WO2016186465A1 - Liquid crystal compound and liquid crystal composition comprising same - Google Patents

Liquid crystal compound and liquid crystal composition comprising same Download PDF

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Publication number
WO2016186465A1
WO2016186465A1 PCT/KR2016/005326 KR2016005326W WO2016186465A1 WO 2016186465 A1 WO2016186465 A1 WO 2016186465A1 KR 2016005326 W KR2016005326 W KR 2016005326W WO 2016186465 A1 WO2016186465 A1 WO 2016186465A1
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Prior art keywords
liquid crystal
formula
independently
compound
crystal composition
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PCT/KR2016/005326
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French (fr)
Korean (ko)
Inventor
최진욱
송정인
강소희
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주식회사 동진쎄미켐
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Priority to CN201680022091.6A priority Critical patent/CN107532084A/en
Publication of WO2016186465A1 publication Critical patent/WO2016186465A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40

Definitions

  • Liquid crystal compound and liquid crystal composition comprising the same
  • the present invention relates to a liquid crystal compound having high dielectric anisotropy, high refractive index anisotropy and low viscosity, and a liquid crystal composition comprising the same.
  • Liquid crystal display devices are used in watches, electronic calculators, various electrical devices, measuring devices, automotive panels, word processors, electronic notebooks, printers, computers, televisions, and the like.
  • Typical liquid crystal displays include TN (Twist nematic), STN (Super, twisted nematic), In-lane switching (IPS) Fringe Field Switching (FFS), and Virtual Alignment (VA).
  • the liquid crystal material used in such a liquid crystal display device is capable of low voltage driving and high-speed ungdap, and is required to "be operable in a wide temperature range.
  • the liquid crystal material in order to drive stably in a wide temperature range, the liquid crystal material exhibits stable physical properties at about -20 ° C or lower (low temperature stability), and is required to have a transparent point of about 70 ° C or higher. Then, for low voltage driving and high speed response, the liquid crystal material is required to have a high absolute value of dielectric anisotropy, a low rotational viscosity, and an appropriate elastic modulus (K u , K 22) ⁇ 33 average value). It is impossible to satisfy the required physical properties of such liquid crystal materials by using one or two kinds of liquid crystal compounds, and usually seven to twenty kinds of liquid crystal compounds are compounded and stratified.
  • IPS or VA of the liquid crystal display method is characterized by using a liquid crystal material having a negative dielectric anisotropy, unlike the general-purpose TN or STN.
  • the negative liquid crystal material having negative dielectric anisotropy has a problem that a polar substituent exists on the side of the molecule, and the rotational viscosity is greatly increased even if the dielectric anisotropy is slightly changed compared to the positive liquid crystal material. Accordingly, In order to provide an IPS or VA type liquid crystal display device capable of high speed response, development of a liquid crystal compound having a negative dielectric anisotropy, a large absolute value, and a low viscosity is required.
  • the present invention is to provide a liquid crystal compound having high anisotropy, high refractive index anisotropy and low viscosity, and a method for producing the same.
  • the present invention is to provide a liquid crystal composition comprising at least one of the above liquid crystal compounds.
  • this invention is providing the liquid crystal display element containing the said liquid crystal composition.
  • the present invention provides a liquid crystal compound represented by the following formula (1):
  • Li, L 2 , L 3 and L 4 are each independently hydrogen or halogen
  • R represents hydrogen, d-) alkyl, C 2 - 10 alkenyl, or CHO, and alkoxy, and
  • nl and n2 are each independently an integer of 0 to 2, and the sum of nl and n2 is 0 or more and 2 or less.
  • the liquid crystal compound represented by Chemical Formula 1 is a liquid crystal compound having negative dielectric anisotropy, and may lower the viscosity of the liquid crystal by connecting the phenyl group with ethylene (-c3 ⁇ 4-c3 ⁇ 4-), thereby optimizing the liquid crystal phase. can do.
  • the sock end of Formula 1 has a 2,3-difluorophenyl group, at least one terminal does not have an alkyl group as a substituent, By having a negative dielectric constant anisotropy, it can exhibit a high dielectric constant value.
  • the liquid crystal compound of Chemical Formula 1 may be composed of only benzene rings, and may have a high refractive index anisotropy value by adjusting the number of benzene rings according to nl and n2, thereby realizing a quick response rate of the liquid crystal display device.
  • the, and L 4 are each independently hydrogen or fluoro eu
  • Ll and L 2 are the same.
  • L 3 and L 4 are the same.
  • L 2 may be both hydrogen or all fluoro.
  • R is hydrogen, methyl, ethyl, methoxy or ethoxy.
  • the liquid crystal compound may contain 2, 3 or 4 benzene rings.
  • Can have Representative examples of the liquid crystal compound represented by Formula 1 are as follows:
  • the present invention provides a method for producing a liquid crystal compound represented by Chemical Formula 1, as shown in Scheme 1 below.
  • Step 1 is a compound represented by the formula (4) by reacting the compound represented by the formula (2) and the compound represented by the formula (3).
  • a step of preparing a compound a step of combining two compounds with an ethene (—CH ⁇ CH—) bond. It is preferable to use THF as a solvent. It is also preferred to react in the presence of Potassium tertiary-butoxide. The reaction temperature is preferably 0 ° C. or less.
  • Addition step 2 is to react the compound represented by the formula (4) with hydrogen
  • the compound is a step of preparing a compound represented by the formula (1). Hydrogenation catalysts can be used for this reaction, for example palladium / activated carbon.
  • the compound represented by Formula 2 as the starting material may be prepared by the same method as in Scheme 2 below.
  • the Reaction refers to bromo of the compound represented by Formula 5 by reacting the compound represented by Formula 5 with PPh 3 and adding P + Ph 3 Br. It is a reaction to substitute with —.
  • the present invention provides a liquid crystal composition comprising at least one liquid crystal compound represented by the formula (1).
  • the liquid crystal composition may include one or more liquid crystal compounds represented by Formula 1 in 3 wt% or more or 4 wt% or more based on the total weight of the liquid crystal composition. If the content of the liquid crystal compound represented by the formula (1) is less than the above range, the effect of improving the response rate can be insignificant.
  • the liquid crystal composition may include one or more liquid crystal compounds represented by Chemical Formula 1 in an amount of 60 wt% or less, 40 wt% or less, 30 wt% or 20 wt% or less, based on the total weight of the liquid crystal composition. If the content of the liquid crystal compound represented by the formula (1) exceeds the above range, the phase transition temperature of the liquid crystal composition is greatly increased may cause a problem that the liquid crystal phase cannot be secured in the low temperature region.
  • the liquid crystal composition may further include various liquid crystal compounds for overall performance of the liquid crystal display device in addition to the liquid crystal compound of Formula 1.
  • the liquid crystal composition may further include one or more liquid crystal compounds selected from the group consisting of the following Chemical Formulas 2 to 5 below.
  • the liquid crystal composition may further include a known low viscosity liquid crystal compound. As such a low viscosity liquid crystal compound, a liquid crystal compound represented by the following formula (2) may be used.
  • a 3 and A 4 are each independently cyclonuylene or phenylene. Transparent point, rotational viscosity, and the like of the liquid crystal composition while maintaining a high specific resistance using at least one liquid crystal compound selected from the group consisting of compounds represented by the following Formulas 2-1 and 2-2 as the liquid crystal compound represented by Formula 2
  • the refractive index anisotropy and the dielectric anisotropy can be easily adjusted.
  • R 11 and R 12 may be defined as R 11 and R 12 of formula (II).
  • the liquid crystal composition in a liquid crystal phase transition 0 the known compound It may further include a liquid crystal compound exhibiting a high temperature or high refractive index.
  • a liquid crystal compound represented by the following formula (3) may be used.
  • R 13 and R 14 are each independently a radical of any one of hydrogen, alkyl of 1 to 15 carbon atoms and alkoxy of 1 to 15 carbon atoms, or -c3 ⁇ 4- of at least one of the radicals is not directly linked to oxygen atoms ⁇ c-,
  • -CH CH-, -CF 2 0-, -0-, -COO- or — 0C0— or a radical substituted with one or more H of the radicals is replaced by halogen,
  • a 5 and A 7 are each independently cyclonuylene or phenylene
  • a 6 is cyclonuylene, phenylene or phenyl substituted with halogen and p is an integer of 1 or 2.
  • the liquid crystal compound represented by Chemical Formula 3 by using one or more liquid crystal compounds selected from the group consisting of Chemical Formulas 3-1 to 3-5, the transparent point, rotational viscosity, refractive index anisotropy and control of the liquid crystal composition may be maintained while maintaining high specific resistance. have.
  • R 13 and R 14 may be defined as in the general formula R 3 "and R 14.
  • the liquid crystal composition in addition to oil-in-water dielectric constant liquid crystal the known compound
  • a liquid crystal compound represented by the following Chemical Formula 4 may be used.
  • R 15 and R 16 are each independently a radical of any one of hydrogen, alkyl having 1 to 15 carbon atoms and alkoxy having 1 to 15 carbon atoms, or -c3 ⁇ 4- at least one of the radicals is not directly linked to oxygen atoms.
  • ⁇ c-, -CH CH-, -CF 2 0-, -0-, -COO- or -0C0- or a radical substituted with one or more H of said radicals,
  • a 8 and A 9 are each independently cyclonuylene, ' tetrahydropyranylene, phenylene or phenyl substituted with halogen,
  • q is an integer between 0 and 2.
  • Transparent point, rotational viscosity, refractive index anisotropy and dielectric constant of the liquid crystal composition while maintaining a high resistivity using at least one liquid crystal compound selected from the group consisting of the following Chemical Formulas 4-1 to 4-4 as the liquid crystal compound represented by Chemical Formula 4 Anisotropy etc. can be adjusted easily.
  • R 15 and R 16 may be defined as R 15 and R 16 of formula (4).
  • the liquid crystal composition may further include a conventional high dielectric constant liquid crystal compound.
  • a liquid crystal compound represented by the following formula (5) may be used.
  • a 10 , A 11 and A 12 are each independently one of cyclonuclear styrene, tetrahydropyranylene, phenylene and phenylene substituted with halogen,
  • Z 4 and Z 5 are each independently -CH 2 CH 2- , -CH-CH-, —C ⁇ C ⁇ , — C3 ⁇ 40-,-0CH 2- , -CH 2 CF 2- , -CHFCHF-, -CF 2 CH 2- , -CH 2 CHF-, -CHFCH 2- , -C 2 F 4 _, -C00-,-0C0-, -CF 2 0-, -OCF2- or -0-,
  • r and v are 0 or 1 or 2
  • s and w are integers between 0 and 2.
  • Transparent point, rotational viscosity, refractive index anisotropy, and dielectric anisotropy of the liquid crystal composition while maintaining a high resistivity using at least one liquid crystal compound selected from the group consisting of the following Formulas 5—1 to 5-4 as the liquid crystal compound represented by Formula 5 Etc. can be easily adjusted.
  • R 17 and R 18 may be defined as R 17 and R 18 of formula (5).
  • the liquid crystal composition can 'be suitably comprises a liquid crystal compound and the intended use of at least one of liquid crystal compounds represented by considering the effect by the above formula (2) to formula (5) to the liquid crystal composition.
  • the liquid crystal composition may include a liquid crystal compound represented by Formula 2, Formula 3, and Formula 4 in order to balance various physical properties of the liquid crystal composition.
  • at least one liquid crystal compound may be used as the liquid crystal compound represented by Formulas 2 to 4, respectively.
  • the liquid crystal composition may further include various additives commonly used in the art to which the present invention belongs, in addition to the liquid crystal compound.
  • the liquid crystal composition may further include an antioxidant.
  • the liquid crystal composition may further include a reactive mesogen.
  • a reactive mesogen may be defined as a compound having a mesogenic group exhibiting liquid crystal phase behavior and an unsaturated functional group capable of photopolymerization, photocrosslinking or photocuring at least one end thereof, for example, a vinyl group, a (meth) acryl group, or an epoxy group.
  • any compound that satisfies this definition may be included as the semi-ungsogenic mesogen.
  • the semi-ungsogenic mesogen may include a diacrylate monomer having a liquid crystal skeleton or a dimethacrylate monomer having a liquid crystal skeleton.
  • the liquid crystal composition may further include a UV stabilizer.
  • the present invention provides a liquid crystal display device comprising the liquid crystal composition.
  • the liquid crystal composition according to the present invention exhibits high negative dielectric anisotropy and high refractive index anisotropy even under low rotational viscosity, and in particular, VA Virtical Alignment (MVA), Multidomain Virtical Alignment (MVA), Patterned Virtical Alignment (PVA), It is expected that high speed response can be achieved while maintaining excellent overall performance of liquid crystal display devices such as PS-VA (Polymer Stabilized Virtical Alignment) or IPS (In-Plane Switching) mode.
  • PS-VA Polymer Stabilized Virtical Alignment
  • IPS In-Plane Switching
  • the liquid crystal compound according to the present invention has high dielectric anisotropy, high refractive index anisotropy and low viscosity, and therefore various liquid crystal display devices, especially VA, MVA, PVA, PS-VA, PALC, FFS, PS-FFS, which require fast response time.
  • the liquid crystal composition optimized for the liquid crystal display element of the IPS or PS-IPS mode can be provided.
  • the bromine salt compound (Formula 1-1, 40 ⁇ 0 , 18.8 g) was dissolved in anhydrous THF, and potassium tertiary-butoxide (48.1 ⁇ ol, 5.4 g) was slowly added with stirring at -30 ° C for 30 minutes. Stirred.
