JP2011213787A - Liquid crystal composition with reduced impurity content - Google Patents
Liquid crystal composition with reduced impurity content Download PDFInfo
- Publication number
- JP2011213787A JP2011213787A JP2010081246A JP2010081246A JP2011213787A JP 2011213787 A JP2011213787 A JP 2011213787A JP 2010081246 A JP2010081246 A JP 2010081246A JP 2010081246 A JP2010081246 A JP 2010081246A JP 2011213787 A JP2011213787 A JP 2011213787A
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- Japan
- Prior art keywords
- group
- liquid crystal
- general formula
- crystal composition
- formula
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 127
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 109
- 239000012535 impurity Substances 0.000 title abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 117
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 44
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- -1 naphthalene compound Chemical class 0.000 claims abstract description 31
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 13
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims abstract description 13
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims abstract description 12
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 12
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims abstract description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 49
- 229910052801 chlorine Inorganic materials 0.000 claims description 37
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 35
- 238000001514 detection method Methods 0.000 claims description 33
- 125000003342 alkenyl group Chemical group 0.000 claims description 13
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 11
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 10
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 63
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 30
- 230000006866 deterioration Effects 0.000 abstract description 9
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 238000001953 recrystallisation Methods 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 150000002790 naphthalenes Chemical class 0.000 description 11
- 0 CC1CCC(C*(c(cc(ccc(*)c2II)c2c2F)c2F)=C)CC1 Chemical compound CC1CCC(C*(c(cc(ccc(*)c2II)c2c2F)c2F)=C)CC1 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000001939 inductive effect Effects 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DKWBHFPTCMHAEG-UHFFFAOYSA-N 2-(3,4-difluorophenyl)-1-fluoro-6-propylnaphthalene Chemical compound C1=CC2=CC(CCC)=CC=C2C(F)=C1C1=CC=C(F)C(F)=C1 DKWBHFPTCMHAEG-UHFFFAOYSA-N 0.000 description 2
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- WALWCNCXTHJRCW-ZWGSZDQZSA-N C(CC)[C@@H]1CC[C@H](CC1)CC[C@@H]1CC[C@H](CC1)COC=1C(=C(C2=C(C(=CC=C2C1)OCCC)F)F)F Chemical compound C(CC)[C@@H]1CC[C@H](CC1)CC[C@@H]1CC[C@H](CC1)COC=1C(=C(C2=C(C(=CC=C2C1)OCCC)F)F)F WALWCNCXTHJRCW-ZWGSZDQZSA-N 0.000 description 2
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- GOTAHZOPIWLFOQ-UHFFFAOYSA-N CCC(CC1)CCC1C1CCCCC1 Chemical compound CCC(CC1)CCC1C1CCCCC1 GOTAHZOPIWLFOQ-UHFFFAOYSA-N 0.000 description 2
- UFKHLGZVXUHRJG-UHFFFAOYSA-N CCCC1=CC2=C(C=C1)C(=C(C=C2)C3=CC(=C(C=C3)F)F)Cl Chemical compound CCCC1=CC2=C(C=C1)C(=C(C=C2)C3=CC(=C(C=C3)F)F)Cl UFKHLGZVXUHRJG-UHFFFAOYSA-N 0.000 description 2
- OSYHAVOYLWXGAF-QAQDUYKDSA-N CCCCC[C@H]1CC[C@H](COC(C(F)=C(C2=C3Cl)F)=CC2=CC=C3OCC)CC1 Chemical compound CCCCC[C@H]1CC[C@H](COC(C(F)=C(C2=C3Cl)F)=CC2=CC=C3OCC)CC1 OSYHAVOYLWXGAF-QAQDUYKDSA-N 0.000 description 2
- BTRSQGCFGKKJDA-IYARVYRRSA-N CCCCC[C@H]1CC[C@H](COC(C(F)=C(C2=C3Cl)F)=CC2=CC=C3OCCC)CC1 Chemical compound CCCCC[C@H]1CC[C@H](COC(C(F)=C(C2=C3Cl)F)=CC2=CC=C3OCCC)CC1 BTRSQGCFGKKJDA-IYARVYRRSA-N 0.000 description 2
- WTJYFOBQCORKAF-WKILWMFISA-N CCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1C(C=C1C=C2F)=CC=C1C(Cl)=C2F Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1C(C=C1C=C2F)=CC=C1C(Cl)=C2F WTJYFOBQCORKAF-WKILWMFISA-N 0.000 description 2
- IDLYGPNLBKJNCA-WKILWMFISA-N CCC[C@H](CC1)CC[C@@H]1C(C=C1C=C2)=CC=C1C(Cl)=C2C(C=C1F)=CC(F)=C1F Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C1C=C2)=CC=C1C(Cl)=C2C(C=C1F)=CC(F)=C1F IDLYGPNLBKJNCA-WKILWMFISA-N 0.000 description 2
- TZFSCBMGBRQNRS-KBQPQWKXSA-N CCC[C@H]1CC[C@H](CC[C@H]2CC[C@H](COC(C(F)=C(C3=C4Cl)F)=CC3=CC=C4OCC)CC2)CC1 Chemical compound CCC[C@H]1CC[C@H](CC[C@H]2CC[C@H](COC(C(F)=C(C3=C4Cl)F)=CC3=CC=C4OCC)CC2)CC1 TZFSCBMGBRQNRS-KBQPQWKXSA-N 0.000 description 2
- GXBVDBIWXAEKPD-ZWGSZDQZSA-N CCC[C@H]1CC[C@H](CC[C@H]2CC[C@H](COC(C(F)=C(C3=C4Cl)F)=CC3=CC=C4OCCC)CC2)CC1 Chemical compound CCC[C@H]1CC[C@H](CC[C@H]2CC[C@H](COC(C(F)=C(C3=C4Cl)F)=CC3=CC=C4OCCC)CC2)CC1 GXBVDBIWXAEKPD-ZWGSZDQZSA-N 0.000 description 2
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- SBZXMMQKZHBHOD-UHFFFAOYSA-N ClC1=C(C=CC2=CC(=CC=C12)CCC)C1=CC(=C(C(=C1)F)F)F Chemical compound ClC1=C(C=CC2=CC(=CC=C12)CCC)C1=CC(=C(C(=C1)F)F)F SBZXMMQKZHBHOD-UHFFFAOYSA-N 0.000 description 2
- RNXKKVXTWQQIAH-QAQDUYKDSA-N ClC=1C(=CC=C2C=C(C(=C(C12)F)F)OC[C@@H]1CC[C@H](CC1)CCC)OCCCC Chemical compound ClC=1C(=CC=C2C=C(C(=C(C12)F)F)OC[C@@H]1CC[C@H](CC1)CCC)OCCCC RNXKKVXTWQQIAH-QAQDUYKDSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000005264 electron capture Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 230000004044 response Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ABJSOROVZZKJGI-OCYUSGCXSA-N (1r,2r,4r)-2-(4-bromophenyl)-n-[(4-chlorophenyl)-(2-fluoropyridin-4-yl)methyl]-4-morpholin-4-ylcyclohexane-1-carboxamide Chemical compound C1=NC(F)=CC(C(NC(=O)[C@H]2[C@@H](C[C@@H](CC2)N2CCOCC2)C=2C=CC(Br)=CC=2)C=2C=CC(Cl)=CC=2)=C1 ABJSOROVZZKJGI-OCYUSGCXSA-N 0.000 description 1
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 description 1
