application of the invention

The invention relates to the use of crystalline liquid nematic Substances in electro-optical arrangements for modulating the light passing through or incident, as well as for reproducing digits, characters and images; also as an orienting medium for spectroscopy and gas chromatography.

Characteristics of the known technical solutions

It is known that nematic liquid crystals can be reoriented in electric fields and thus for production of electro-optical arrangements can be used / M. Tobias, International Handbook of Liquid Crystal Displays 1975-1976 Ovum Ltd. London 1976 /.

Furthermore, liquid crystals are used as an orienting medium in spectroscopy in the visible and near UV range, in in nuclear magnetic resonance spectroscopy as well as in gas chromatography / G. Meier, E. Sackmann, J.G. Grabmaier, Applications of Liquid Crystals, Springer-Verlag, Berlin-Heidelberg-New York 1975 /.

809833/0689

For the purposes mentioned, the subatitu-

ated phenyl benzoate / DDR WP 86 269; R. Steinsträsser, Z. Naturforsch. 27b, 774 (1972) / used. These esters have a relatively high viscosity, which is especially true at low Temperatures in electro-optical components cause undesirably long switch-on and switch-off times. Partly they are Clear points are undesirably low or the melting points are too high.

Object of the invention

The aim of the invention is to use new crystalline liquid Substances that have a high chemical and thermal stability, no inherent color in the visible spectral range, have sufficiently high clearing points with sufficiently low melting points and low viscosity values, in electro-optical arrangements for modulating the passing or incident light and for reproducing digits, Signs and images, as well as an orienting medium for spectroscopy and gas chromatography.

Explain the essence of the invention

It has been found that nematic crystalline liquid substances zen of the general formulas

where R ¹ =

^r4 ■

X-R

as

with η = 1 to 9

-> ° η ^Η 2η ₊ 1 ° - ^C n ^H 2n ₊ 1 ^C0 ° - ' ^C n ^H 2n ₊ 1 ^0C0 ° -

η - 1 to 9

-CH, -Cl, -Br, -C ₂ H ₄ CJN

or -00C- (h

H, -CH ₃ , -C ₂ H ₅ , -Cl, -Br, -CH,

° Q ^H 2n + 1

^{or C} n ^H 2n + 1 ° "

η = 0 to 9

809833/0689

■ V

mean in electro-optical arrangements for modulating the passing or incident light as well as for reproduction of numbers, characters and images, also used as an orienting medium for spectroscopy and gas chromatography can be. The substances have high chemical and thermal stability, no inherent color in the visible Spectral range, high clearing points with sufficiently low melting points and low viscosity values.

By producing mixtures, in particular eutectic mixtures, the melting points are still greatly reduced and with little change in the clearing points, the operating temperature ranges are still significantly increased. The transition temperatures substances according to the invention can be found in Tables 1 to 3 below.

The mixtures can be colored by adding dyes in concentrations of up to 5 % and can then be used for electro-optical components based on the guest-host effect.

809833/0689

Table 1

R ¹ -

H) -C

- O

No. R

R Pp, unchangeable. KIp,

em - em - am - Hem.

1 CH ₃ - CH ₃ O- H 107 - ■ - 229 CVJ CH ₃ - C ₄ H ₉ O- H 81 - (70) 197.5 3 CH ₃ - C ₇ H ₁₅ o- H 81 - - 187 4th CH ₃ - ^C 8 ^H 17 ° - H 67 - 83 170 VJl CH ₃ - C ₄ H ₉ - H 73 - - 159 6th C ₂ H ₅ - CH ₃ - H 62 - - 188 7th C ₂ H ₅ - CH ₃ O- H 80 - 88 245 8th C ₂ H ₅ - C ₄ H ₉ - H 66 - 110 180 9 C ₂ H ₅ - C ₇ H ₁₅ O- H 63 - 126 184 10 C ₂ H ₅ - C ₈ H ₁₇ O- H 58 - 175 11 C ₃ H ₇ - CH ₃ O- H 94— - - 245 12th C ₃ H ₇ - C ₂ H ₅ O- H 112 - 238 13th C ₃ H ₇ - C ₄ H ₉ O- H 75 222 14th C ₃ H ₇ - C ₅ H ₁₁ O- H 67.5 - 214 15th C ₃ H ₇ . C ₇ H ₁₅ O- H 75 203 16 C ₃ H ₇ - CH ₃ - H 72-73 240 17th C ₃ H ₇ - C ₄ H ₉ - H 74-75 198 18th C ₄ H ₉ - CH ₃ O- H 121 236 19th C ₄ H ₉ - C ₂ H ₅ O- H 104 231 20th C ₄ H ₉ - C ₄ H ₉ O- H 74-75 218 21st C ₄ H ₉ - C ₅ H ₁₁ O- H 71-72 206.5 22nd C ₄ H ₉ - C ₇ H ₁₅ O- H 66-67 196