  • the aldehyde compound (Formula 1-2, 43.7 mmol, 8.13 g) was added dropwise in THF at -30 ° C. After the temperature was lowered to -10 ° C and stirred for 1 hour, water and toluene 1: 1 solvent were added to the reaction vessel to terminate the reaction.
  • ethene compound (Formula 1-3, 60%, 7.1 g).
  • the obtained ethene compound (Formula 1-3, 24 ⁇ 0 1, 7.1 g) and palladium / activated carbon (10 ⁇ vt., 1.5 g) were dissolved in THF and methanol 1: 1 solvent and reacted for 3 hours in a hydrogen reactor. Filtered. After the filtrate was concentrated, the target compound (Formula 1, 94%, 6.7 g) was obtained through column chromatography.
  • bromine salt compound (Formula 2-1 , 40 ⁇ ol, 18.8 g) was dissolved in anhydrous THF
  • the bromine salt compound (Formula 3-2, 27.3 ⁇ ol, 14 g) was dissolved in anhydrous THF, and potassium tertiary-butoxide (32.7 ⁇ ol, 3.7 g) was slowly added with stirring at ⁇ 30 ° C. and stirred for 30 minutes. It was.
  • the aldehyde compound (Formula 3-1, 29.7 ⁇ ol, 6.49 g) was added dropwise in THF at -30 ° C. After raising the temperature to -KC and stirred for 1 hour, the reaction was terminated by adding water and toluene 1: 1 solvent in the reaction vessel.
  • the organic solvent layer was extracted, and the solid obtained by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 3-3, 65%, 6.6 g).
  • the obtained ethene compound (Formula 3-3, 17.7 ⁇ ol, 6.6 g) and palladium / activated carbon (10 wt.%, 1.65 g) were dissolved in THF and methanol 1: 1 solvent and reacted for 3 hours in a hydrogen reactor, followed by filtration. It was.
  • the filtrate was concentrated and then subjected to column chromatography to give the target compound (Formula 3, 94%, 6.24 g).
  • the bromine salt compound (Formula 4-1, 21.3 ⁇ ol, 10 g) was dissolved in anhydrous THF and potassium tertiary-butoxide (25.6 mmol, 2.9 g) was added slowly with stirring at -30 ° C and stirred for 30 minutes. .
  • the aldehyde compound (Formula 4-2, 23.2 ⁇ ol, 7.86 g) was added dropwise in THF at -30 ° C. After raising the temperature with -KTC and stirring for 1 hour, the reaction vessel was terminated by adding water and toluene 1: 1 solvent.
  • the organic solvent was extracted and the solid produced by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 4-3, 59, 5.64 g).
  • the obtained ethene compound (Formula 4-3, 12.6 ⁇ 0 1, 5.64 g) and palladium / activated carbon (10 wt.%, 1.4 g) were dissolved in THF and methane in a 1: 1 solvent and reacted for 3 hours in a hydrogen reactor. And filtered. The filtrate was concentrated and then subjected to column chromatography to give the target compound (Formula 4, 97%, 3.9 g).
  • the bromine salt compound (Formula 5-2, 20.2 ⁇ ol, 12.5. G) was dissolved in anhydrous THF, and then potassium tertiary-subside (25.4 ⁇ ol, 2.86 g) was added slowly with stirring at -30 ° C for 30 minutes. Stirred.
  • the aldehyde compound (Formula 5-1, 23.1 ⁇ ol, 5.04 g) was added dropwise in THF at -30 ° C. After the temperature was raised to -10 ° C and stirred for 1 hour, water and toluene 1: 1 solvent were added to the reaction vessel to terminate the reaction.
  • the organic solvent layer was extracted, and the solid obtained by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 5-3, 74%, 7 g).
  • the obtained ethene compound (Formula 5-3, 15.6 ⁇ ol, 7 g) and palladium / activated carbon (10 wt.%, 1.75 g) were dissolved in THF and methanol 1: 1 solvent and reacted for 3 hours in a hydrogen reactor, followed by filtration. It was.
  • the filtrate was concentrated and then subjected to column chromatography to give the target compound (Formula 5, 81%, 5.69 g).
  • the brine compound (Formula 6-2, 15.6 ⁇ ol, 8 g) was dissolved in anhydrous THF, and then potassium tertiary-buside (18.7 ⁇ ol, 2.1 g) was added slowly with stirring at -30 ° C and stirred for 30 minutes. It was.
  • the aldehyde compound (Formula 6-1, 16.99 ⁇ ol, 5 g) was added dropwise in THF at -30 ° C. After raising the temperature to -10 ° C and stirred for 1 hour, the reaction vessel was terminated by adding water and toluene 1: 1 solvent.
  • the organic solvent layer was extracted, and the solid obtained by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 6-3, 90%, 6.29 g).
  • the obtained ethene compound (Formula 6-3, 14 ⁇ ol, 6.29 g) and palladium / activated carbon (10 wt.%, 1.6 g) were dissolved in a 1: 1 solvent of THF and methane, and then hydrogen The reaction was reacted for 3 hours in the reactor and filtered. The filtrate was concentrated and then subjected to column chromatography to give the target compound (Formula 6, 79%, 5 g).
  • the physical properties of the liquid crystal compounds prepared in Preparation Examples and Comparative Preparation Examples were evaluated. Specifically, the physical properties of the liquid crystal compound were defined as an extrapolation value obtained by substituting the measured value of the sample prepared by mixing 10 wt% of the liquid crystal compound to be measured with 90 wt% of the mother liquid crystal. In this case, as the mother liquid crystal, a transparent point Tni of 78 ° C. and an refractive index anisotropy [ ⁇ ] of 0.10 were used.
  • TA-series differential scanning calorimetry of ⁇ was used to observe the phase transition temperature by heating and concentrating 1 cycle of the liquid crystal compound to Tni + 50 ° C at room temperature at a rate of rc / min under nitrogen.
  • Cry, Sm, N, ISO means crystalline phase, Smetic phase, nematic phase, isotropic phase, respectively,
  • the temperature between means the corresponding phase transition temperature.
  • the Tni of the liquid crystal compound is measured by observing the temperature when a liquid crystal compound is placed on a hot plate of a melting point measuring device equipped with a polarization microscope and heated at a rate of 3 ° C./min to change a part of the liquid crystal compound into an isotropic liquid on the liquid crystal phase. It was.
  • SCHOTT CT52 equipment was used for the viscosity measurement, and 2 mL of the liquid crystal composition to be measured after mounting a capillary viscometer capable of measuring the viscosity for a volume of 2 mL. Thereafter, the liquid crystal composition was stabilized at 20 ° C. for 30 minutes, and then the liquid crystal composition was pulled down to the measurement site using a sporad louver. Subsequently, the rate at which the liquid crystal composition fell was measured through a timer, and the viscosity (mm 2 / s) was obtained through the timer. The results are shown in Table 2 below.
  • each value means weight%.
  • the liquid crystal compound was placed on a hot plate of a melting point measuring device equipped with a silver polarization microscope of the liquid crystal compound, and heated at a rate of 3 ° C./min to observe the temperature when a part of the liquid crystal compound changed to an isotropic liquid on the liquid crystal phase. It was.

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Abstract

The liquid crystal compound represented by chemical formula 1 according to the present invention has high dielectric anisotropy, high refractive index anisotropy and low viscosity, and thus can provide a liquid crystal composition optimized for various liquid crystal display devices, particularly, liquid crystal display devices of VA, MVA, PVA, PS-VA, PALC, FFS, PS-FFS, IPS or PS-IPS modes which require fast response times (wherein L1, L2, L3 and L4 are each independently hydrogen or halogen, R is hydrogen, C1-10 alkyl, C2-10 alkenyl or C1-10 alkoxy, and n1 and n2 are each independently an integer ranging from 0 to 2, and the sum of n1 and n2 is from 0 to 2).

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
액정 화합물 및 이를 포함하는 액정 조성물  Liquid crystal compound and liquid crystal composition comprising the same
【기술분야]  Technical Field
본 발명은 고유전율 이방성， 고굴절률 이방성 및 낮은 점도를 가지는 액정 화합물 및 이를 포함하는 액정 조성물에 관한 것이다.  The present invention relates to a liquid crystal compound having high dielectric anisotropy, high refractive index anisotropy and low viscosity, and a liquid crystal composition comprising the same.
【배경기술】  Background Art
액정 표시 소자 (LCD)는 시계， 전자 계산기를 비롯하여 각종 전기 기기， 측정 기기， 자동차용 패널, 워드 프로세서, 전자 수첩， 프린터， 컴퓨터， 텔레비전 등에 사용되고 있다. 액정 표시 방식에는 대표적으로 TN(Twist nematic), STN(Superᅳ twisted nematic) IPS( In- lane switching) FFS( Fringe field switching) 및 VA(Virt ical alignment) 등이 있다. 이러한 액정 표시 소자에 사용되는 액정 재료는 저전압 구동 및 고속 웅답이 가능하며，' 넓은 온도 범위에서 동작 가능할 것이 요구된다. 구체적으로， 넓은.온도 범위에서 안정적으로 구동하기 위하여 액정 재료는 약 -20 °C 이하에서 안정적인 제반 물성을 나타내며 (저온 안정성)， 약 70°C 이상의 투명점을 가질 것이 요구된다. 그리고， 저전압 구동 및 고속 웅답을 위하여， 액정 재료는 유전율 이방성의 절대값이 크고, 회전 점도가 작으며， 적절한 탄성 계수 (Ku, K22) Κ33 평균값)를 가질 것이 요구된다. 이와 같은 액정 재료의 요구 물성은 1 내지 2 종류의 액정 화합물을 사용하여 만족시키는 것은 불가능하며, 통상적으로 7 내지 20 종류의 액정 화합물을 배합하여 층족시키고 있다. 한편， 상기 액정 표시 방식 중 IPS 혹은 VA 등은 현재 범용의 TN이나 STN과 달리 유전율 이방성이 음 (-)인 액정 재료를 사용한다는 특징을 갖는다. 그러나， 유전율 이방성이 음인 네가티브 액정 재료는 분자 측면에 극성 치환기가 존재하여 포지티브 액정 재료에 비하여 유전율 이방성을 조금만 변화시켜도 회전 점도가 크게 상승하는 문제가 있다. 이에 따라， 고속 웅답이 가능한 IPS 혹은 VA형 액정 표시 소자를 제공하기 위하여 유전율 이방성이 음이며， 절대값이 크고， 점성이 낮은 액정 화합물의 개발이 요구되고 있다. Liquid crystal display devices (LCDs) are used in watches, electronic calculators, various electrical devices, measuring devices, automotive panels, word processors, electronic notebooks, printers, computers, televisions, and the like. Typical liquid crystal displays include TN (Twist nematic), STN (Super, twisted nematic), In-lane switching (IPS) Fringe Field Switching (FFS), and Virtual Alignment (VA). The liquid crystal material used in such a liquid crystal display device is capable of low voltage driving and high-speed ungdap, and is required to "be operable in a wide temperature range. Specifically, in order to drive stably in a wide temperature range, the liquid crystal material exhibits stable physical properties at about -20 ° C or lower (low temperature stability), and is required to have a transparent point of about 70 ° C or higher. Then, for low voltage driving and high speed response, the liquid crystal material is required to have a high absolute value of dielectric anisotropy, a low rotational viscosity, and an appropriate elastic modulus (K u , K 22) κ 33 average value). It is impossible to satisfy the required physical properties of such liquid crystal materials by using one or two kinds of liquid crystal compounds, and usually seven to twenty kinds of liquid crystal compounds are compounded and stratified. On the other hand, IPS or VA of the liquid crystal display method is characterized by using a liquid crystal material having a negative dielectric anisotropy, unlike the general-purpose TN or STN. However, the negative liquid crystal material having negative dielectric anisotropy has a problem that a polar substituent exists on the side of the molecule, and the rotational viscosity is greatly increased even if the dielectric anisotropy is slightly changed compared to the positive liquid crystal material. Accordingly, In order to provide an IPS or VA type liquid crystal display device capable of high speed response, development of a liquid crystal compound having a negative dielectric anisotropy, a large absolute value, and a low viscosity is required.
【발명의 내용】  [Content of invention]
【해결하려는 과제】  [Problem to solve]
본 발명은 고유전을 이방성， 고굴절률 이방성 및 낮은 점도를 가지는 액정 화합물 및 이의 제조 방법을 제공하기 위한 것이다.  The present invention is to provide a liquid crystal compound having high anisotropy, high refractive index anisotropy and low viscosity, and a method for producing the same.
또한，. 본 발명은 상기 액정 화합물을 1종 이상 포함하는 액정 조성물을 제공하기 위한 것이다. Also,. The present invention is to provide a liquid crystal composition comprising at least one of the above liquid crystal compounds.
또한， 본 발명은 상기 액정 조성물을 포함하는 액정 표시 소자를 제공하기 위한 것이다.  Moreover, this invention is providing the liquid crystal display element containing the said liquid crystal composition.
【과제의 해결 수단】 . [Measures for the problem] .