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- CRNZDXXICRYJLA-UHFFFAOYSA-N 1,2,8-trifluoro-7-propoxynaphthalene Chemical compound C1=CC(F)=C(F)C2=C(F)C(OCCC)=CC=C21 CRNZDXXICRYJLA-UHFFFAOYSA-N 0.000 description 1
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- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
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- CBXGVGSJJIJMHL-UHFFFAOYSA-N 1-fluoro-6-propyl-2-(3,4,5-trifluorophenyl)naphthalene Chemical compound C1=CC2=CC(CCC)=CC=C2C(F)=C1C1=CC(F)=C(F)C(F)=C1 CBXGVGSJJIJMHL-UHFFFAOYSA-N 0.000 description 1
- NPRYCHLHHVWLQZ-TURQNECASA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynylpurin-8-one Chemical compound NC1=NC=C2N(C(N(C2=N1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C NPRYCHLHHVWLQZ-TURQNECASA-N 0.000 description 1
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- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000062 cyclohexylmethoxy group Chemical group [H]C([H])(O*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Abstract
Description
液晶組成物の信頼性の低下を惹き起こすナフタレン化合物の塩素置換体の含有量を減少させた液晶組成物の提供及びこれを構成する高信頼性組成物及び液晶表示素子更にその組成物の精製法に関する。 Providing a liquid crystal composition in which the content of a chlorine-substituted naphthalene compound causing a decrease in the reliability of the liquid crystal composition is reduced, a highly reliable composition constituting the same, a liquid crystal display device, and a method for purifying the composition About.
液晶表示素子は液晶テレビ、携帯電話やパソコンなどをはじめとする民生用途から産業用途まで広く使用されており、その生産高はブラウン管を凌駕するまでになってきた。これに伴い、液晶表示素子に対する要求特性は多様かつ高度なものとなってきている。例えば動画をスムーズに表示させるための高速応答化や優れた表示特性を実現する高コントラスト化等がある。これら表示特性は製品寿命に至るまで保持する必要があり、液晶表示素子が経時的な劣化を惹き起こさないことも求められている。このため液晶表示素子に使用される液晶組成物に対しても、長期にわたり品質の劣化を惹き起こさないことが必要となっている。 Liquid crystal display elements are widely used from consumer applications such as liquid crystal televisions, mobile phones and personal computers to industrial applications, and their production has surpassed CRTs. As a result, the required characteristics for liquid crystal display elements have become diverse and sophisticated. For example, there are high-speed response for displaying a moving image smoothly and high contrast for realizing excellent display characteristics. These display characteristics must be maintained until the end of the product life, and the liquid crystal display element is also required not to cause deterioration over time. For this reason, it is necessary that the liquid crystal composition used in the liquid crystal display element does not cause deterioration of quality over a long period of time.
液晶組成物の品質を向上させるために、これまでに多くの研究がなされてきた。例えば、液晶組成物を構成する液晶化合物中の水分や金属イオンを除去する方法として、液晶化合物をシリカゲルと接触させる方法（特許文献１参照）、活性アルミナと接触させる方法（特許文献２参照）、イオン交換樹脂で処理する方法（特許文献３参照）、ゼオライトと接触させる方法（特許文献４参照）が開示されている。更に、対向する一対の電極間に液晶化合物を入れ、電界をかけることにより、電界による移動度の比較的大きなＮａ＋、Ｋ＋等の金属イオンや、ＳＯ４ ２−、ＮＯ３ −、Ｃｌ−等のイオン性不純物を除去する方法等（特許文献５〜７参照）が開示されている。 Many studies have been made so far in order to improve the quality of the liquid crystal composition. For example, as a method for removing moisture and metal ions in the liquid crystal compound constituting the liquid crystal composition, a method of bringing the liquid crystal compound into contact with silica gel (see Patent Document 1), a method of bringing into contact with activated alumina (see Patent Document 2), A method of treating with an ion exchange resin (see Patent Document 3) and a method of contacting with zeolite (see Patent Document 4) are disclosed. Furthermore, by putting a liquid crystal compound between a pair of electrodes facing each other and applying an electric field, metal ions such as Na + and K + having a relatively high mobility due to the electric field, SO 4 2− , NO 3 − , Cl − and the like can be used. Methods for removing ionic impurities and the like (see Patent Documents 5 to 7) are disclosed.
しかし、上記精製法により除去される不純物はそれ自体が、液晶組成物の電圧保持率等を低下させる原因物質であり、液晶化合物と大きく構造が異なるものである。これらの成分を除去した液晶組成物は、除去した直後こそ電圧保持率や比抵抗値が向上するものの、経時的な劣化は進行していくことがわかった。このため、長期にわたり、品質の劣化を起こさない液晶組成物の提供が求められるようになった。 However, the impurities removed by the above purification method are themselves causative substances that lower the voltage holding ratio of the liquid crystal composition, and are greatly different in structure from the liquid crystal compounds. It has been found that the liquid crystal composition from which these components have been removed is improved with time, although the voltage holding ratio and specific resistance value are improved immediately after the removal. For this reason, provision of the liquid crystal composition which does not cause deterioration of quality over a long period of time has been demanded.
高速応答化や高コントラスト化を可能とする液晶組成物として、ナフタレン誘導体を含む液晶組成物が開発されている。例えば、Δεが正の化合物として式（III−１）を含む液晶組成物（特許文献８参照）やΔεが負の化合物として式（IV−１）を含む液晶組成物（特許文献９参照）が開示されている。 A liquid crystal composition containing a naphthalene derivative has been developed as a liquid crystal composition enabling high-speed response and high contrast. For example, a liquid crystal composition containing Formula (III-1) as a compound with positive Δε (see Patent Document 8) or a liquid crystal composition containing Formula (IV-1) as a compound with negative Δε (see Patent Document 9). It is disclosed.
しかしこれらの化合物は製造の際に、反応条件や使用する反応剤の純度、更に製造装置の洗浄の状況によって、未知の不純物成分が生成することがあり、これによって電圧保持率や比抵抗値の低下が起こり、表示不良等が生じることがあった。従来は、未知の不純物についての言及が行われていなかったため、有効な精製方法等が確立できず、高度化した液晶組成物に対する高信頼性の要求に応えることが困難となっていた。 However, when these compounds are produced, unknown impurity components may be produced depending on the reaction conditions, the purity of the reactants used, and the cleaning conditions of the production equipment. Decrease occurred and display defect etc. may occur. Conventionally, since there has been no mention of unknown impurities, an effective purification method or the like cannot be established, and it has been difficult to meet the demand for high reliability for advanced liquid crystal compositions.