() moaotropic conversion 809833/0689

Table 1 continued

No ... R ¹ R ² R ³ Pp. Conversion. KIp.

sm-sm. sm-nem.

23 C ₄ H ₉ - CH ₃ - H 78 - 208 24 C ₄ H ₉ - C ₃ H ₇ - H 82 92 206 25th C ₄ H ₉ - C ₄ H ₉ - H 65 115 192 26th C ₅ H ₁₁ - CH ₃ O- H 97-98 (59) 237 27 C ₅ H ₁₁ - C ₂ H ₅ O- H 103 - 236 28 C ₅ H ₁₁ - C ₄ H ₉ O- H 85 (70) 124 216 29 C ₅ H ₁₁ - C ₇ H ₁₅ O- H 66 88 150 202 30th C ₅ H ₁₁ - CH ₃ - H 56-57 90 215 31 C ₅ H ₁₁ - C ₃ H ₇ - H 78 121 209 32 ^c 5 ^H ir C ₄ H ₉ - H 78-79 136 195 33 C ₄ H ₉ - NC- H 98-99 - 255 34 CH ₃ - C ₇ H ₁₅ o- CJ ₂ H ₅ - 47.5 - - 88 35 C ₃ H ₇ - C ₇ H ₁₅ o- C ₂ H ₅ - 62-63 - 123 36 C ₅ H ₁₁ - C ₇ H ₁₅ O- C ₂ H ₅ - 51-52 - 120 37 ^C 6 ^H 13 " C ₇ H ₁₅ O- C ₂ H ₅ - 44-45 - 116.5 38 CH ₃ - C ₇ H ₁₅ O- Cl- 80 - 142 39 C ₂ H ₅ - C ₄ H ₉ O- Cl- 78 - 175 40 C ₂ H ₅ - C ₇ H ₁₅ O- Cl- 73 - 151 41 C ₄ H ₉ - C ₄ H ₉ O- Cl- 77-78 - 188 42 C ₃ H ₇ - C ₇ H ₁₅ O- Cl- 73 - 174 43 C ₄ H ₉ - C ₇ H ₁₅ O- Cl- 73-74 - 166 44 C ₅ H ₁₁ - C ₇ H ₁₅ O- Cl- 66-67 - 154

() monotropic conversion

809833/0689

Tabel

No. ^R 1 ^R 2 Pp KIp. 45 C ₂ H ₅ - CH ₃ - 92 142.5 46 C ₄ H ₉ - CH ₃ - 88 179-180 47 C ₅ H ₁₁ - CH ₃ - 76 185 48 CH ₃ - H- 68-69 (48) 49 C ₃ H ₇ - C ₂ H ₅ - 47 130 50 C ₄ H ₉ - C ₂ H ₅ - 50-51 129 51 ^C 5 ^H 11 " C ₂ H ₅ - 42-43 133-134 52 ^C 6 ^H 13 " C ₂ H ₅ - 53 122 53 C ₃ H ₇ - Cl- 73 186 54 C ₄ H ₉ - Cl- 83 181 55 C ₅ H ₁₁ - Cl- 69-70 190

809833/0689

Tabel

-COO-

-COO- (H) -R

R.

Pp

Urawandl. am — no.

KIp.