상기 과제를 해결하기 위하여， 본 발명은 하기 화학식 1로 표시되는 액정 화합물을 제공한다:  In order to solve the above problems, the present invention provides a liquid crystal compound represented by the following formula (1):
Figure imgf000003_0001
Figure imgf000003_0001
상기 식에서,  Where
Li , L2 , L3 및 L4는 각각 독립적으로 수소 또는 할로겐이고， Li, L 2 , L 3 and L 4 are each independently hydrogen or halogen,
R은 수소, d- ) 알킬， C2-10 알케닐 또는 CHO 알콕시이고， 및 R represents hydrogen, d-) alkyl, C 2 - 10 alkenyl, or CHO, and alkoxy, and
nl 및 n2는 각각 독립적으로 0 내지 2의 정수이고， nl 및 n2의 합은 0 이상 2 이하이다. 상기 화학식 1로 표시되는 액정 화합물은， 음의 유전율 이방성을 가지는 액정 화합물로서， 상기 페닐기를 에틸렌 (-c¾-c¾-)으로 연결함에 따라 액정의 점도를 낮출 수 밌으며， 이에 따라 액정상을 최적화할 수 있다. 또한， 상기 화학식 1의 양말단은 2，3-디플루오로페닐기를 가지고， 적어도 하나의 말단에는 치환기로 알킬기를 가지지 않으며， 이러한 구조에 의하여 음의 유전율 이방성을 가질 수 있으며 , 높은 유전율 값을 나타낼 수 있다. 또한， 상기 화학식 1의 액정 화합물은 벤젠 고리 만으로 구성되어 있고， nl 및 n2에 따라 벤젠 고리의 개수를 조절하여 높은 굴절률 이방성 값을 가질 수 있으며， 따라서 액정 표시 소자의 빠른 웅답 속도를 구현할 수 있다. 바람직하게는, 상기 ， , 및 L4는 각각 독립적으로 수소 또는 플루오로이다ᅳ 또한 바람직하게는， 상기 Ll 및 L2가 동일하다. 또한 바람직하게는， 상기 L3 및 L4가 동일하다. 예컨대， 및 L2는 모두 수소이거나 모두 플루오로일 수 있다. 또한 바람직하게는， R은 수소， 메틸， 에틸 , 메톡시 또는 에록시이다ᅳ 또한， nl 및 n2의 합이 0 이상 2 이하이므로, 상기 액정 화합물은 벤젠 고리를 2개， 3개 또는 4개를 가질 수 있다. 상기 화학식 1로 표시되는 액정 화합물의 대표적인 예를 다음과 같다: nl and n2 are each independently an integer of 0 to 2, and the sum of nl and n2 is 0 or more and 2 or less. The liquid crystal compound represented by Chemical Formula 1 is a liquid crystal compound having negative dielectric anisotropy, and may lower the viscosity of the liquid crystal by connecting the phenyl group with ethylene (-c¾-c¾-), thereby optimizing the liquid crystal phase. can do. In addition, the sock end of Formula 1 has a 2,3-difluorophenyl group, at least one terminal does not have an alkyl group as a substituent, By having a negative dielectric constant anisotropy, it can exhibit a high dielectric constant value. In addition, the liquid crystal compound of Chemical Formula 1 may be composed of only benzene rings, and may have a high refractive index anisotropy value by adjusting the number of benzene rings according to nl and n2, thereby realizing a quick response rate of the liquid crystal display device. Preferably, the,, and L 4 are each independently hydrogen or fluoro eu Preferably, Ll and L 2 are the same. Also preferably, L 3 and L 4 are the same. For example, and L 2 may be both hydrogen or all fluoro. Also preferably, R is hydrogen, methyl, ethyl, methoxy or ethoxy. In addition, since the sum of nl and n2 is 0 or more and 2 or less, the liquid crystal compound may contain 2, 3 or 4 benzene rings. Can have Representative examples of the liquid crystal compound represented by Formula 1 are as follows:
Figure imgf000004_0001
Figure imgf000004_0001
Figure imgf000005_0001
또한， 본 발명은 하기 반응식 1과 같이， 상기 화학식 1로 표시되는 액정 화합물의 제조 방법을 제공한다.
Figure imgf000005_0001
In addition, the present invention provides a method for producing a liquid crystal compound represented by Chemical Formula 1, as shown in Scheme 1 below.
Figure imgf000005_0002
Figure imgf000005_0002
(상기 반웅식 1에서， ， , , L4, , nl 및 n2는 앞서 정의한 바와 같다) ' 상기 단계 1은， 화학식 2로 표시되는 화합물과 화학식 3으로 표시되는 화합물을 반웅시켜 화학식 4로 표시되는 화합물을 제조하는 단계로서， 에텐 (-CH=CH-) 결합으로 두 화합물을 결합하는 단계이다. 용매로는 THF를 사용하는 것이 바람직하다. 또한, 포타슴 터셔리- 부톡사이드의 존재하에 반응시키는 것이 바람직하다. 반응 온도는 0°C 이하가 바람직하다. 상가 단계 2는 화학식 4로 표시되는 화합물을 수소와 반웅시켜 목적 화합물은 화학식 1로 표시되는 화합물을 제조하는 단계이다. 상기 반응을 위하여 수소화 촉매를 사용할 수 있으며， 예컨대 팔라듐 /활성탄을 사용할 수.있다. 또한， 앝례로， 상기 출발 물질인 화학식 2로 표시되는 화합물은 하기 반응식 2와 같은 방법으로 제조할 수 있다. (In the reaction formula 1,,,, L 4 ,, nl and n2 are as defined above.) ' Step 1 is a compound represented by the formula (4) by reacting the compound represented by the formula (2) and the compound represented by the formula (3). As a step of preparing a compound, a step of combining two compounds with an ethene (—CH═CH—) bond. It is preferable to use THF as a solvent. It is also preferred to react in the presence of Potassium tertiary-butoxide. The reaction temperature is preferably 0 ° C. or less. Addition step 2 is to react the compound represented by the formula (4) with hydrogen The compound is a step of preparing a compound represented by the formula (1). Hydrogenation catalysts can be used for this reaction, for example palladium / activated carbon. In addition, in general, the compound represented by Formula 2 as the starting material may be prepared by the same method as in Scheme 2 below.
Figure imgf000006_0001
Figure imgf000006_0001
(상기 반웅식 2에서， LI , L2 , nl 및 n2는 앞서 정의한 바와 같다) 상기 반웅은， 화학식 5로 표시되는 화합물을 PPh3와 반웅시켜 화학식 5로 표시되는 화합물의 브로모를 P+Ph3Br—로 치환시키는 반웅이다. 또한， 본 ,발명은 상기 화학식 1로 표시되는 액정 화합물을 1종 이상 포함하는 액정 조성물을 제공한다. 상기 액정 조성물은 액정 조성물 전체 중량에 대하여 3 중량 % 이상 또는 4 중량 % 이상으로 상기 화학식 1로 표시되는 1종 이상의 액정 화합물을 포함할 수 있다. 만일 화학식 1로 표시되는 액정 화합물의 함량이 상기 범위 미만이면， 이로 인한 웅답 속도의 향상 효과가 미미할 수 있다. 또한， 상기 액정 조성물은 액정 조성물 전체 중량에 대하여 60 중량 % 이하， 40 중량 % 이하， 30 중량 이하 또는 20 중량 ¾> 이하로 상기 화학식 1로 표시되는 1 종 이상의 액정 화합물을 포함할 수 있다. 만일 화학식 1로 표시되는 액정 화합물의 함량이 상기 범위를 초과하면, 액정 조성물의 상전이 온도가 크게 증가되어 저온 영역에서 액정상을 확보할 수 없다는 문제가 초래될 수 있다. 상기 액정 조성물은 화학식 1의 액정 화합물 외에도 액정 표시 소자의 제반 성능을 위하여 다양한 액정 화합물을 추가로 포함할 수 있다. 일례로， 상기 액정 조성물은 후술할 하기 화학식 2 내지 5로 이루어진 군에서 선택되는 하나 이상의 액정 화합물을 추가로 포함할 수 있다. 상기 액정 조성물은 기존에 알려진 저점도의 액정 화합물을 추가로 포함할 수 있다. 이러한 저점도의 액정 화합물로는 하기 화학식 2로 표시되는 액정 화합물 등을 사용할 수 있다. (In Reaction Formula 2, LI, L2, nl, and n2 are as defined above.) The Reaction refers to bromo of the compound represented by Formula 5 by reacting the compound represented by Formula 5 with PPh 3 and adding P + Ph 3 Br. It is a reaction to substitute with —. In addition, the present invention provides a liquid crystal composition comprising at least one liquid crystal compound represented by the formula (1). The liquid crystal composition may include one or more liquid crystal compounds represented by Formula 1 in 3 wt% or more or 4 wt% or more based on the total weight of the liquid crystal composition. If the content of the liquid crystal compound represented by the formula (1) is less than the above range, the effect of improving the response rate can be insignificant. In addition, the liquid crystal composition may include one or more liquid crystal compounds represented by Chemical Formula 1 in an amount of 60 wt% or less, 40 wt% or less, 30 wt% or 20 wt% or less, based on the total weight of the liquid crystal composition. If the content of the liquid crystal compound represented by the formula (1) exceeds the above range, the phase transition temperature of the liquid crystal composition is greatly increased may cause a problem that the liquid crystal phase cannot be secured in the low temperature region. The liquid crystal composition may further include various liquid crystal compounds for overall performance of the liquid crystal display device in addition to the liquid crystal compound of Formula 1. For example, the liquid crystal composition may further include one or more liquid crystal compounds selected from the group consisting of the following Chemical Formulas 2 to 5 below. The liquid crystal composition may further include a known low viscosity liquid crystal compound. As such a low viscosity liquid crystal compound, a liquid crystal compound represented by the following formula (2) may be used.
[화학삭 2]  [Chemical Machining 2]
RH_A3_A4_R12 상기 화학식 2에서， RH_ A 3_ A 4_ R 12 In Chemical Formula 2 ,
R11 및 R12는 각각 독립적으로 수소, 탄소수 1 내지 15의 알킬 및 탄소수 1 내지 15의 알콕시 중 어느 하나의 라디칼이거나， 흑은 상기 라디칼 중 하나 이상의 -CH2-가 산소 원자들이 직접 연결되지 않도록 -C≡C -， -CH=CH -， -CF20- , -0-， -COO- 또는 -0C0-로 치환되거나 또는 상기 라디칼 중 하나 이상의 H가 할로겐으로 대체된 라디칼이고， R 11 and R 12 are each independently a radical of any one of hydrogen, alkyl of 1 to 15 carbon atoms and alkoxy of 1 to 15 carbon atoms, or black so that one or more of the radicals of -CH 2 -do not directly connect oxygen atoms; -C≡C-, -CH = CH-, -CF 2 0-, -0-, -COO- or -0C0- is substituted, or at least one H of the radicals is a radical substituted by halogen,
. A3 및 A4는 각각 독립적으로 사이클로핵실렌 또는 페닐렌이다. 상기 화학식 2로 표시되는 액정 화합물로 하기 화학식 2-1 및 화학식 2-2로 표시되는 화합물로 이루어진 군에서 선택된 1종 이상의 액정 화합물을 사용하여 높은 비저항을 유지하면서 액정 조성물의 투명점， 회전 점도， 굴절률 이방성 및 유전율 이방성 등을 용이하게 조절할 수 있다. . A 3 and A 4 are each independently cyclonuylene or phenylene. Transparent point, rotational viscosity, and the like of the liquid crystal composition while maintaining a high specific resistance using at least one liquid crystal compound selected from the group consisting of compounds represented by the following Formulas 2-1 and 2-2 as the liquid crystal compound represented by Formula 2 The refractive index anisotropy and the dielectric anisotropy can be easily adjusted.
Figure imgf000007_0001
Figure imgf000007_0001
상기 화학식 2-1 및 2-2에서， R11 및 R12는 화학식 2의 R11 및 R12와 같이 정의될 수 있다. 다른 예로， 상기 액정 조성물은 기존에 알려진 액정 화합물로 상전0 온도가 높거나 고굴절률을 나타내는 액정 화합물을 추가로 포함할 수 았다. 이러한 액정 화합물로는 하기 화학식 3으로 표시되는 액정 화합물 등을 사용할 수 있다. In Formula 2-1 and 2-2, R 11 and R 12 may be defined as R 11 and R 12 of formula (II). As another example, the liquid crystal composition in a liquid crystal phase transition 0 the known compound It may further include a liquid crystal compound exhibiting a high temperature or high refractive index. As such a liquid crystal compound, a liquid crystal compound represented by the following formula (3) may be used.
[화학식 3]  [Formula 3]
R13_A5_ (A6 ) p_A7_R14 상기 화학식 3에서， R 13_ A 5_ (A 6 ) p _ A 7_ R 14 In Chemical Formula 3,
R13 및 R14는 각각 독립적으로 수소， 탄소수 1 내지 15의 알킬 및 탄소수 1 내지 15의 알콕시 중 어느 하나의 라디칼이거나， 혹은 상기 라디칼 중 하나 이상의 -c¾-가 산소 원자들이 직접 연결되지 않도록 -c≡c- ,R 13 and R 14 are each independently a radical of any one of hydrogen, alkyl of 1 to 15 carbon atoms and alkoxy of 1 to 15 carbon atoms, or -c¾- of at least one of the radicals is not directly linked to oxygen atoms ≡c-,
-CH=CH -， -CF20- , -0-， -COO- 또는 — 0C0—로 치환되거나 또는 상기 라디칼 중 하나 이상의 H가 할로겐으로 대체된 라디칼이고， -CH = CH-, -CF 2 0-, -0-, -COO- or — 0C0— or a radical substituted with one or more H of the radicals is replaced by halogen,
A5 및 A7은 각각 독립적으로 사이클로핵실렌 또는 페닐렌이며， A 5 and A 7 are each independently cyclonuylene or phenylene,
A6은 사이클로핵실렌， 페닐렌 또는 할로겐으로 치환된 페닐렌이고 p는 1 또는 2의 정수이다. 상기 화학식 3으로 표시되는 액정 화합물로 하기 화학식 3-1 내지 3- 5로 이루어진 군에서 선택된 1종 이상의 액정 화합물을 사용하여 높은 비저항을 유지하면서 액정 조성물의 투명점， 회전 점도， 굴절률 이방성 및 조절할 수 있다. A 6 is cyclonuylene, phenylene or phenyl substituted with halogen and p is an integer of 1 or 2. As the liquid crystal compound represented by Chemical Formula 3, by using one or more liquid crystal compounds selected from the group consisting of Chemical Formulas 3-1 to 3-5, the transparent point, rotational viscosity, refractive index anisotropy and control of the liquid crystal composition may be maintained while maintaining high specific resistance. have.