長期に渡り高い電圧保持率及び高い比抵抗値を保つ液晶組成物及び液晶表示素子を提供することであり、これを達成するために不純物であるナフタレン化合物の塩素置換体の含有量を低下させた組成物及びその精製法を提供することである。 The object is to provide a liquid crystal composition and a liquid crystal display device that maintain a high voltage holding ratio and a high specific resistance value over a long period of time, and in order to achieve this, the content of the chlorine substitution product of the naphthalene compound as an impurity is reduced. It is to provide a composition and a method for its purification.
液晶組成物の経時劣化の原因を鋭意調査したところ、化学的に不安定であり液晶材料と構造が近似する不純物が液晶組成物に含まれている場合に、バックライトの発する紫外線や熱に曝されることにより経時分解が進行することがわかった。具体的には、式（III−１）や式（IV−１）を合成する際に、式（III−２）や式（IV−２）、（ＩＶ−３） When the cause of deterioration of the liquid crystal composition over time has been intensively investigated, when the liquid crystal composition contains impurities that are chemically unstable and have a structure similar to that of the liquid crystal material, the liquid crystal composition is exposed to ultraviolet rays or heat emitted from the backlight. As a result, it was found that the degradation over time progressed. Specifically, when synthesizing Formula (III-1) or Formula (IV-1), Formula (III-2), Formula (IV-2), or (IV-3)
で表される化合物を不純物として数百ｐｐｍから数％副生することがあることが明らかとなった。ナフタレン上の塩素原子がフッ素原子に比べ脱離能が高く、化学的に不安定であることから、紫外線照射や加熱によりこれらの化合物から塩素原子が脱離してしまう。不純物としてこれらの化合物を含まない純粋な式（III−１）や式（IV−１）のみであればフッ素原子の脱離能は低いため、これらを含む液晶表示素子の経時的な表示不良等は起こらない。しかし式（III−２）や式（IV−２）を含む液晶組成物を使用した液晶表示素子は経時的な式（III−２）や式（IV−２）からの塩素原子の脱離により液晶組成物中のイオン成分が増加し、電圧保持率や比抵抗値の低下が起こり、表示不良等が生じてしまうことが明らかとなった。 It has been clarified that the compound represented by the formula may be by-produced from several hundred ppm to several percent as impurities. Since the chlorine atom on naphthalene has higher desorption ability than the fluorine atom and is chemically unstable, the chlorine atom is desorbed from these compounds by ultraviolet irradiation or heating. If only pure formula (III-1) or formula (IV-1) that does not contain these compounds as impurities is present, the ability to remove fluorine atoms is low. Does not happen. However, a liquid crystal display device using a liquid crystal composition containing the formula (III-2) or the formula (IV-2) is caused by the detachment of chlorine atoms from the formula (III-2) or the formula (IV-2) over time. It has been clarified that the ionic component in the liquid crystal composition is increased, the voltage holding ratio and the specific resistance value are lowered, and display defects are caused.
これらの知見より、特定の化合物を除去した液晶組成物を提供することにより、液晶組成物の品質を飛躍的に向上できることを見出し、本発明を完成するに至った。 Based on these findings, it has been found that the quality of a liquid crystal composition can be dramatically improved by providing a liquid crystal composition from which a specific compound is removed, and the present invention has been completed.
本願は一般式（Ｉ） The present application relates to the general formula (I)
(式中、Ｒ１及びＲ２はそれぞれ独立的にフッ素原子、ジフルオロメトキシ基、トリフルオロメトキシ基、トリフルオロメチル基、炭素原子数１から７の直鎖状アルキル基、炭素原子数１から７の直鎖状アルコキシル基、炭素原子数２から７の直鎖状アルケニル基又は炭素原子数２から７の直鎖状アルケニルオキシ基を表し、１個又は２個以上の炭素原子が−Ｏ−、−Ｃ＝Ｃ−又は−Ｃ≡Ｃ−により置き換えられても良く、１個又は２個以上の水素原子がフッ素原子、フッ素化されていても良いアルキル基、フッ素化されていても良いアルコキシル基により置き換えられても良く、分子内に不斉炭素原子を持つ場合にはラセミ体であっても光学活性体であっても良い。Ａ及びＢはそれぞれ独立的にトランス−１，４−シクロへキシレン基、１，４−シクロヘキセニレン基、１，４−ビシクロ［２．２．２］オクチレン基、１，４−フェニレン基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基を表し、これら基中に含まれる１個又は２個以上の水素原子はフッ素原子により置き換えられても良く、これら基中に存在する１個又は２個以上の−ＣＨ２−は−Ｏ−により置き換えられても良く、Ｚ１及びＺ２はそれぞれ独立的に単結合、−ＣＨ２ＣＨ２−、−（ＣＨ２）４−、−ＣＨＣＨ３ＣＨ２−、−ＣＨ２ＣＨＣＨ３−、−ＣＨＣＨ３Ｏ−、−ＯＣＨＣＨ３−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、−ＣＦ２ＣＦ２−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表し、Ｘ１、Ｘ２、Ｘ３、Ｘ４、Ｘ５及びＸ６はそれぞれ独立的に水素原子、フッ素原子、トリフルオロメトキシ基、ジフルオロメトキシ基又はトリフルオロメチル基を表し、ｍ及びｎはそれぞれ独立的に０、１、２又は３を表すが、ｍ及び／又はｎが２又は３を表す場合において２個あるいは３個存在するＡ、Ｂ、Ｚ１及び／又はＺ２は同一であっても異なっていても良い。)で表される化合物を１種又は２種以上含有し、更に一般式（Ｉ）で表される化合物においてＸ１、Ｘ２、Ｘ３、Ｘ４、Ｘ５、Ｘ６、ｍが０を表す場合のＲ１、ｎが０を表す場合のＲ２が、フッ素原子を表す場合に、そのうち少なくとも１個以上のフッ素原子が塩素原子に置換した一般式（ＩＩ） (Wherein R 1 and R 2 are each independently a fluorine atom, a difluoromethoxy group, a trifluoromethoxy group, a trifluoromethyl group, a linear alkyl group having 1 to 7 carbon atoms, or a carbon atom having 1 to 7 carbon atoms). A straight-chain alkoxyl group, a straight-chain alkenyl group having 2 to 7 carbon atoms or a straight-chain alkenyloxy group having 2 to 7 carbon atoms, wherein one or two or more carbon atoms are -O-, -C = C- or -C≡C- may be substituted, one or two or more hydrogen atoms may be fluorine atoms, fluorinated alkyl groups, fluorinated alkoxyl groups In the case where the molecule has an asymmetric carbon atom, it may be a racemate or an optically active substance, and A and B are each independently trans-1,4-cyclo Xylene group, 1 4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, 1,4-phenylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1 , 2,3,4-tetrahydronaphthalene-2,6-diyl group, and one or more hydrogen atoms contained in these groups may be replaced by fluorine atoms, and exist in these groups One or more of —CH 2 — may be replaced by —O—, and Z 1 and Z 2 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, -CHCH 3 CH 2 -, - CH 2 CHCH 3 -, - CHCH 3 O -, - OCHCH 3 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O -, - CF 2 CF 2 -, - CF = CF- Represents -CH = CH- or -C≡C-, X 1, X 2, X 3, X 4, X 5 and X 6 are each independently a hydrogen atom, a fluorine atom, a trifluoromethoxy group, difluoromethoxy group Or a trifluoromethyl group, and m and n each independently represent 0, 1, 2 or 3, but when m and / or n represents 2 or 3, 2 or 3 A, B , Z 1 and / or Z 2 may be the same or different.) 