56 C ₄ H ₉ - C ₄ H ₉ - 68 - 161 57 ^C 6 ^H 13 " CH ₃ - 60 - 105 58 ^C 6 ^H 13 " C ₅ H ₁₁ - 73 - 146 59 C ₂ H ₅ - C ₄ H ₉ O- 120 - 141 60 CH ₃ O- C ₄ H ₉ - 110 - 212 61 C ₂ H ₅ O- C ₄ H ₉ - 108 - 212 62 C ₆ H ₁₃ O- H 125 218 255 63 S.
VoJ 50 63 151 64 t) 1 3 C ₄ H ₉ - 72 82 200 65 C ₆ H ₁₃ O- C ₄ H ₉ O- 66 173 183 66 CH ₃ O- C ₄ H ₉ O- 110 - 145 67 C ₂ H ₅ O- C ₄ H ₉ O- 95 - 150

809833/0689

Embodiments Example 1:

The compounds with X = -C00- ^ 3 ~ are prepared by reacting the 4-n-Alkylcyclohexanoylchloride with the substituted 4-Hydroxybenzoic acid phenyl esters according to the scheme

-C-Cl + B

H) -COO- (O) -COO

The reaction takes place in fyridine at room temperature, the substances are purified by repeated recrystallization achieved from methanol.

10 Example 2:

The compounds with X * -0CC- / hV are prepared by reacting the 4-n-alkylcyclohexanoyl chlorides with the 2-substituted hydroquinones according to the scheme

2 R ¹

The reaction takes place in pyridine at room temperature, the substances are purified by repeated recrystallization achieved from methanol.

Example 3:

Substance no. 51 shows the dynamic scattering effect in the usual electro-optical arrangements · At 50 Hz alternating voltage, a threshold voltage of U ₀ «7.5 V is found, with direct voltage a threshold voltage of U _Q = 5.5 V. Tensions that make up 2.5 times the value of U, good contrasts of 20: 1 or higher are achieved. Even when voltages up to 60 V are applied, no signs of decomposition are observed.

809833/0689

Example 4:

Substance No. 57 has positive dielectric anisotropy and a is for electro-optical arrangements based on field effects (Fresdericksz rearrangement, Schadt-Helfrich effect, guest-host effect) suitable. In a Schadt-Helfrich cell (twist cell) a threshold voltage of 4 V / 50 Hz was found, the complete reorientation was reached at 8 V / 50 Hz.

Example 5:

17o methyl red is mixed with substance no. 57 and an oriented preparation with a horizontal layer is made. When irradiated with polarized light, the typical absorption band of methyl red is found when the polarization plane of the light is arranged parallel to the preferred direction of the nematic layer. In contrast, no absorption can be detected if the plane of polarization of the light is arranged perpendicular to the preferred direction of the nematic layer. This proof of the dichroism of the dye methyl red is based on the directional incorporation of the dye molecules according to the orientation of the nematic matrix. Since the substances according to the invention show no absorption in the visible spectral region, they can advantageously be used for spectroscopy in this region. With the help of electric fields (5 V / 50 Hz) the originally lying layer is erected in electro-optical components and a color change from red to pale pink is achieved.

809833/0689

Claims (2)

Invention claim 1. Crystalline liquid substances for electro-optical arrangements for modulating the continuous or conspicuous Light as well as for the reproduction of digits, characters, images, also as an orienting medium for spectroscopy and gas chromatography, characterized in that substances of general formula rVhvc XR ² and R ² -dn> -C ( -COO- (H) -R ^C n ^H 2n ₊ r ^C n ^H 2n ₊ 1 ° - where R - w_ "o_." _{wLt n m 1 to 9j} Po ^ i ^ OÖ-, C H- ^ ₁ OCOO-, ι 2n + 1 η 2n + 1 ' with η - 1 to 9, -CN, -Cl, -Br, -C ₂ H ^ CN X = -COO - ^^ - or -OOC-ZhV R ^ ^ m TI i ^ U ^^ f ^ TT f % "1 ΊΟ ^ * f" IUf rttj ffKE ^{R =} ° n ^H 2n + i "» ^C n ^H 2n + 1 ° " with η = 0 to 9 mean, to be used 2. Crystalline liquid substances according to Funct 1, characterized in that the substances of the general formula rVh ' -X-R ' respectively· further crystalline-liquid or non-crystalline-liquid Substances, especially dyes, are added. 809833/0699 ORIGINAL INSPECTED