Figure imgf000008_0001
Figure imgf000008_0001
[화학식 3-5]
Figure imgf000009_0001
[Formula 3-5]
Figure imgf000009_0001
상기 화학식 3-1 내지 3-5에서， R13 및 R14는 화학식 3의 R" 및 R14와 같이 정의될 수 있다. 또 다른 예로, 상기 액정 조성물은 기존에 알려진 중유전율 액정 화합물을 추가로 포함할 수 있다. 이러한 중유전율 액정 화합물로는 하기 화학식 4로 표시되는 액정 화합물 등을 사용할 수 있다. In Formula 3-1 to 3-5, R 13 and R 14 may be defined as in the general formula R 3 "and R 14. In another example, the liquid crystal composition in addition to oil-in-water dielectric constant liquid crystal the known compound As the medium dielectric constant liquid crystal compound, a liquid crystal compound represented by the following Chemical Formula 4 may be used.
[  [
R1 R 1
Figure imgf000009_0002
Figure imgf000009_0002
상기 화학식 4에서，  In Chemical Formula 4,
R15 및 R16은 각각 독립적으로 수소， 탄소수 1 내지 15의 알킬 및 탄소수 1 내지 15의 알콕시 중 어느 하나의 라디칼이거나， 혹은 상기 라디칼 중 하나 이상의 -c¾-가 산소 원자들이 직접 연결되지 않도록 -c≡c- , -CH=CH- , -CF20- , -0-， -COO- 또는 -0C0-로 치환되거나 또는 상기 라디칼 중 하나 이상의 H가 할로겐으로 대체된 라디칼이고， R 15 and R 16 are each independently a radical of any one of hydrogen, alkyl having 1 to 15 carbon atoms and alkoxy having 1 to 15 carbon atoms, or -c¾- at least one of the radicals is not directly linked to oxygen atoms. ≡c-, -CH = CH-, -CF 2 0-, -0-, -COO- or -0C0- or a radical substituted with one or more H of said radicals,
A8 및 A9는 각각 독립적으로 사이클로핵실렌， '테트라하이드로피라닐렌， 페닐렌 또는 할로겐으로 치환된 페닐렌이며， A 8 and A 9 are each independently cyclonuylene, ' tetrahydropyranylene, phenylene or phenyl substituted with halogen,
q는 0 내지 2 사이의 정수이다. 상기 화학식 4로 표시되는 액정 화합물로 하기 화학식 4-1 내지 화학식 4-4로 이루어진 군에서 선택된 1종 이상의 액정 화합물을 사용하여 높은 비저항을 유지하면서 액정 조성물의 투명점， 회전 점도， 굴절률 이방성 및 유전율 이방성 등을 용이하게 조절할 수 있다.  q is an integer between 0 and 2. Transparent point, rotational viscosity, refractive index anisotropy and dielectric constant of the liquid crystal composition while maintaining a high resistivity using at least one liquid crystal compound selected from the group consisting of the following Chemical Formulas 4-1 to 4-4 as the liquid crystal compound represented by Chemical Formula 4 Anisotropy etc. can be adjusted easily.
Figure imgf000009_0003
Figure imgf000009_0003
Figure imgf000010_0001
Figure imgf000010_0001
상기 화학식 4-1 내자 4-4에서， R15 및 R16는 화학식 4의 R15 및 R16과 같이 정의될 수 있다. 또 다른 예로， 상기 액정 조성물은 기존에 알려진 고유전율 액정 화합물을 추가로 포함할 수 있다. 이러한 액정 화합물로는 하기 화학식 5로 표시되는 액정 화합물 등을 사용할 수 있다.
Figure imgf000010_0002
In Formula 4-1 naeja 4-4, R 15 and R 16 may be defined as R 15 and R 16 of formula (4). As another example, the liquid crystal composition may further include a conventional high dielectric constant liquid crystal compound. As such a liquid crystal compound, a liquid crystal compound represented by the following formula (5) may be used.
Figure imgf000010_0002
상기 화학식 5에서，  In Chemical Formula 5,
R17 및 R18은 각각 독립적으로 수소， 탄소수 1 내지 15의 알킬 및 탄소수 1 내지 15의 알콕시 중 어느 하나의 라디칼이거나， 혹은 상기 라디칼 중 하나 이상의 -CH2-가 산소 원자들이 직접 연결되지 않도록 -C≡C -， 一 CH=CH— , -CF2O-, -0-， -COO- 또는 -0C0-로 치환되거나 또는 상기 라디칼 중 하나 이상의 H가 할로겐으로 대체된 라디칼이며， R 17 and R 18 are each independently a radical of any one of hydrogen, alkyl of 1 to 15 carbon atoms and alkoxy of 1 to 15 carbon atoms, or one or more of -CH 2 -of the radicals do not directly connect oxygen atoms; Is a radical substituted with C≡C-, one CH = CH—, -CF 2 O-, -0-, -COO- or -0C0- or at least one of the radicals is replaced by halogen,
A10, A11 및 A12는 각각 독립적으로 사이클로핵실렌， 테트라하이드로피라닐렌， 페닐렌 및 할로겐으로 치환된 페닐렌 중 어느 하나이고， A 10 , A 11 and A 12 are each independently one of cyclonuclear styrene, tetrahydropyranylene, phenylene and phenylene substituted with halogen,
Z4 및 Z5는 각각 독립적으로 -CH2CH2-, -CH-CH-, — C≡C―， — C¾0-, - 0CH2-, -CH2CF2-, -CHFCHF-, -CF2CH2-, -CH2CHF-, -CHFCH2-, -C2F4_, -C00-, - 0C0-, -CF20-, -OCF2- 또는 -0-이며， Z 4 and Z 5 are each independently -CH 2 CH 2- , -CH-CH-, —C≡C― ， — C¾0-,-0CH 2- , -CH 2 CF 2- , -CHFCHF-, -CF 2 CH 2- , -CH 2 CHF-, -CHFCH 2- , -C 2 F 4 _, -C00-,-0C0-, -CF 2 0-, -OCF2- or -0-,
r 및 v는 0 또는 1이고, r + v는 1 또는 2이며，  r and v are 0 or 1, r + v is 1 or 2,
s 및 w는 0 내지 2 사이의 정수이다. 상기 화학식 5로 표시되는 액정 화합물로 하기 화학식 5—1 내지 5- 4로 이루어진 군에서 선택된 1종 이상의 액정 화합물을 사용하여 높은 비저항을 유지하면서 액정 조성물의 투명점， 회전 점도, 굴절률 이방성 및 유전율 이방성 등을 용이하게 조절할 수 있다. s and w are integers between 0 and 2. Transparent point, rotational viscosity, refractive index anisotropy, and dielectric anisotropy of the liquid crystal composition while maintaining a high resistivity using at least one liquid crystal compound selected from the group consisting of the following Formulas 5—1 to 5-4 as the liquid crystal compound represented by Formula 5 Etc. can be easily adjusted.
Figure imgf000011_0001
Figure imgf000011_0001
상기 화학식 5-1 내지 5-4에서， R17 및 R18은 화학식 5의 R17 및 R18과 같이 정의될 수 있다. 상기 액정 조성물은 액정 조성물의 목적하는 용도 및 효과를 고려하여 상기 화학식 2 내지 화학식 5로 표시되는 액정 화합물 중 1 이상의 액정 화합물을 적절히 포함할 '수 있다. 특히， 상기 액정 조성물은 액정 조성물의 다양한 제반 물성을 균형 았게 향상시키기 위하여 화학식 2， 화학식 3 및 화학식 4로 표시되는 액정 화합물을 포함할 수 있다. 이때， 화학식 2 내지 화학식 4로 표시되는 액정 화합물로 각각 1종 이상의 액정 화합물을 사용할 수 있다. 상기 액정 조성물은 액정 화합물 외에도 본 발명이 속하는 기술분야에서 통상적으로 사용하는 다양한 첨가제를 추가로 포함할 수 있다. 일례로， 상기 액정 조성물은 산화 방지제를 추가로 포함할 수 있다. 또한， 상기 액정 조성물은 반응성 메소젠을 추가로 포함할 수 있다. 이러한 반응성 메소젠은 액정상 거동을 나타내는 메소젠기와， 적어도 일측 말단에 광중합， 광가교 또는 광경화 가능한 불포화 작용기， 예를 들어， 비닐기， (메트)아크릴기 또는 에폭시기 등을 갖는 화합물로 정의될 수 있고, 이러한 정의를 층족하는 임의의 화합물을 반웅성 메소젠으로서 포함할 수 있다. 일례로， 상기 반웅성 메소젠으로， 액정 골격을 갖는 디아크릴레이트 단량체 또는 액정 골격을 갖는 디메타크릴레이트 단량체를 포함할 수 있다. 또한， 상기 액정 조성물은 UV 안정제를 추가로 포함할 수 있다. 이러한 UV 안정제로는 Hals (Hindered amine light stabilizer) 계열을 사용할 수 있다. 또한， 본 발명은 상기 액정 조성물을 포함하는 액정 표시 소자를 제공한다. 본 발명에 따른 액정 조성물은 낮은 회전 점도 하에서도 높은 음의 유전율 이방성 및 고굴절률 이방성을 나타내어， 특히 네가티브 액정 재료를 사용하는 VA Virtical Alignment), MVA(Multidomain Virtical Alignment), PVA(Patterned Virtical Alignment), PS-VA( Polymer Stabilized Virtical Alignment) 또는 IPS( In-Plane Switching) 모드 등의 액정 표시 소자의 우수한 제반 성능을 유지하면서 고속 웅답을 실현할 수 있을 것으로 기대된다. In Formula 5-1 to 5-4, R 17 and R 18 may be defined as R 17 and R 18 of formula (5). The liquid crystal composition can 'be suitably comprises a liquid crystal compound and the intended use of at least one of liquid crystal compounds represented by considering the effect by the above formula (2) to formula (5) to the liquid crystal composition. In particular, the liquid crystal composition may include a liquid crystal compound represented by Formula 2, Formula 3, and Formula 4 in order to balance various physical properties of the liquid crystal composition. In this case, at least one liquid crystal compound may be used as the liquid crystal compound represented by Formulas 2 to 4, respectively. The liquid crystal composition may further include various additives commonly used in the art to which the present invention belongs, in addition to the liquid crystal compound. For example, the liquid crystal composition may further include an antioxidant. In addition, the liquid crystal composition may further include a reactive mesogen. Such reactive mesogen may be defined as a compound having a mesogenic group exhibiting liquid crystal phase behavior and an unsaturated functional group capable of photopolymerization, photocrosslinking or photocuring at least one end thereof, for example, a vinyl group, a (meth) acryl group, or an epoxy group. And any compound that satisfies this definition may be included as the semi-ungsogenic mesogen. As an example, the semi-ungsogenic mesogen may include a diacrylate monomer having a liquid crystal skeleton or a dimethacrylate monomer having a liquid crystal skeleton. In addition, the liquid crystal composition may further include a UV stabilizer. These UV stabilizers can be used Hals (Hindered amine light stabilizer) series. In addition, the present invention provides a liquid crystal display device comprising the liquid crystal composition. The liquid crystal composition according to the present invention exhibits high negative dielectric anisotropy and high refractive index anisotropy even under low rotational viscosity, and in particular, VA Virtical Alignment (MVA), Multidomain Virtical Alignment (MVA), Patterned Virtical Alignment (PVA), It is expected that high speed response can be achieved while maintaining excellent overall performance of liquid crystal display devices such as PS-VA (Polymer Stabilized Virtical Alignment) or IPS (In-Plane Switching) mode.
【발명의 효과】  【Effects of the Invention】
본 발명에 따른 액정 화합물은 고유전율 이방성， 고굴절률 이방성 및 낮은 점도를 가지며， 따라서 다양한 액정 표시 소자， 특히 신속한 응답 시간을 요구하는 VA, MVA, PVA, PS-VA, PALC, FFS, PS-FFS, IPS 또는 PS- IPS모드의 액정 표시 소자에 최적화된 액정 조성물을 제공할 수 있다.  The liquid crystal compound according to the present invention has high dielectric anisotropy, high refractive index anisotropy and low viscosity, and therefore various liquid crystal display devices, especially VA, MVA, PVA, PS-VA, PALC, FFS, PS-FFS, which require fast response time. The liquid crystal composition optimized for the liquid crystal display element of the IPS or PS-IPS mode can be provided.
【발명을 실시하기 위한 구체적인 내용】  [Specific contents to carry out invention]
이하， 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐， 이에 의해 본 발명의 내용이 한정되는 것은 아니다. 이하의 실시예， 비교예 및 실험예에 있어서, 액정 화합물의 표기는 하기 표 1과 같다. Hereinafter, preferred embodiments of the present invention are provided to aid in understanding the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto. In the following Examples, Comparative Examples and Experimental Examples, the notation of a liquid crystal compound is shown in Table 1 below.
【표 1】  Table 1
Figure imgf000013_0002
Figure imgf000013_0002
― 중심 그 Φ과연 ¾ 그 "사이는별도푀 표 큼  ― Center Φ indeed ¾ the “between the separate 푀 big
- 증' 그 Φ과맣단그를은 " -" 로 구분.  -Increase the Φ and black dang by "-".