1 or 2 or more kinds of compounds represented by formula (I), and X 1 in the compound represented by formula (I) , X 2 , X 3 , X 4 , X 5 , X 6 , R 1 when m represents 0, and R 2 when n represents 0, when R 2 represents a fluorine atom, at least one of them General formula (II) in which a fluorine atom is replaced by a chlorine atom
（式中、Ａ、Ｂ、ｍ、ｎ、Ｚ１及びＺ２は一般式（Ｉ）において選択したＡ、Ｂ、ｍ、ｎ、Ｚ１及びＺ２と同一のものを表し、Ｒ１１はｍが０を表す場合一般式（Ｉ）において選択したＲ１と同一のもの又は塩素原子を表し、ｍが１、２又は３を表す場合一般式（Ｉ）において選択したＲ１と同一のものを表し、Ｒ１２はｍが０を表す場合一般式（Ｉ）において選択したＲ２と同一のもの又は塩素原子を表し、ｍが１、２又は３を表す場合一般式（Ｉ）において選択したＲ１と同一のものを表し、Ｘ１１は一般式（Ｉ）において選択したＸ１と同一のもの又は塩素原子を表し、Ｘ１２は一般式（Ｉ）において選択したＸ２と同一のもの又は塩素原子を表し、Ｘ１３は一般式（Ｉ）において選択したＸ３と同一のもの又は塩素原子を表し、Ｘ１４は一般式（Ｉ）において選択したＸ４と同一のもの又は塩素原子を表し、Ｘ１５は一般式（Ｉ）において選択したＸ５と同一のもの又は塩素原子を表し、Ｘ１６は一般式（Ｉ）において選択したＸ６と同一のもの又は塩素原子を表すが、Ｒ１１、Ｒ１２、Ｘ１１、Ｘ１２、Ｘ１３、Ｘ１４、Ｘ１５及びＸ１６のうち１個又は２個以上は塩素原子を表す。）で表される化合物を１種又は２種以上含有し、１種含有する場合にはその含有量が一般式（ＩＩ）で表される化合物の検出下限値が液晶組成物中１ｐｐｍ以下である測定手段における検出下限値未満から５ｐｐｍの間であり、一般式（ＩＩ）で表される化合物を２種以上含有する場合にはその各々の含有量の合計が一般式（ＩＩ）で表される化合物の検出下限値が液晶組成物中１ｐｐｍ以下である測定手段における検出下限値未満から５ｐｐｍの間であることを特徴とする液晶組成物を提供する。 (Expressed in the formula, A, B, m, n , Z 1 and Z 2 A selected in the general formula (I), B, m, n, a the same as Z 1 and Z 2, R 11 is m When R represents 0, it represents the same R 1 selected in general formula (I) or a chlorine atom, and when m represents 1, 2 or 3, the same as R 1 selected in general formula (I) R 12 represents the same as R 2 selected in general formula (I) or a chlorine atom when m represents 0, or R selected in general formula (I) when m represents 1, 2 or 3 represents one same as, X 11 is formula represents X 1 elements the same as or chlorine atom selected in (I), X 12 is the general formula (I) same or chlorine and X 2 selected in X 13 is the same as X 3 selected in formula (I) or a chlorine atom X 14 represents the same or a chlorine atom as X 4 selected in the general formula (I), X 15 represents the same or a chlorine atom as X 5 selected in the general formula (I), and X 16 Represents the same as X 6 selected in the general formula (I) or a chlorine atom, but one of R 11 , R 12 , X 11 , X 12 , X 13 , X 14 , X 15 and X 16 or 2 or more represents a chlorine atom.) One or two or more compounds represented by the formula (II) are contained, and in the case of containing one compound, the lower limit of detection of the compound represented by the general formula (II) Is less than the lower limit of detection in the measuring means of 1 ppm or less in the liquid crystal composition to 5 ppm, and when two or more compounds represented by the general formula (II) are contained, the total of the respective contents is Detection lower limit of the compound represented by the general formula (II) There is provided a liquid crystal composition characterized in that between 5ppm from less than detection limit in the measurement means is less than 1ppm in the liquid crystal composition.
本発明の化学的に不安定な不純物の含有量を減少させた組成物を提供することにより、これを含有する液晶組成物の経時的な品質の低下が抑えられ、製品寿命に至るまで初期の表示特性から劣化が生じない液晶表示素子の製造が可能となった点において有用である。 By providing a composition having a reduced content of chemically unstable impurities according to the present invention, the deterioration of the quality of the liquid crystal composition containing the same over time can be suppressed, and the initial life until the product lifetime is reached. This is useful in that a liquid crystal display element that does not deteriorate from display characteristics can be manufactured.
以下に本発明について詳細に説明する。 The present invention is described in detail below.
一般式（Ｉ）及び（ＩＩＩ）で表される化合物は、公知の化合物であり、当業者が容易に入手することができる。一般式（ＩＩ）で表される化合物は一般式（Ｉ）で表される化合物の製造の際に不可避的に生じる化合物であり、一般式（Ｉ）で表される化合物のナフタレン骨格へフッ素原子を導入する際にフッ素原子ではなく塩素原子が導入された化合物又は、製造工程中でフッ素原子が塩素原子に置換してしまった化合物である。 The compounds represented by the general formulas (I) and (III) are known compounds and can be easily obtained by those skilled in the art. The compound represented by the general formula (II) is a compound inevitably generated in the production of the compound represented by the general formula (I), and a fluorine atom is added to the naphthalene skeleton of the compound represented by the general formula (I). Is a compound in which a chlorine atom is introduced instead of a fluorine atom, or a compound in which a fluorine atom is substituted with a chlorine atom during the production process.
製造工程において、一般式（Ｉ）で表される化合物は反応終了後には一般式（ＩＩ）で表される化合物を１種又は２種以上含んだ組成物となっている。一般式（Ｉ）で表される化合物は１度に１種のみを製造することもできるし、２種を同時に製造することもできる。また、１種の一般式（Ｉ）で表される化合物を合成する際に不純物として他の一般式（Ｉ）で表される化合物を含有することもある。 In the production process, the compound represented by the general formula (I) is a composition containing one or more compounds represented by the general formula (II) after completion of the reaction. Only one compound represented by the general formula (I) can be produced at a time, or two can be produced simultaneously. Moreover, when synthesizing one compound represented by the general formula (I), the compound represented by another general formula (I) may be contained as an impurity.
一般式（Ｉ）で表される化合物は、誘電率異方性が正のいわゆるｐ型液晶材料（概ね１より大きい）であっても、誘電率異方性が負のいわゆるｎ型液晶材料（概ね−１より小さい）であっても、誘電率異方性がほぼ０である液晶材料（概ね−１から１）であってもよい。 Even if the compound represented by the general formula (I) is a so-called p-type liquid crystal material having a positive dielectric anisotropy (approximately larger than 1), a so-called n-type liquid crystal material having a negative dielectric anisotropy ( It may be a liquid crystal material (generally −1 to 1) having a dielectric anisotropy of substantially 0.
ｎ型液晶材料としてはＸ１、Ｘ２及びＸ３は少なくとも２個以上がフッ素原子が好ましく、３個ともフッ素原子がより好ましい。Ｒ１及びＲ２は炭素原子数１から７の直鎖状アルキル基、炭素原子数１から７の直鎖状アルコキシル基、炭素原子数２から７の直鎖状アルケニル基又は炭素原子数２から７の直鎖状アルケニルオキシ基が好ましい。Ａ及びＢは１個又は２個以上の水素原子はフッ素原子により置き換えられても良いトランス−１，４−シクロへキシレン基、１，４−フェニレン基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基を表す化合物が好ましく、トランス−１，４−シクロへキシレン基、１個又は２個以上の水素原子はフッ素原子により置き換えられても良い１，４−フェニレン基が更に好ましい。Ｚ１及びＺ２は単結合、−ＣＨ２ＣＨ２−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、−ＣＦ２ＣＦ２−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−が好ましく、単結合、−ＣＨ２ＣＨ２−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−又は−ＣＦ２Ｏ−が更に好ましい。ｍ＋ｎは１、２又は３が好ましく、１又は２が更に好ましい。ｍ及び／又はｎが２又は３を表す場合において２個あるいは３個存在するＡ、Ｂ、Ｚ１及び／又はＺ２は同一であっても異なっていても良い。 As the n-type liquid crystal material, at least two of X 1 , X 2 and X 3 are preferably fluorine atoms, and all three are more preferably fluorine atoms. R 1 and R 2 are each a linear alkyl group having 1 to 7 carbon atoms, a linear alkoxyl group having 1 to 7 carbon atoms, a linear alkenyl group having 2 to 7 carbon atoms, or 2 carbon atoms. 7 linear alkenyloxy groups are preferred. A and B are trans-1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-2,6-diyl group, deca, wherein one or more hydrogen atoms may be replaced by fluorine atoms. A compound representing a hydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is preferred, a trans-1,4-cyclohexylene group, one or more The hydrogen atom is more preferably a 1,4-phenylene group which may be replaced by a fluorine atom. Z 1 and Z 2 are a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —CF 2 CF 2 —, —CF═CF—. , —CH═CH— or —C≡C— is preferable, and a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 — or —CF 2 O— is more preferable. m + n is preferably 1, 2 or 3, more preferably 1 or 2. When m and / or n represents 2 or 3, two or three A, B, Z 1 and / or Z 2 may be the same or different.
ｐ型液晶材料としてはＲ１及びＲ２はフッ素原子、ジフルオロメトキシ基、トリフルオロメトキシ基、トリフルオロメチル基、炭素原子数１から７の直鎖状アルキル基、炭素原子数１から７の直鎖状アルコキシル基、炭素原子数２から７の直鎖状アルケニル基又は炭素原子数２から７の直鎖状アルケニルオキシ基が好ましく、Ｒ１は炭素原子数１から７の直鎖状アルキル基、炭素原子数１から７の直鎖状アルコキシル基、炭素原子数２から７の直鎖状アルケニル基又は炭素原子数２から７の直鎖状アルケニルオキシ基が更に好ましく、
炭素原子数１から５の直鎖状アルキル基、炭素原子数１から５の直鎖状アルコキシル基、炭素原子数２から５の直鎖状アルケニル基又は炭素原子数２から５の直鎖状アルケニルオキシ基が更に好ましく、Ｒ２はフッ素原子、ジフルオロメトキシ基、トリフルオロメトキシ基、トリフルオロメチル基が更に好ましい。Ａ及びＢは１個又は２個以上の水素原子はフッ素原子により置き換えられても良いトランス−１，４−シクロへキシレン基、１，４−フェニレン基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基を表す化合物が好ましく、トランス−１，４−シクロへキシレン基、１個又は２個以上の水素原子はフッ素原子により置き換えられても良い１，４−フェニレン基が更に好ましい。Ｚ１及びＺ２は単結合、−ＣＨ２ＣＨ２−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、−ＣＦ２ＣＦ２−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−が好ましく、単結合、−ＣＨ２ＣＨ２−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｏ−又は−Ｃ≡Ｃ−が更に好ましい。Ｘ１、Ｘ２又はＸ６はフッ素原子、トリフルオロメトキシ基、ジフルオロメトキシ基又はトリフルオロメチル基が好ましく、Ｘ１、Ｘ２又はＸ６はフッ素原子が更に好ましく、Ｘ３、Ｘ４又はＸ５は水素原子が好ましい。ｍ＋ｎは１、２又は３が好ましく、１又は２が更に好ましい。ｍ及び／又はｎが２及び３を表す場合において２個あるいは３個存在するＡ、Ｂ、Ｚ１及び／又はＺ２は同一であっても異なっていても良い。
As p-type liquid crystal materials, R 1 and R 2 are fluorine atom, difluoromethoxy group, trifluoromethoxy group, trifluoromethyl group, linear alkyl group having 1 to 7 carbon atoms, straight chain having 1 to 7 carbon atoms. A linear alkoxyl group, a linear alkenyl group having 2 to 7 carbon atoms or a linear alkenyloxy group having 2 to 7 carbon atoms is preferable, and R 1 is a linear alkyl group having 1 to 7 carbon atoms, More preferably a linear alkoxyl group having 1 to 7 carbon atoms, a linear alkenyl group having 2 to 7 carbon atoms or a linear alkenyloxy group having 2 to 7 carbon atoms,
A linear alkyl group having 1 to 5 carbon atoms, a linear alkoxyl group having 1 to 5 carbon atoms, a linear alkenyl group having 2 to 5 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms An oxy group is more preferable, and R 2 is more preferably a fluorine atom, a difluoromethoxy group, a trifluoromethoxy group, or a trifluoromethyl group. A and B are trans-1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-2,6-diyl group, deca, wherein one or more hydrogen atoms may be replaced by fluorine atoms. A compound representing a hydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is preferred, a trans-1,4-cyclohexylene group, one or more The hydrogen atom is more preferably a 1,4-phenylene group which may be replaced by a fluorine atom. Z 1 and Z 2 are a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —CF 2 CF 2 —, —CF═CF—. , —CH═CH— or —C≡C— is preferable, a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— or —C≡. C- is more preferable. X 1 , X 2 or X 6 is preferably a fluorine atom, a trifluoromethoxy group, a difluoromethoxy group or a trifluoromethyl group, and X 1 , X 2 or X 6 is more preferably a fluorine atom, and X 3 , X 4 or X 5 is preferably a hydrogen atom. m + n is preferably 1, 2 or 3, more preferably 1 or 2. In the case where m and / or n represents 2 and 3, two or three A, B, Z 1 and / or Z 2 may be the same or different.