-.말단과말단은 " ." 으로구분, 말단은 마지막에 작성 - . The end and end are "." Separated into, the terminal is written at the end
Figure imgf000013_0001
제조예 FNF-H.02)
Figure imgf000013_0001
Preparation Example FNF-H.02)
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0002
브롬 염 화합물 (화학식 1-1， 40 誦 01， 18.8g)을 무수 THF에 녹인 후 -30°C에서 교반하면서 포타슘 터셔리 -부록사이드 (48.1 匪 ol, 5.4 g)를 서서히 가하고 30분 동안 교반하였다. -30°C에서 알데하이드 화합물 (화학식 1-2, 43.7 mmol, 8.13 g)을 THF에 녹여 적가하였다. -10°C로 온도를 을린 뒤 1시간 동안 교반한 후 반웅 용기에 물과 를루엔 1:1 용매를 넣어 반응을 종결시켰다. 유기 용매층을 추출하고 감압증류하여 생긴 고체를 컬럼 크로마토그래피를 통해 분리하여 에텐화합물 (화학식 1-3， 60 %, 7.1 g)을 수득하였다. 수득한 에텐화합물 (화학식 1-3, 24 瞧 01, 7.1 g)과 팔라듐 /활성탄 (10 \vt. , 1.5 g)을 THF와 메탄올 1:1 용매에 녹인 후 수소반응기에서 3시간 동안 반응시키고 여과하였다. 여과액을 농축한 후， 컬럼 크로마토 그래피를 통해 목적 화합물 (화학식 1， 94 %, 6.7 g)을 수득하였다. The bromine salt compound (Formula 1-1, 40 誦0 , 18.8 g) was dissolved in anhydrous THF, and potassium tertiary-butoxide (48.1 匪 ol, 5.4 g) was slowly added with stirring at -30 ° C for 30 minutes. Stirred. The aldehyde compound (Formula 1-2, 43.7 mmol, 8.13 g) was added dropwise in THF at -30 ° C. After the temperature was lowered to -10 ° C and stirred for 1 hour, water and toluene 1: 1 solvent were added to the reaction vessel to terminate the reaction. The organic solvent layer was extracted, and the solid obtained by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 1-3, 60%, 7.1 g). The obtained ethene compound (Formula 1-3, 24 瞧0 1, 7.1 g) and palladium / activated carbon (10 \ vt., 1.5 g) were dissolved in THF and methanol 1: 1 solvent and reacted for 3 hours in a hydrogen reactor. Filtered. After the filtrate was concentrated, the target compound (Formula 1, 94%, 6.7 g) was obtained through column chromatography.
¾ NMR (300 MHz, CDC13) δ 7.01 (m, 2H), 6.87 (t, 1H), 6.75 (t, 1H), 6.63 (t, 1H), 4.11 (q, 2H), 2.95 (m, 4H)， 1.45 (t, 3H); MS m/z 298 (M+); mp 55.9°C ¾ NMR (300 MHz, CDC1 3 ) δ 7.01 (m, 2H), 6.87 (t, 1H), 6.75 (t, 1H), 6.63 (t, 1H), 4.11 (q, 2H), 2.95 (m, 4H ), 1.45 (t, 3 H); MS m / z 298 (M + ); mp 55.9 ° C
Figure imgf000014_0003
Figure imgf000014_0003
2  2
브롬 염 화합물 (화학식 2-1， 40隱 ol, 18.8 g)을 무수 THF에 녹인 후 After bromine salt compound (Formula 2-1 ， 40 隱 ol, 18.8 g) was dissolved in anhydrous THF
-30°C에서 교반하면서 포타슘 터셔리 -부톡사이드 (48.1 隱 ol, 5.4 g)를 서서히 가하고 30분 동안 교반하였다. -3CTC에서 알데하이드 화합물 (화학식 2-2, 43.7 隱 ol, 11.45 g)을 THF에 녹여 적가 하였다. -10°C로 온도를 올린 뒤 1시간 동안 교반한 다음， 반웅 용기에 물과 를루엔 1:1 용매를 넣어 반웅을 종결시켰다. 유기 용매층을 추출하고 감압증류하여 생긴 고체를 컬럼 크로마토그래피를 통해 분리하여 에텐화합물 (화학식 2-3， 57 , 8.5 g)을 수득하였다. 수득한 에텐화합물 (화학식 2-3， 22.83 隱 ol, 8.5 g)과 팔라듐 /활성탄 (10 wt.%, 2.1 g)을 THF와 메탄올 1:1 용매에 녹인 후 수소 반응기에서 3시간 동안 반응시키고 여과하였다. 여과액을 농축시킨 뒤 컬럼 크로마토그래피를 통해 목적 화합물 (화학식 2， 91 %, 7.8 g)을수득하였다. Potassium tertiary-butoxide (48.1 隱 ol, 5.4 g) with stirring at -30 ° C Slowly added and stirred for 30 minutes. At -3CTC, an aldehyde compound (Formula 2-2, 43.7 隱 ol, 11.45 g) was added dropwise in THF. After raising the temperature to -10 ° C and stirred for 1 hour, the reaction was terminated by adding water and toluene 1: 1 solvent in a reaction vessel. The organic solvent layer was extracted, and the solid obtained by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 2-3, 57, 8.5 g). The obtained ethene compound (Formula 2-3, 22.83 隱 ol, 8.5 g) and palladium / activated carbon (10 wt.%, 2.1 g) were dissolved in THF and methanol 1: 1 solvent, reacted in a hydrogen reactor for 3 hours, and filtered. It was. The filtrate was concentrated and then subjected to column chromatography to obtain the target compound (Formula 2, 91%, 7.8 g).
¾ NMR (300 丽 z, CDCls) δ 7.44 (d, 2H), 7.27 (d, 2H), 7.11 (m, 4H), 6.81 (t, 1H), 4.19 (q, 2H), 3.00 (m, 4H) , 1.55 (t, 3H); MS m/z 374 (M+); mp 64.9°C ¾ NMR (300 liza, CDCls) δ 7.44 (d, 2H), 7.27 (d, 2H), 7.11 (m, 4H), 6.81 (t, 1H), 4.19 (q, 2H), 3.00 (m, 4H ), 1.55 (t, 3 H); MS m / z 374 (M + ); mp 64.9 ° C
Figure imgf000015_0001
Figure imgf000015_0001
브롬 염 화합물 (화학식 3—2， 27.3醒 ol, 14 g)을 무수 THF에 녹인 후 -30°C에서 교반하면서 포타슘 터셔리 -부특사이드 (32.7 隱 ol, 3.7 g)를 서서히 가하고 30분 동안 교반하였다. -30°C에서 알데하이드 화합물 (화학식 3-1， 29.7 隱 ol, 6.49 g)을 THF에 녹여 적가하였다. -K C로 온도를 올린 뒤 1시간 동안 교반한 후 반웅 용기에 물과 를루엔 1:1 용매를 넣어 반웅을 종결시켰다. 유기 용매층을 추출하고 감압증류하여 생긴 고체를 컬럼 크로마토그래피를 통해 분리하여 에텐화합물 (화학식 3-3， 65 %, 6.6 g)을 수득하였다. 수득한 에텐화합물 (화학식 3-3， 17.7 隱 ol, 6.6 g)과 팔라듐 /활성탄 (10 wt.%, 1.65 g)을 THF와 메탄올 1:1 용매에 녹인 후 수소 반응기에서 3시간 동안 반웅시키고 여과하였다. 여과액을 농축시킨 뒤 컬럼 크로마토그래피를 통해 목적 화합물 (화학식 3， 94 %, 6.24 g)을 수득하였다. Ή NMR (300 腿 z, CDCI3) δ 7.47 (d, 2H), 7.27 (d, 2H), 7.20 (m, 3H), 6.79 (t, 1H), 6.65 (t, 1H), 4.12 (q, 2H), 2.93 (m, 4H) , 1.55 (t, 3H); MS m/z 374 (M+); mp 88 °C The bromine salt compound (Formula 3-2, 27.3 醒 ol, 14 g) was dissolved in anhydrous THF, and potassium tertiary-butoxide (32.7 隱 ol, 3.7 g) was slowly added with stirring at −30 ° C. and stirred for 30 minutes. It was. The aldehyde compound (Formula 3-1, 29.7 隱 ol, 6.49 g) was added dropwise in THF at -30 ° C. After raising the temperature to -KC and stirred for 1 hour, the reaction was terminated by adding water and toluene 1: 1 solvent in the reaction vessel. The organic solvent layer was extracted, and the solid obtained by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 3-3, 65%, 6.6 g). The obtained ethene compound (Formula 3-3, 17.7 隱 ol, 6.6 g) and palladium / activated carbon (10 wt.%, 1.65 g) were dissolved in THF and methanol 1: 1 solvent and reacted for 3 hours in a hydrogen reactor, followed by filtration. It was. The filtrate was concentrated and then subjected to column chromatography to give the target compound (Formula 3, 94%, 6.24 g). Ή NMR (300 腿 z, CDCI 3 ) δ 7.47 (d, 2H), 7.27 (d, 2H), 7.20 (m, 3H), 6.79 (t, 1H), 6.65 (t, 1H), 4.12 (q, 2H), 2.93 (m, 4H), 1.55 (t, 3H); MS m / z 374 (M + ); mp 88 ° C
Figure imgf000016_0001
Figure imgf000016_0001
4  4
브롬 염 화합물 (화학식 4—1, 21.3 瞧 ol, 10 g)을 무수 THF에 녹인 후 -30°C에서 교반하면서 포타슘 터셔리 -부록사이드 (25.6 mmol, 2.9 g)를 서서히 가하고 30분 동안 교반하였다. -30°C에서 알데하이드 화합물 (화학식 4-2, 23.2 隱 ol, 7.86 g)을 THF에 녹여 적가하였다. -KTC로 온도를 올린 뒤 1시간 동안 교반한 후 반응 용기에 물과 를루엔 1:1 용매를 넣어 반웅을 종결시켰다. 유기 용매충을 추출하고 감압증류하여 생긴 고체를 컬럼 크로마토그래피를 통해 분리하여 에텐화합물 (화학식 4-3， 59 ， 5.64 g)을 수득하였다. 수득한 에텐화합물 (화학식 4-3， 12.6 隱 01， 5.64 g)과 팔라듐 /활성탄 (10 wt.%, 1.4 g)을 THF와 메탄을 1:1 용매에 녹인 후 수소 반응기에서 3시간 동안 반웅시키고 여과하였다. 여과액을 농축시킨 뒤 컬럼 크로마토그래피를 통해 목적 화합물 (화학식 4， 97 %， 3.9 g)을 수득하였다. The bromine salt compound (Formula 4-1, 21.3 瞧 ol, 10 g) was dissolved in anhydrous THF and potassium tertiary-butoxide (25.6 mmol, 2.9 g) was added slowly with stirring at -30 ° C and stirred for 30 minutes. . The aldehyde compound (Formula 4-2, 23.2 隱 ol, 7.86 g) was added dropwise in THF at -30 ° C. After raising the temperature with -KTC and stirring for 1 hour, the reaction vessel was terminated by adding water and toluene 1: 1 solvent. The organic solvent was extracted and the solid produced by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 4-3, 59, 5.64 g). The obtained ethene compound (Formula 4-3, 12.6 隱0 1, 5.64 g) and palladium / activated carbon (10 wt.%, 1.4 g) were dissolved in THF and methane in a 1: 1 solvent and reacted for 3 hours in a hydrogen reactor. And filtered. The filtrate was concentrated and then subjected to column chromatography to give the target compound (Formula 4, 97%, 3.9 g).
¾ NMR (300 MHz, CDC13) δ 7.67 (d, 2Η), 7.59 (t, 4H) , 7.29 (d, 2H), 7.17 (t, 1H), 7.05 (m, 3H), 6.84 (t, 1H), 4.20 (q, 2H), 3.03 (m, 4H), 1.51 (t, 3H); MS m/z 450 (M+); mp 209 °C ¾ NMR (300 MHz, CDC1 3 ) δ 7.67 (d, 2Η), 7.59 (t, 4H), 7.29 (d, 2H), 7.17 (t, 1H), 7.05 (m, 3H), 6.84 (t, 1H ), 4.20 (q, 2H), 3.03 (m, 4H), 1.51 (t, 3H); MS m / z 450 (M + ); mp 209 ° C
Figure imgf000016_0002
Figure imgf000016_0002
5 브롬 염 화합물 (화학식 5-2， 20.2 隱 ol, 12.5. g)을 무수 THF에 녹인 후 -30°C에서 교반하면서 포타슘 터셔리 -부특사이드 (25.4 誦 ol, 2.86 g)를 서서히 가하고 30분 동안 교반하였다. -30°C에서 알데하이드 화합물 (화학식 5-1， 23.1 腿 ol, 5.04 g)을 THF에 녹여 적가하였다. -10°C로 온도를 올린 뒤 1시간 동안 교반한 후 반응 용기에 물과 를루엔 1:1 용매를 넣어 반응을 종결시켰다. 유기 용매층을 추출하고 감압증류하여 생긴 고체를 컬럼 크로마토그래피를 통해 분리하여 에텐화합물 (화학식 5-3， 74 %, 7 g)을 수득하였다. 수득한 에텐화합물 (화학식 5-3， 15.6 隱 ol, 7 g)과 팔라듐 /활성탄 (10 wt.%, 1.75 g)을 THF와 메탄올 1:1 용매에 녹인 후 수소 반응기에서 3시간 동안 반웅시키고 여과하였다. 여과액을 농축시킨 뒤 컬럼 크로마토그래피를 통해 목적 화합물 (화학식 5， 81 %, 5.69 g)을 수득하였다. 5 The bromine salt compound (Formula 5-2, 20.2 隱 ol, 12.5. G) was dissolved in anhydrous THF, and then potassium tertiary-subside (25.4 誦 ol, 2.86 g) was added slowly with stirring at -30 ° C for 30 minutes. Stirred. The aldehyde compound (Formula 5-1, 23.1 腿 ol, 5.04 g) was added dropwise in THF at -30 ° C. After the temperature was raised to -10 ° C and stirred for 1 hour, water and toluene 1: 1 solvent were added to the reaction vessel to terminate the reaction. The organic solvent layer was extracted, and the solid obtained by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 5-3, 74%, 7 g). The obtained ethene compound (Formula 5-3, 15.6 隱 ol, 7 g) and palladium / activated carbon (10 wt.%, 1.75 g) were dissolved in THF and methanol 1: 1 solvent and reacted for 3 hours in a hydrogen reactor, followed by filtration. It was. The filtrate was concentrated and then subjected to column chromatography to give the target compound (Formula 5, 81%, 5.69 g).