誘電率異方性がほぼ０である液晶材料としては、Ｒ１及びＲ２は炭素原子数１から７の直鎖状アルキル基、炭素原子数１から７の直鎖状アルコキシル基、炭素原子数２から７の直鎖状アルケニル基又は炭素原子数２から７の直鎖状アルケニルオキシ基が好ましく、炭素原子数１から５の直鎖状アルキル基、炭素原子数１から５の直鎖状アルコキシル基、炭素原子数２から５の直鎖状アルケニル基又は炭素原子数２から５の直鎖状アルケニルオキシ基が更に好ましい。Ａ及びＢはトランス−１，４−シクロへキシレン基又は１個又は２個以上の水素原子がフッ素原子により置き換えられても良い１，４−フェニレン基が好ましく、トランス−１，４−シクロへキシレン基又は１，４−フェニレン基が更に好ましい。Ｚ１及びＺ２は単結合、−ＣＨ２ＣＨ２−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、−ＣＦ２ＣＦ２−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−が好ましく、単結合、−ＣＨ２ＣＨ２−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、又は−Ｃ≡Ｃ−が更に好ましい。Ｘ１、Ｘ２、Ｘ３、Ｘ４、Ｘ５及びＸ６は水素原子又はフッ素原子が好ましく、そのうち４個以上が水素原子であることが更に好ましく、そのうち５個以上が水素原子であることが更に好ましく、すべてが水素原子であることが更に好ましい。ｍ＋ｎは１、２又は３が好ましく、１又は２が更に好ましい。ｍ及び／又はｎが２又は３を表す場合において２個あるいは３個存在するＡ、Ｂ、Ｚ１及び／又はＺ２は同一であっても異なっていても良い。 As the liquid crystal material having a dielectric anisotropy of almost 0, R 1 and R 2 are linear alkyl groups having 1 to 7 carbon atoms, linear alkoxyl groups having 1 to 7 carbon atoms, carbon atoms A linear alkenyl group having 2 to 7 carbon atoms or a linear alkenyloxy group having 2 to 7 carbon atoms is preferable, a linear alkyl group having 1 to 5 carbon atoms, or a linear alkoxyl group having 1 to 5 carbon atoms. More preferably a straight-chain alkenyl group having 2 to 5 carbon atoms or a straight-chain alkenyloxy group having 2 to 5 carbon atoms. A and B are preferably a trans-1,4-cyclohexylene group or a 1,4-phenylene group in which one or two or more hydrogen atoms may be replaced by a fluorine atom. A xylene group or a 1,4-phenylene group is more preferable. Z 1 and Z 2 are a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —CF 2 CF 2 —, —CF═CF—. , —CH═CH— or —C≡C— is preferred, and a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, or —C ≡C- is more preferable. X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are preferably hydrogen atoms or fluorine atoms, more preferably 4 or more of which are hydrogen atoms, and 5 or more of which are hydrogen atoms. Are more preferable, and all are more preferably hydrogen atoms. m + n is preferably 1, 2 or 3, more preferably 1 or 2. When m and / or n represents 2 or 3, two or three A, B, Z 1 and / or Z 2 may be the same or different.
一般式（ＩＩＩ）で表される化合物としては、R３及びＲ４は１個又は２個以上の−ＣＨ２−はそれぞれ独立して酸素原子が相互に直接結合しないものとして−Ｏ−により置き換えられても良い炭素数１〜１５のアルキル基又は炭素数２〜１５のアルケニル基が好ましく、炭素原子数１から７の直鎖状アルキル基、炭素原子数１から７の直鎖状アルコキシル基、炭素原子数２から７の直鎖状アルケニル基又は炭素原子数２から７の直鎖状アルケニルオキシ基が更に好ましく、炭素原子数１から５の直鎖状アルキル基、炭素原子数１から５の直鎖状アルコキシル基、炭素原子数２から５の直鎖状アルケニル基又は炭素原子数２から５の直鎖状アルケニルオキシ基が更に好ましい。Ｃは１個又は２個以上の水素原子がフッ素原子により置き換えられても良いトランス−１，４−シクロへキシレン基、１，４−フェニレン基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基及び１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基が好ましく、トランス−１，４−シクロへキシレン基、１，４−フェニレン基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基又は１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基が更に好ましく、トランス−１，４−シクロへキシレン基、１，４−フェニレン基、ナフタレン−２，６−ジイル基又はデカヒドロナフタレン−２，６−ジイル基が更に好ましく、トランス−１，４−シクロへキシレン基及び１，４−フェニレン基が更に好ましい。Ｚ３は単結合、−ＣＨ２ＣＨ２−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、−ＣＦ２ＣＦ２−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−が好ましく、単結合、−ＣＨ２ＣＨ２−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−が更に好ましく、単結合、−ＣＨ２ＣＨ２−又は−Ｃ≡Ｃ−が更に好ましい。ｐは２、３又は４が好ましく、ｐが２、３又は４を表す場合において２、３又は４個存在するＣ及び／又はＺ３は同一であっても異なっていても良い。 In the compound represented by the general formula (III), R 3 and R 4 are each replaced by —O— in which one or two or more —CH 2 — are each independently an oxygen atom not directly bonded to each other. An alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms which may be used, a linear alkyl group having 1 to 7 carbon atoms, a linear alkoxyl group having 1 to 7 carbon atoms, A straight chain alkenyl group having 2 to 7 carbon atoms or a straight chain alkenyloxy group having 2 to 7 carbon atoms is more preferable, a straight chain alkyl group having 1 to 5 carbon atoms, or a straight chain alkenyloxy group having 1 to 5 carbon atoms. A linear alkoxyl group, a linear alkenyl group having 2 to 5 carbon atoms, or a linear alkenyloxy group having 2 to 5 carbon atoms is more preferable. C is a trans-1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-2,6-diyl group, decahydronaphthalene, in which one or more hydrogen atoms may be replaced by fluorine atoms -2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-2,6-diyl group are preferable, trans-1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-2, A 6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is more preferred, a trans-1,4-cyclohexylene group, 4-phenylene group, naphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group is more preferred, and trans-1,4-cyclohexylene group and 1,4- Eniren group are more preferable. Z 3 is a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, —CF 2 CF 2 —, —CF═CF—, —CH ═CH— or —C≡C— is preferred, a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH— or —C≡C— is more preferred, and a single bond , —CH 2 CH 2 — or —C≡C— is more preferable. p is preferably 2, 3 or 4, and when p represents 2, 3 or 4, 2, 3 or 4 C and / or Z 3 may be the same or different.