¾ NMR (300 MHz, CDC13) δ 7.49 (d, 2H) , 7.45 (d, 2Η), 7.32 (t, 4H), 7.21 (m, 4H), 6.82 (t, 1H) , 4.19 (q, 2H)， 3.01 (m, 4H), 1.50 (t, 3H); MS m/z 450 (M+); mp 150 °C ¾ NMR (300 MHz, CDC1 3 ) δ 7.49 (d, 2H), 7.45 (d, 2Η), 7.32 (t, 4H), 7.21 (m, 4H), 6.82 (t, 1H), 4.19 (q, 2H ), 3.01 (m, 4H), 1.50 (t, 3H); MS m / z 450 (M + ); mp 150 ° C
Figure imgf000017_0001
브름 염 화합물 (화학식 6-2， 15.6 誦 ol, 8 g)을 무수 THF에 녹인 후 -30°C에서 교반하면서 포타슘 터셔리 -부특사이드 (18.7 隱 ol, 2.1 g)를 서서히 가하고 30분 동안 교반하였다. -30°C에서 알데하이드 화합물 (화학식 6-1, 16.99 隱 ol, 5 g)을 THF에 녹여 적가하였다. -10°C로 온도를 올린 뒤 1시간 동안 교반한 후 반응 용기에 물과 를루엔 1:1 용매를 넣어 반웅을 종결시켰다. 유기 용매층을 추출하고 감압증류하여 생긴 고체를 컬럼 크로마토그래피를 통해 분리하여 에텐화합물 (화학식 6-3， 90 %, 6.29 g)을 수득하였다. 수득한 에텐화합물 (화학식 6-3, 14 隱 ol, 6.29 g)과 팔라듐 /활성탄 (10 wt.%, 1.6 g)을 THF와 메탄을 1:1 용매에 녹인 후 수소 반응기에서 3시간 동안 반웅시키고 여과하였다. 여과액을 농축시킨 뒤 컬럼 크로마토그래피를 통해 목적 화합물 (화학식 6， 79 %， 5 g)을 수득하였다.
Figure imgf000017_0001
The brine compound (Formula 6-2, 15.6 誦 ol, 8 g) was dissolved in anhydrous THF, and then potassium tertiary-buside (18.7 隱 ol, 2.1 g) was added slowly with stirring at -30 ° C and stirred for 30 minutes. It was. The aldehyde compound (Formula 6-1, 16.99 隱 ol, 5 g) was added dropwise in THF at -30 ° C. After raising the temperature to -10 ° C and stirred for 1 hour, the reaction vessel was terminated by adding water and toluene 1: 1 solvent. The organic solvent layer was extracted, and the solid obtained by distillation under reduced pressure was separated by column chromatography to obtain an ethene compound (Formula 6-3, 90%, 6.29 g). The obtained ethene compound (Formula 6-3, 14 隱 ol, 6.29 g) and palladium / activated carbon (10 wt.%, 1.6 g) were dissolved in a 1: 1 solvent of THF and methane, and then hydrogen The reaction was reacted for 3 hours in the reactor and filtered. The filtrate was concentrated and then subjected to column chromatography to give the target compound (Formula 6, 79%, 5 g).
¾ 證 (300 匪 z, CDC13) δ 7.69 (d, 2H), 7.63 (d, 2H), 7.58 (d, 2H), 7.28 (m, 5H), 6.79 (t, 1H), 6.65 (t, 1H) , 4.12 (q, 2H), 2.94 (m, 4H), 1.46 (t, 3H); MS m/z 450 (M+); mp 174 °C ¾ 證 (300 匪 z, CDC1 3 ) δ 7.69 (d, 2H), 7.63 (d, 2H), 7.58 (d, 2H), 7.28 (m, 5H), 6.79 (t, 1H), 6.65 (t, 1H), 4.12 (q, 2H), 2.94 (m, 4H), 1.46 (t, 3H); MS m / z 450 (M + ); mp 174 ° C
Figure imgf000018_0001
Figure imgf000018_0001
제조예 1과 동일한 방법으로 제조하되， 화학식 1-2로 표시되는 화합물로 에특시 대신 메특시를 치환기로 가지는 화합물을 사용하여， 목적 화합물을 수득하였다. - Prepared in the same manner as in Preparation Example 1, using the compound represented by the formula (1-2), instead of the specialty mexiche as a substituent, to obtain the target compound. -
¾ NMR (300 MHz, CDCI3) δ 7.01 (m, 2H), 6.87 (t, 1H), 6.75 (t, 1H), 6.63 (t, 1H), 3.87 (s, 3H) , 2.95 (m, 4H); MS m/z 284 (M+) ¾ NMR (300 MHz, CDCI 3 ) δ 7.01 (m, 2H), 6.87 (t, 1H), 6.75 (t, 1H), 6.63 (t, 1H), 3.87 (s, 3H), 2.95 (m, 4H ); MS m / z 284 (M + )
Figure imgf000018_0002
Figure imgf000018_0002
제조예 1과 동일한 방법으로 제조하되， 화학식 1-2로 표시되는 화합물로 에특시 대신 메틸을 치환기로 가지는 화합물을 사용하여， 목적 화합물을 수득하였다.  Prepared in the same manner as in Preparation Example 1, using a compound having methyl as a substituent instead of special compounds represented by the formula 1-2, to obtain the target compound.
¾ NMR (300 MHz, CDC13) δ 7.01 (m, 2H), 6.88 (t, 1H), 6.79 (t,¾ NMR (300 MHz, CDC1 3 ) δ 7.01 (m, 2H), 6.88 (t, 1H), 6.79 (t,
1H), 6.72 (t, 1H), 2.96 (m, 4H) , 2.25 (s, 3H); MS m/z 268 (M+) 1H), 6.72 (t, 1H), 2.96 (m, 4H), 2.25 (s, 3H); MS m / z 268 (M + )
Figure imgf000018_0003
Figure imgf000018_0003
제조예 1과 동일한 방법으로 제조하되， 화학식 1-2로 표시되는 화합물로 에특시 대신 에틸을 치환기로 가지는 화합물을 사용하여, 목적 화합물을 수득하였다. Prepared in the same manner as in Preparation Example 1, using a compound represented by the formula 1-2, having a substituent as an ethyl instead of special, The compound was obtained.
¾ NMR (300 MHz, CDC13) δ 7.24 (m, 2H) , 6.87 (m, 2Η), 6.82 (m, 1H), 2.97 (m, 4H), 2.68 (q, 2H) , 1.23 (t, 3H); MS. m/z 282 (M+) ¾ NMR (300 MHz, CDC1 3 ) δ 7.24 (m, 2H), 6.87 (m, 2Η), 6.82 (m, 1H), 2.97 (m, 4H), 2.68 (q, 2H), 1.23 (t, 3H ); MS. m / z 282 (M + )
Figure imgf000019_0001
Figure imgf000019_0001
제조예 2와 동일한 방법으로 제조하되, 화학식 2-2로 표시되는 화합물로 에톡시 대신 메틸을 치환기로 가지는 화합물을 사용하여， 목적 화합물을 수득하였다.  Prepared in the same manner as in Preparation Example 2, using the compound represented by the formula (2-2) having a substituent as methyl instead of ethoxy, the target compound was obtained.
¾ NMR (300 腿 z, CDCls) δ 7.45 (d, 2H) , 7.24 (m, 3Η), 7.11 (m, 4H), 3.01 (m, 4H), 2.33 (s, 3H); MS m/z 344 (M+) ¾ NMR (300 Hz z, CDCls) δ 7.45 (d, 2H), 7.24 (m, 3Η), 7.11 (m, 4H), 3.01 (m, 4H), 2.33 (s, 3H); MS m / z 344 (M + )
Figure imgf000019_0002
Figure imgf000019_0002
제조예 2와 동일한 방법으로 제조하되， 화학식 2-2로 표시되는 화합물로 에록시 대신 에틸을 치환기로 가지는 화합물을 사용하여， 목적 화합물을 수득하였다.  Prepared in the same manner as in Preparation Example 2, using a compound having ethyl as a substituent instead of hydroxy as a compound represented by the formula 2-2, to obtain the target compound.
¾ NMR (300 MHz, CDC13) δ 7.46 (d, 2H), 7.26 (d, 2H) , 7.11-6.89 (m, 5H), 3.02 (m, 4H), 2.74 (q, 2H), 1.53 (t, 3H); MS m/z 358 (M+) ¾ NMR (300 MHz, CDC1 3 ) δ 7.46 (d, 2H), 7.26 (d, 2H), 7.11-6.89 (m, 5H), 3.02 (m, 4H), 2.74 (q, 2H), 1.53 (t , 3H); MS m / z 358 (M + )
Figure imgf000019_0003
Figure imgf000019_0003
제조예 5와 동일한 방법으로 제조하되， 화학식 5-2로 표시되는 화합물로 에특시 대신 메틸을 치환기로 가지는 화합물을 사용하여, 목적 화합물을 수득하였다.  Prepared in the same manner as in Preparation Example 5, using the compound represented by the formula (5-2) having a methyl substituent as a substituent instead of special properties, to obtain the target compound.
¾ NMR (300 MHz, CDC13) δ 7.46 (m, 4H)， 7.28 (m, 4H)， 7.08—6.92 5H), 2.98 (ni, 4H), 2.30 (s, 3H); MS m/z 420 (M+) ¾ NMR (300 MHz, CDC1 3 ) δ 7.46 (m, 4H), 7.28 (m, 4H), 7.08—6.92 5H), 2.98 (ni, 4H), 2.30 (s, 3H); MS m / z 420 (M + )
Figure imgf000020_0001
Figure imgf000020_0001
제조예 5와 동일한 방법으로 제조하되， 화학식 5-2로 표시되는 화합물로 에특시 대신 에틸을 치환기로 가지는 화합물을 사용하여， 목적 화합물을 수득하였다.  Prepared in the same manner as in Preparation Example 5, using a compound having ethyl as a substituent instead of a special compound represented by the formula 5-2, to obtain the target compound.
¾ NMR (300 MHz, CDC13) δ 7.48 (m, 4H), 7.31 (m, 4H)， 7.19-6.98 (m, 5H), 3.01 (m, 4H) , 2.74 (q, 2H) , 1.28 (t, 3H); MS m/z 434 (M+) ¾ NMR (300 MHz, CDC1 3 ) δ 7.48 (m, 4H), 7.31 (m, 4H), 7.19-6.98 (m, 5H), 3.01 (m, 4H), 2.74 (q, 2H), 1.28 (t , 3H); MS m / z 434 (M + )
Figure imgf000020_0002
Figure imgf000020_0002
상기 제조예 1과 동일한 방법으로 제조하되, 화학식 1-1의 브롬염 화합물 및 화학식 1-2의 알테하이드 화합물 대신 각각 (4-부틸 -2,3- 디플루오로벤질)트리페닐포스포니움 브로마이드 및 2， 3-디볼루오로 -4- 메특시벤즈알데하이드를 사용하여 상기 구조의 화합물을 제조하였다.  Prepared in the same manner as in Preparation Example 1, but instead of the bromine salt compound of Formula 1-1 and the aldehyde compound of Formula 1-2, respectively (4-butyl-2,3-difluorobenzyl) triphenylphosphonium bromide And 2, 3-divoluo-4-methoxybenzaldehyde to prepare a compound of the above structure.
¾ NMR (300 腿 z, CDCls) δ 6.98 (m, 3H), 6.73 (t, 1H), 3.98 (m, 3H), 2.91 (m, 4H), 2.63 (t, 2H) 1.45 (m, 4H), 0.91 (t, 3H) ； MS m/z 340 (M+) ¾ NMR (300 腿 z, CDCls) δ 6.98 (m, 3H), 6.73 (t, 1H), 3.98 (m, 3H), 2.91 (m, 4H), 2.63 (t, 2H) 1.45 (m, 4H) , 0.91 (t, 3H); MS m / z 340 (M + )
Figure imgf000020_0003
Figure imgf000020_0003
상기 제조예 2와 동일한 방법으로 제조하되， 화학식 2-1의 브롬염 화합물 대신 트리페닐 (4-프로필벤질)포스포니움 브로마이드를 사용하여， 상기 구조의 화합물을 제조하였다.  Prepared in the same manner as in Preparation Example 2, using triphenyl (4-propylbenzyl) phosphonium bromide instead of the bromine salt compound of Formula 2-1, to prepare a compound of the above structure.