一般式（ＩＩ）で表される化合物は組成物又は液晶組成物中に含有すると経時的に分解し、その電圧保持率や比抵抗値を低下させる。このような品質劣化を抑制するためには組成物又は液晶組成物中に含まれる一般式（ＩＩ）で表される化合物の含有量を制御する必要がある。一般式（Ｉ）で表される化合物を製造すると、一般式（ＩＩ）で表される化合物を含有する組成物として得られる。このため、液晶組成物への一般式（Ｉ）で表される化合物の添加量を多くすれば一般式（ＩＩ）で表される化合物の混入量も多くなる。液晶組成物中の一般式（ＩＩ）で表される化合物は１種である場合もあるし、２種以上である場合もある。 When the compound represented by the general formula (II) is contained in the composition or the liquid crystal composition, it is decomposed over time, and its voltage holding ratio and specific resistance value are lowered. In order to suppress such quality deterioration, it is necessary to control the content of the compound represented by the general formula (II) contained in the composition or the liquid crystal composition. When the compound represented by general formula (I) is manufactured, it is obtained as a composition containing the compound represented by general formula (II). For this reason, if the addition amount of the compound represented by the general formula (I) to the liquid crystal composition is increased, the amount of the compound represented by the general formula (II) is also increased. The compound represented by the general formula (II) in the liquid crystal composition may be one type, or may be two or more types.
１種である場合はその含有量は５ｐｐｍ以下であることが好ましい。この値が２ｐｐｍ以下であると更に好ましい。液晶組成物中に一般式（ＩＩ）の化合物を全く含有しないことが最も好ましいが、用いる測定手段の検出下限値を下回る含有量は確認できないため、充分に低い検出下限値を持った分析手段における検出下限値未満であることが最も好ましい。このため液晶組成物中に含まれる一般式（ＩＩ）で表される化合物の含有量を測定する手段の検出下限値は１ｐｐｍ以下であることが好ましく、３００ｐｐｂ以下であると更に好ましく、１００ｐｐｂ以下であると更に好ましい。 In the case of one type, the content is preferably 5 ppm or less. This value is more preferably 2 ppm or less. It is most preferable that the liquid crystal composition does not contain the compound of the general formula (II) at all, but since the content below the lower limit of detection of the measuring means used cannot be confirmed, in the analytical means having a sufficiently low detection lower limit Most preferably, it is less than the lower limit of detection. For this reason, it is preferable that the detection lower limit of the means for measuring the content of the compound represented by the general formula (II) contained in the liquid crystal composition is 1 ppm or less, more preferably 300 ppb or less, and 100 ppb or less. More preferably.
２種以上である場合はその含有量の合計が５ｐｐｍ以下であることが好ましい。２ｐｐｍ以下であると更に好ましい。液晶組成物中に一般式（ＩＩ）の化合物を全く含有しないことが最も好ましいが、用いる測定手段の検出下限値を下回る含有量は確認できないため、充分に低い検出下限値を持った分析手段における検出下限値未満であることが最も好ましい。このため液晶組成物中に含まれる一般式（ＩＩ）で表される化合物の含有量を測定する手段の検出下限値は１ｐｐｍ以下であることが好ましく、３００ｐｐｂ以下であると更に好ましく、１００ｐｐｂ以下であると更に好ましい。 In the case of 2 or more types, the total content is preferably 5 ppm or less. More preferably, it is 2 ppm or less. It is most preferable that the liquid crystal composition does not contain the compound of the general formula (II) at all, but since the content below the lower limit of detection of the measuring means used cannot be confirmed, in the analytical means having a sufficiently low detection lower limit Most preferably, it is less than the lower limit of detection. For this reason, it is preferable that the detection lower limit of the means for measuring the content of the compound represented by the general formula (II) contained in the liquid crystal composition is 1 ppm or less, more preferably 300 ppb or less, and 100 ppb or less. More preferably.
液晶組成物中に存在する一般式（ＩＩ）で表される化合物の含有量に関しては上記のとおりであるが、これらは一般式（Ｉ）とともに液晶組成物中に持ち込まれる。よって一般式（Ｉ）に含まれる一般式（ＩＩ）で表される化合物の量が少ない方が好ましい。液晶組成物を構成する成分として一般式（Ｉ）で表される化合物の含有量がａ質量％であれば、液晶組成物中に持ち込まれる一般式（ＩＩ）で表される化合物の量は一般式（Ｉ）で表される化合物中に含まれる量にａ／１００を掛けた値となる。よって、一般式（Ｉ）で表される化合物中に含まれる一般式（ＩＩ）で表される化合物の量の好ましい値は、液晶組成物中に含まれる一般式（ＩＩ）で表される化合物の量の好ましい値をａ／１００で割った値となる。つまり、５÷（ａ／１００）ｐｐｍ以下であることが好ましい。２÷（ａ／１００）ｐｐｍ以下であると更に好ましい。組成物又は液晶組成物中に一般式（ＩＩ）の化合物を全く含有しないことが最も好ましいが、用いる測定手段の検出下限値を下回る含有量は確認できないため、充分に低い検出下限値を持った分析手段における検出下限値未満であることが最も好ましい。このため液晶組成物中に含まれる一般式（ＩＩ）で表される化合物の含有量を測定する手段の検出下限値は１ｐｐｍ以下であることが好ましく、３００ｐｐｂ以下であると更に好ましく、１００ｐｐｂ以下であると更に好ましい。 The content of the compound represented by the general formula (II) present in the liquid crystal composition is as described above, and these are brought into the liquid crystal composition together with the general formula (I). Therefore, it is preferable that the amount of the compound represented by the general formula (II) contained in the general formula (I) is small. If the content of the compound represented by the general formula (I) as a component constituting the liquid crystal composition is a mass%, the amount of the compound represented by the general formula (II) brought into the liquid crystal composition is generally This is a value obtained by multiplying the amount contained in the compound represented by the formula (I) by a / 100. Therefore, a preferable value of the amount of the compound represented by the general formula (II) contained in the compound represented by the general formula (I) is a compound represented by the general formula (II) contained in the liquid crystal composition. The preferred value of the amount is divided by a / 100. That is, it is preferably 5 ÷ (a / 100) ppm or less. More preferably, it is 2 ÷ (a / 100) ppm or less. Most preferably, the composition or liquid crystal composition does not contain the compound of the general formula (II) at all, but since the content below the lower limit of detection of the measuring means used cannot be confirmed, it has a sufficiently low lower limit of detection. Most preferably, it is less than the lower limit of detection in the analysis means. For this reason, it is preferable that the detection lower limit of the means for measuring the content of the compound represented by the general formula (II) contained in the liquid crystal composition is 1 ppm or less, more preferably 300 ppb or less, and 100 ppb or less. More preferably.