¾ NMR (300 MHz, CDCI3) δ 7.89 (m, 1H), 7.36 (m, 4H) , 7.09 (m, 5H), 4.09 (m, 2H) , 2,82 (m, 4H), 2.61 (t; 2H) 1.65 (m, 2H), 1.35 (t, 3H), 0.91 (t, 3H) ； MS m/z 380 (M+) ¾ NMR (300 MHz, CDCI 3 ) δ 7.89 (m, 1H), 7.36 (m, 4H), 7.09 (m, 5H), 4.09 (m, 2H), 2,82 (m, 4H), 2.61 (t 2H) 1.65 (m, 2H), 1.35 (t, 3H), 0.91 (t, 3H); MS m / z 380 (M + )
Figure imgf000021_0001
Figure imgf000021_0001
상기 제조예 5와 동일한 방법으로 제조하되, 화학식 5-1의 알데하이드 화합물 대신 4-(4-프로필사이클로핵실)벤즈알데하이드를 사용하여 , 상기 구조의 화합물을 제조하였다.  Prepared in the same manner as in Preparation Example 5, but instead of the aldehyde compound of formula 5-1 using 4- (4-propylcyclonucleosil) benzaldehyde to prepare a compound of the structure.
¾ NMR (300 MHz, CDC13) δ 7.85 (m, 1H), 7.40 (m, 4H)， 7.07 (m, 5H), 4.09 (m, 2H), 2,82 (m, 4H), 2.71 (t, 1H) 1.81-1.70 (m, 14H), 1.19 (m, 2H), 0.92 (t, 3H) ； MS m/z 462 (M+) 실험예 1: 액정 화합물의 물성 평가 ¾ NMR (300 MHz, CDC1 3 ) δ 7.85 (m, 1H), 7.40 (m, 4H), 7.07 (m, 5H), 4.09 (m, 2H), 2,82 (m, 4H), 2.71 (t , 1H) 1.81-1.70 (m, 14H), 1.19 (m, 2H), 0.92 (t, 3H); MS m / z 462 (M + ) Experimental Example 1: Evaluation of physical properties of liquid crystal compound
상기 제조예 및 비교 제조예에서 제조한 액정 화합물의 물성을 평가하였다. 구체적으로 액정 화합물의 물성은， 물성을 측정하고자 하는 액정 화합물 10 중량 ¾>와 모액정 90 중량 %를 흔합하여 제조한 시료의 측정값을 하기 식 1에 대입하여 얻은 외삽값으로 규정하였다. 이때， 상기 모액정으로는 투명점 (Tni)이 78°C이고， 굴절률 이방성 [Δη]이 0.10인 것을 사용하였다. The physical properties of the liquid crystal compounds prepared in Preparation Examples and Comparative Preparation Examples were evaluated. Specifically, the physical properties of the liquid crystal compound were defined as an extrapolation value obtained by substituting the measured value of the sample prepared by mixing 10 wt% of the liquid crystal compound to be measured with 90 wt% of the mother liquid crystal. In this case, as the mother liquid crystal, a transparent point Tni of 78 ° C. and an refractive index anisotropy [Δη] of 0.10 were used.
[식 1]  [Equation 1]
외삽값 = [모액정의 측정값] + [{(시료의 측정값) - (모액정의 측정값) } / (액정 화합물의 중량 %) 100] 1) 상전이 온도 (DSC)  Extrapolation = [measured value of mother liquid crystal] + [{(measured value of sample)-(measured value of mother liquid crystal)} / (weight% of liquid crystal compound) 100] 1) Phase transition temperature (DSC)
ΤΑ사의 TA-series 시차주사열량계 (DSC)를 사용하여 질소 하에서 rc/min의 속도로 상온에서 액정 화합물의 Tni + 50°C까지 1 cycle 가열 및 넁각하여 상전이 온도를 관찰하였다. 하기 표 2에서， Cry, Sm, N, ISO는 각각 결정상， 스메틱상, 네마틱상, 이소트로픽상을 의미하며， 각 부호 사이의 온도가 이에 해당하는 상전이 온도를 의미한다 . TA-series differential scanning calorimetry (DSC) of ΤΑ was used to observe the phase transition temperature by heating and concentrating 1 cycle of the liquid crystal compound to Tni + 50 ° C at room temperature at a rate of rc / min under nitrogen. In the following Table 2, Cry, Sm, N, ISO means crystalline phase, Smetic phase, nematic phase, isotropic phase, respectively, The temperature between means the corresponding phase transition temperature.
2) ΔΤηΐ 2) ΔΤηΐ
액정 화합물의 Tni은 편광 현미경을 장치한 융점 측정 장치의 핫 플레이트에 액정 화합물을 놓고 3°C /분의 속도로 가열하여 액정 화합물의 일부가 액정상에서 등방성 액체로 변화했을 때의 온도를 관찰하여 측정하였다. The Tni of the liquid crystal compound is measured by observing the temperature when a liquid crystal compound is placed on a hot plate of a melting point measuring device equipped with a polarization microscope and heated at a rate of 3 ° C./min to change a part of the liquid crystal compound into an isotropic liquid on the liquid crystal phase. It was.
3) 액정 화합물의 굴절를 이방성 ( Δη) 3) Anisotropy in the Refraction of the Liquid Crystal Compound (Δη)
20°C에서 589 nm 파장의 광을 사용하여 접안경에 편광판을 장착한 아베 굴절계로 측정하였다. 주프리즘의 표면을 한 방향으로 러빙한 후， 시료를 주프리즘에 적하하였다. 이후， 편광의 방향이 러빙의 방향과 평행할 때의 굴절률 (n il )과 편광의 방향이 러빙의 방향과 수직일 때의 굴절를 (n丄)을 측정하였다. 그리고, 상기 굴절를 값을 식 2에 대입하여 굴절률 이방성 ( Δη)을 측정하였다. It was measured with an Abbe refractometer equipped with a polarizing plate on the eyepiece using light at a wavelength of 589 nm at 20 ° C. After rubbing the surface of the main prism in one direction, the sample was dropped into the main prism. Then, the refractive index (n il) when the direction of polarization was parallel to the direction of rubbing and the refractive index (n 丄) when the direction of polarization was perpendicular to the direction of rubbing were measured. In addition, the refractive index anisotropy (Δη) was measured by substituting the above value into the equation (2).
[식 2] Equation 2
Δη = η I！ - η丄  Δη = η I！-η 丄
4) 액정 화합물의 유전율 이방성 ( Δ ε ) 4) dielectric anisotropy (Δ ε) of liquid crystal compound
하기와 같이 측정된 ε II 및 ε 丄를 식 3에 대입하여 계산하였다. Ε II and ε 된 measured as follows were calculated by substituting Equation 3.
¾ [식 3] ¾ [Equation 3]
ᅀ ε = ε II - ε 丄  Ε ε = ε II-ε 丄
① 유전율 ε il의 측정 : 2장의 유리 기판의 IT0 패턴이 형성된 면에 수직 배향제를 도포하여 수직 배향막을 형성하였다. 이어서， 수직 배향막이 서로 마주보며 2장의 유리 기판 사이의 간격 (셀 갭 )이 4 가 되도록 2장의 유리 기판 중 어느 하나의 기판에 스페이서를 도포한 후 2장의 유리 기판을 합착시켰다. 그리고， 이 소자에 시료를 주입하고， 자외선으로 경화시키는 ¾착제로 밀폐하였다. 이후， Agi lent에서 제조한 4294A 장비에 사용하여， 이 소자의 20°C에서 유전율 ε II을 측정하였다. ② 유전율 ε丄의 측정: 2장의 유리 기판의 ΠΌ 패턴이 형성된 면에 수평 배향제를 도포하여 수평 배향막을 형성하였다. 이어서， 수평 배향막이 서로 마주보며 2장의 유리 기판 사이의 간격 (셀 갭 )이 4 /皿가 되도록 2장의 유리 기판 중 어느 하나의 기판에 스페이서를 도포한 후 2 장의 유리 기판을 합착시켰다. 그리고， 이 소자에 시료를 주입하고， 자외선으로 경화시키는 접착제로 밀폐하였다. 이후， Agilent에서 제조한 4294A 장비에 사용하여， 이 소자의 20°C에서 유전율 ε丄을 측정하였다. 5) 점도 ① Measurement of dielectric constant epsilon il: The vertical alignment agent was apply | coated to the surface in which the IT0 pattern of two glass substrates was formed, and the vertical alignment film was formed. Subsequently, spacers were applied to any one of the two glass substrates such that the vertical alignment films faced each other and the gap (cell gap) between the two glass substrates was 4, and then the two glass substrates were bonded together. Then, a sample was injected into the device and sealed with a ¾ complex which was cured by ultraviolet rays. Then, using the 4294A equipment manufactured by Agi lent, the dielectric constant ε II at 20 ° C of this device was measured. (2) Measurement of dielectric constant epsilon [epsilon]: The horizontal alignment film was apply | coated to the surface in which the (Ό) pattern of two glass substrates was formed, and the horizontal alignment film was formed. Subsequently, the spacers were applied to any one of the two glass substrates so that the horizontal alignment films faced each other and the gap (cell gap) between the two glass substrates was 4 / mm, and then the two glass substrates were bonded together. Then, a sample was injected into the device and sealed with an adhesive that was cured with ultraviolet rays. Then, using the 4294A equipment manufactured by Agilent, the dielectric constant ε 丄 at 20 ° C of this device was measured. 5) viscosity
점도 측정을 위해 SCHOTT 사의 CT52 장비를 이용하였으며， 이에 2mL의 부피에 대해 점도 측정이 가능한 capillary viscometer를 장착 후 측정하고자 하는 액정 조성물 2 mL를 주빕하였다. 이후， 액정 조성물을 20°C에서 30 분간 안정화시킨 후 스포아드 루버를 사용하여 측정 부위까지 액정 조성물을 끌어 을렸다. 이어서， 액정 조성물이 홀러내리는 속도를 타이머를 통해 측정하고， 이를 통해 점도 (mm2/s)를 구하였다. 상기 결과를 하기 표 2에 나타내었다. SCHOTT CT52 equipment was used for the viscosity measurement, and 2 mL of the liquid crystal composition to be measured after mounting a capillary viscometer capable of measuring the viscosity for a volume of 2 mL. Thereafter, the liquid crystal composition was stabilized at 20 ° C. for 30 minutes, and then the liquid crystal composition was pulled down to the measurement site using a sporad louver. Subsequently, the rate at which the liquid crystal composition fell was measured through a timer, and the viscosity (mm 2 / s) was obtained through the timer. The results are shown in Table 2 below.
【표 2】  Table 2
상전이 온도 (DSC) ΔΤηί ᅀ n ᅀ ε ᄌ도 비교 제조예 1 Heat ing Cry 49.3 I so -89 0.01 -3.5 43.53  Phase Transition Temperature (DSC) ΔΤηί ᅀ n ᅀ ε Degree of Comparison Comparative Preparation Example 1 Heating Cry 49.3 I so -89 0.01 -3.5 43.53
Heating Cry 79.81 N 103.52  Heating Cry 79.81 N 103.52
비교 제조예 2 103.1 0.21 -3.5 - I so  Comparative Preparation Example 2 103.1 0.21 -3.5-I so
Heating Cry 36.96 N 97.35  Heating Cry 36.96 N 97.35
비교 제조예 3 105 0.13 -2.7 - I so  Comparative Preparation Example 3 105 0.13 -2.7-I so
Heat ing Cry 69.1 I so  Heat ing Cry 69.1 I so
제조예 1 -63.2 0.02 -3.1 43.09  Preparation Example 1 -63.2 0.02 -3.1 43.09
Cool ing Cry 55.92 I so  Cool ing Cry 55.92 I so
Heating Cry 76.4 I so  Heating Cry 76.4 I so
제조예 2 14 0.16 -6.3 - Preparation Example 2 14 0.16 -6.3-
Cool ing Cry 64.95 I so Cool ing Cry 64.95 I so
Heat ing Cry 89 I so  Heat ing Cry 89 I so
제조예 3 25 0.15 -5.1 -.  Preparation Example 3 25 0.15 -5.1-.
Cool ing Cry 48.5 I so . Cool ing Cry 48.5 I so .
Heating Cry 130.9 Sm 169.1 N  Heating Cry 130.9 Sm 169.1 N
205.5 I so  205.5 I so
제조예 4 238 0.25 -5.1 ᅳ  Preparation Example 4 238 0.25 -5.1 ᅳ
Cooling Cry 108.6 Sm 166.2 N  Cooling Cry 108.6 Sm 166.2 N
203.3 I so  203.3 I so
Heating Cry 115.6 N 155 I so  Heating Cry 115.6 N 155 I so
제조예 5 109 0.24 -5.1 一  Preparation Example 5 109 0.24 -5.1 一
Cooling Cry 72.0 N 149.9 Iso Heat ing Cry 116.8 Sm 136.4 N Cooling Cry 72.0 N 149.9 Iso Heat ing Cry 116.8 Sm 136.4 N
174.1 I so  174.1 I so
제조예 6 126 0.24 -5.7  Preparation Example 6 126 0.24 -5.7
Cool ing Cry 85.2 Sm 129.2 N  Cool ing Cry 85.2 Sm 129.2 N
171.3 I so  171.3 I so
Heat ing Cry 62.6 I so  Heat ing Cry 62.6 I so
제조예 7 —134.5 0.0221 38.45  Preparation Example 7 —134.5 0.0221 38.45
Cool ing Cry 48.1 I so  Cool ing Cry 48.1 I so
Heat ing Cry 23.7 I so  Heat ing Cry 23.7 I so
제조예 8 -117.9 - 23.18  Preparation Example 8 -117.9-23.18
Cool ing Cry -16.7 Iso  Cool ing Cry -16.7 Iso
상온액체  Room temperature liquid
제조예 9 -47.3 - 19.87 상온액체  Preparation Example 9 -47.3-19.87 Room temperature liquid
Heat ing Cry 62.6 Iso  Heat ing Cry 62.6 Iso
제조예 10 16. 1 0. 1331 30.65  Preparation Example 10 16. 1 0. 1331 30.65
Cool ing Cry 40. 1 Iso  Cool ing Cry 40. 1 Iso
Heat ing Cry 44.1 Iso  Heat ing Cry 44.1 Iso
제조예 11 -21.9 0. 1120 46.83  Preparation 11 -21.9 0. 1120 46.83
Cool ing Cry -12.2 Iso  Cool ing Cry -12.2 Iso
Heat ing Cry 117.82 Iso  Heat ing Cry 117.82 Iso
제조예 12 125.4 0.2324 - 69.75  Preparation 12 125.4 0.2324-69.75
Cool ing Cry 93.9 Iso  Cool ing Cry 93.9 Iso
Heat ing Cry 87.0 Iso  Heat ing Cry 87.0 Iso
제조예 13 Cool ing. Cry 32.8 Sm 43.0 N 86.0 0.2318 55.83  Preparation 13 Cool ing. Cry 32.8 Sm 43.0 N 86.0 0.2318 55.83
82.7 Iso 실험예 2: 액정 조성물의 제조 및 물성 평가  82.7 Iso Experimental Example 2: Preparation of Liquid Crystal Composition and Evaluation of Physical Properties
하기 표 3과 같은 조성을 이용하여 액정 조성물을 제초하였다. 하기 표 3에서 액정 화합물은 코드로 표시하였으며， 코드의 의미는 상기 표 1에 기재되어 있다. 하기 표 3에서 각 수치는 중량 %를 의미한다.  To weed the liquid crystal composition using the composition shown in Table 3. In Table 3, the liquid crystal compound is represented by a code, and the meaning of the code is described in Table 1 above. In the following Table 3, each value means weight%.
【표 3】  Table 3
Figure imgf000024_0001
상기 실시예 및 비교예에서 제조한 액정 조성물을 다음과 같은 방법으로 평가하여 그 결과를 하기 표 4에 나타내었다.
Figure imgf000025_0001
Figure imgf000024_0001
The liquid crystal compositions prepared in Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 4 below.
Figure imgf000025_0001
액정 화합물의 은 편광 현미경을 장치한 융점 측정 장치의 핫 플레이트에 액정 화합물을 놓고， 3°C/분의 속도로 가열하여 액정 화합물의 일부가 액정상에서 등방성 액체로 변화했을 때의 온도를 관찰하여 측정하였다. The liquid crystal compound was placed on a hot plate of a melting point measuring device equipped with a silver polarization microscope of the liquid crystal compound, and heated at a rate of 3 ° C./min to observe the temperature when a part of the liquid crystal compound changed to an isotropic liquid on the liquid crystal phase. It was.
2) 액정 조성물의 굴절를 이방성 (Δη), nil 및 n丄의 측정 방법은 앞서 실험예 1과 동일하였다. 2) The method of measuring the anisotropy (Δη), nil, and n 丄 of the refraction of the liquid crystal composition was the same as in Experimental Example 1.
3) 액정 조성물의 유전율 이방성 (Δ ε )의 측정 방법은 앞서 실험예 1과 동일하였다. 3) The measuring method of dielectric anisotropy (Δε) of the liquid crystal composition was the same as in Experimental Example 1.
【표 4】
Figure imgf000025_0002
Table 4
Figure imgf000025_0002

Claims

【특허청구범위】 【Patent Claims】
【청구항 1】 【Claim 1】
하기 화학식 1로 표시되는 액정 화합물: Liquid crystal compound represented by the following formula (1):
Figure imgf000026_0001
Figure imgf000026_0001
상기 식에서， In the above equation,
Li , L2 , L3 및 L4는 각각 독립적으로 수소 또는 할로겐이고， Li, L 2 , L 3 and L 4 are each independently hydrogen or halogen,
R은 수소， d-10 알킬， C2-10 알케닐 또는 Cwo 알콕시이고， 및 nl 및 n2는 각각 독립적으로 0 내지 2의 정수이고， nl 및 n2의 합은 0 이상 2 이하이다. R is hydrogen, d- 10 alkyl, C2-10 alkenyl, or Cwo alkoxy, and nl and n2 are each independently an integer of 0 to 2, and the sum of nl and n2 is 0 or more and 2 or less.
【청구항 2】 【Claim 2】
게 1항에 있어서， In paragraph 1,
Li , , 및 L4는 각각 독립적으로 수소 또는 플루오로인， ' 액정 화합물 . Li, , and L 4 are each independently hydrogen or fluorine, ' liquid crystal compound.
【청구항 3] [Claim 3]
제 2항에 있어서， In paragraph 2,
및 L2가 동일한， and L 2 are the same,
액정 화합물. Liquid crystal compound.
【청구항 4】 【Claim 4】
제 2항에 있어서， In paragraph 2,
및 가 동일한， and are the same,
액정 화합물. Liquid crystal compound.
【청구항 5] [Claim 5]
거 U항에 있어서 R은 수소， 메틸， 에틸, 메록시 또는 에록시인， In Port U R is hydrogen, methyl, ethyl, meroxy or eroxy,
액정 화합물 . Liquid crystal compound.
【청구항 6】 【Claim 6】
제 1항에 있어서， In clause 1,
상기 액정 화합물은 하기 화합물로 구성되는 군으로부터 선택되는 어느 하나인， The liquid crystal compound is any one selected from the group consisting of the following compounds,
Figure imgf000027_0001
【청구항.
Figure imgf000027_0001
【Claim.
7】 7】
제 1항 내지 제 6항 중 어느 한 항의 액정 화합물을 1종 이상 포함하는， 액정 조성물. A liquid crystal composition comprising at least one liquid crystal compound according to any one of claims 1 to 6.
【청구항 8】 【Claim 8】
제 7항에 있어서， In clause 7,
상기 액정 화합물은 상기 액정 조성물 전체 중량 대비 3 내지 60 증량 %로 포함되는， The liquid crystal compound is contained in an increase of 3 to 60% based on the total weight of the liquid crystal composition,
액정 조성물. Liquid crystal composition.
【청구항 9】 【Claim 9】
게 7항에 있어서， In paragraph 7,
하기 화학식 2 내지 5로 이루어진 군에서 선택되는 하나 이상의 액정 화합물을 추가로 포함하는， Further comprising one or more liquid crystal compounds selected from the group consisting of the following formulas 2 to 5,
액정 조성물: Liquid crystal composition:
[화학식 2] [Formula 2]
Rn-A3-A4-R12 R n -A 3 -A 4 -R 12
상기 화학식 2에서， In Formula 2,
R11 및 R12는 각각 독립적으로 수소， 탄소수 1 내지 15의 알킬 및 탄소수 1 내지 15의 알콕시 중 어느 하나의 라디칼이거나， 혹은 상기 라디칼 중 하나 이상의 -c¾-가 산소 원자들이 직접 연결되지 않도록 -c≡c -， R 11 and R 12 are each independently hydrogen, an alkyl group having 1 to 15 carbon atoms, and an alkoxy group having 1 to 15 carbon atoms, or at least one -c¾- of the radicals is -c so that the oxygen atoms are not directly connected. ≡c-，
-CH=CH- , -CF20- , -0- , -COO- 또는 -0C0-로 치환되거나 또는 상기 라디칼 중 하나 이상의 H가 할로겐으로 대체된 라디칼이고， -CH=CH-, -CF 2 0-, -0-, -COO- or -0C0-, or one or more H of the radicals is a radical replaced by halogen,
A3 및 A4는 각각 독립적으로 사이클로핵실렌 또는 페닐렌이고， A 3 and A 4 are each independently cyclohexylene or phenylene,
[화학식 3] [Formula 3]
R13_A5_ (A6 ) p_A7_R14 상기 화학식 3에서， R 13_ A 5_ (A 6 ) p _ A 7_ R 14 In Formula 3,
R13 및 R14는 각각 독립적으로 수소， 탄소수 1 내지 15의 알킬 및 탄소수 1 내지 15의 알콕시 중 어느 하나의 라디칼이거나， 혹은 상기 라디칼 중 하나 이상의 -CH2-가 산소 원자들이 직접 연결되지 않도록 -C≡C -， -CH=CH-, -CF20-, -0-, -COO- 또는 -0C0-로 치환되거나 또는 상기 라디칼 중 하나 이상의 H가 할로겐으로 대체된 라디칼이고, R 13 and R 14 are each independently a radical of hydrogen, alkyl with 1 to 15 carbon atoms, and alkoxy with 1 to 15 carbon atoms, or -CH 2 - of one or more of the radicals is - so that the oxygen atoms are not directly connected. C≡C -， -CH=CH-, -CF 2 0-, -0-, -COO- or -0C0- or a radical in which at least one H of the radicals is replaced by halogen,
A5 및 A7은 각각 독립적으로사이클로핵실렌 또는 페닐렌이며， A 5 and A 7 are each independently cyclohexylene or phenylene,
A6은 사이클로핵실렌, 페닐렌 또는 할로겐으로 치환된 페닐렌이고， p는 1 또는 2의 정수이고， A 6 is cyclohexylene, phenylene, or phenylene substituted with halogen, p is an integer of 1 or 2,
Figure imgf000029_0001
Figure imgf000029_0001
상기 화학식 4에서， In Formula 4 above,
R15 및 R16은 각각 독립적으로 수소， 탄소수 1 내지 15의 알킬 및 탄소수 1 내지 15의 알콕시 증 어느 하나의 라디칼이거나， 혹은 상기 라디칼 중 하나 이상의 -CH2-가 산소 원자들이 직접 연결되지 않도록 -C≡C-, -CH=CH-, -CF20-t ᅳ0-， -C00- 또는 -0C0—로 치환되거나 또는 상기 라디칼 중 하나 이상의 H가 할로겐으로 대체된 라디칼아고， R 15 and R 16 are each independently a radical of hydrogen, alkyl of 1 to 15 carbon atoms, and alkoxyl group of 1 to 15 carbon atoms, or -CH 2 - of one or more of the radicals is - so that the oxygen atoms are not directly connected. C≡C-, -CH=CH-, -CF 2 0- t ᅳ0-, -C00- or -0C0—, or a radical in which one or more H of the radicals is replaced by halogen,
A8 및 A9는 각각 독립적으로 사이클로핵실렌， 테트라하이드로피라닐렌， 페닐렌 또는 할로겐으로 치환된 페닐렌이며， A 8 and A 9 are each independently cyclohexylene, tetrahydropyranylene, phenylene, or phenylene substituted with halogen,
q는 0 내지 2 사이의 정수이고， q is an integer between 0 and 2,
[화학식 5] [Formula 5]
Figure imgf000029_0002
Figure imgf000029_0002
상기 화학식 5에서, In Formula 5 above,
R17 및 R18은 각각 독립적으로 수소， 탄소수 1 내지 15의 알킬 및 탄소수 1 내지 15의 알콕시 중 어느 하나의 라디칼이거나， 혹은 상기 라디칼 중 하나 이상의 — C¾-가 산소 원자들이 직접 연결되지 않도록 -c≡c-, -CH=CH-, -CF20-, -0-， -C00- 또는 -0C0-로 치환되거나 또는 상기 라디칼 중 하나 이상의 H가 할로겐으로 대체된 라디칼이며， R 17 and R 18 are each independently a radical of hydrogen, alkyl with 1 to 15 carbon atoms, and alkoxy with 1 to 15 carbon atoms, or one or more of the radicals — C¾- is -c so that the oxygen atoms are not directly connected. ≡c-, -CH=CH-, -CF 2 0-, -0-, -C00- or -0C0-, or one or more H of the radicals is substituted with halogen,
A10, A11 및 A12는 각각 독립적으로 사이클로핵실렌， 테트라하이드로피라닐렌, 페닐렌 및 할로겐으로 치환된 페닐렌 중 어느 하나이고， A 10 , A 11 and A 12 are each independently any one of cyclohexylene, tetrahydropyranylene, phenylene and phenylene substituted with halogen,
Z4 및 Z5는 각각 독립적으로 -CH2C¾-, -CH=CH-, -C≡C-, -C¾0—， - 0CH2-, -CH2CF2-, -CHFCHF-, -CF2CH2-, -CH2CHF-, -CHFCH2-, — C2F4-, -C00-, - 0C0- , -CF20- , -0CF2- 또는 -0-이며， Z 4 and Z 5 are each independently -CH 2 C¾-, -CH=CH-, -C≡C-, -C¾0—， - 0CH 2 -, -CH 2 CF 2 -, -CHFCHF-, -CF 2 CH 2 -, -CH 2 CHF-, -CHFCH 2 -, — C 2 F 4 -, -C00-, - 0C0-, -CF 2 0-, -0CF 2 - or -0-,
r 및 v는 0 또는 1이고， r + v는 1 또는 2이며， r and v are 0 or 1, r + v is 1 or 2,
s 및 w는 0 내지 2 사이의 정수이다. s and w are integers between 0 and 2.
【청구항 10】 【Claim 10】
제 7항에 있어서， In clause 7,
상기 액정 조성물은 산화 방지제 또는 UV 안정화제를 추가로 포함하는， The liquid crystal composition further contains an antioxidant or UV stabilizer,
액정 조성물. Liquid crystal composition.
【청구항 11】 【Claim 11】
제 7항의 액정 조성물을 포함하는， 액정 표시 소자. A liquid crystal display device comprising the liquid crystal composition of claim 7.
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