一般式（Ｉ）で表される化合物を製造する際に一般式（ＩＩ）で表される化合物は不可避的に生成してしまう。合成反応終了時で数百ｐｐｍから数%ほど含有している。一般式（ＩＩ）で表される化合物は一般式（Ｉ）で表される化合物と構造が極めて似ているため、この含有量を確認しながら以下に示すような精製を行わなければ一般式（Ｉ）で表される化合物に少量含まれる一般式（ＩＩ）で表される化合物を除去することは困難である。 When the compound represented by the general formula (I) is produced, the compound represented by the general formula (II) is inevitably produced. Contained from several hundred ppm to several percent at the end of the synthesis reaction. Since the compound represented by the general formula (II) is very similar in structure to the compound represented by the general formula (I), the general formula ( It is difficult to remove the compound represented by the general formula (II) contained in a small amount in the compound represented by I).
ここで、液晶材料の信頼性を向上させるため、液晶材料は精製を繰り返し行っている。精製した液晶材料の信頼性を比抵抗等の値がある基準値に到達しているかで確認している。この基準値を満たしたものを合格品として使用する。しかし、この判定を物理的な基準値のみで判定を行っていると、不合格品は再度すべての精製工程を繰り返し行わざるを得ない。精製工程を繰り返すと、液晶材料は目減りしてしまうため、結果重量単位あたりの価格が上昇することとなってしまう。これに対し、信頼性を低下させる化合物がわかっていれば、その化合物を重点的に減少させる精製処理が可能となり、効率的な製造が可能となる。また。信頼性の測定にはサンプルを抜き出し、特殊な器具を使用しなければならず、測定中は製造工程を中断させる必要がある。これに対し、問題となる化合物が特定されているとガスクロマトグラフィーや液体クロマトグラフィー等による測定で液晶材料の簡易的な判定が可能となり、製造工程の時間短縮が可能となる。 Here, in order to improve the reliability of the liquid crystal material, the liquid crystal material is repeatedly purified. The reliability of the purified liquid crystal material is confirmed by checking whether the specific resistance value has reached a certain reference value. Those satisfying this standard value are used as acceptable products. However, if this determination is made based only on the physical reference value, the rejected product has to repeat all the purification steps again. If the refining process is repeated, the liquid crystal material is reduced, resulting in an increase in price per unit of weight. On the other hand, if a compound that lowers the reliability is known, a purification treatment that reduces the compound in a focused manner becomes possible, and efficient production becomes possible. Also. To measure reliability, a sample must be extracted and a special instrument must be used, and the manufacturing process must be interrupted during the measurement. On the other hand, if the compound in question is specified, the liquid crystal material can be easily determined by measurement using gas chromatography, liquid chromatography, or the like, and the manufacturing process time can be shortened.
一般式（ＩＩ）で表される化合物の除去は液晶組成物を調製前であっても調製後であってもよい。また、一般式（ＩＩ）で表される化合物として除去してもよいし、化学的に塩素原子を他の原子に置換した後に除去してもよい。また、一般式（Ｉ）で表される化合物の製造方法を検討し、製造時に生じる一般式（ＩＩ）で表される化合物の生成量を減少させてもよいし、製造の中間体を精製し対応する化合物を中間体の段階であらかじめ除去しておいてもよい。またこれらの方法を単独で行ってもよいし、適宜組み合わせてもよい。液晶組成物若しくは一般式（Ｉ）で表される化合物から一般式（ＩＩ）で表される化合物を除去する方法、一般式（ＩＩ）で表される化合物を化学的に変換した後の除去方法又は中間体段階での精製方法としては、カラムクロマトグラフィーによる精製、蒸留、再結晶、吸着剤による吸着除去、昇華、分離膜による精製、透析又は電気透析が好ましく、カラムクロマトグラフィーによる精製、蒸留又は再結晶が更に好ましい。それぞれの精製において、一般式（Ｉ）で表される化合物及び一般式（ＩＩ）で表される化合物及びその他の成分はそのまま精製してもよいし、溶媒に溶解して精製してもよい。溶媒としては炭化水素系の溶媒、エーテル系の溶媒、エステル系の溶媒等を単独又は混合物として使用することができる。また、吸着剤としては活性炭、活性炭素繊維、分子ふるい炭素、シリカゲル、アルミナ又はゼオライト等を使用することができる。塩素原子の化学的な置換方法としては、塩素原子を水素原子に誘導する方法、水酸基に誘導する方法、ニトロ基に誘導する方法、シアノ基に誘導する方法又はアミノ基に誘導する方法が好ましく、水素原子に誘導する方法が更に好ましい。水素原子にする方法としては、水素化リチウムアルミニウム等に代表される水素化金属還元剤やパラジウム等の金属触媒を使用した水素添加により可能である。 Removal of the compound represented by the general formula (II) may be before or after preparing the liquid crystal composition. Further, it may be removed as a compound represented by the general formula (II), or may be removed after chemically substituting the chlorine atom with another atom. In addition, the production method of the compound represented by the general formula (I) may be examined to reduce the amount of the compound represented by the general formula (II) generated during the production, or the production intermediate may be purified. The corresponding compound may be previously removed at the intermediate stage. Moreover, these methods may be performed independently and may be combined suitably. Method for removing compound represented by general formula (II) from liquid crystal composition or compound represented by general formula (I), Method for removing chemical compound represented by general formula (II) Alternatively, the purification method at the intermediate stage is preferably purification by column chromatography, distillation, recrystallization, adsorption removal by adsorbent, sublimation, purification by separation membrane, dialysis or electrodialysis, and purification by column chromatography, distillation or Recrystallization is more preferred. In each purification, the compound represented by the general formula (I), the compound represented by the general formula (II) and other components may be purified as they are, or may be purified by dissolving in a solvent. As the solvent, hydrocarbon solvents, ether solvents, ester solvents and the like can be used alone or as a mixture. As the adsorbent, activated carbon, activated carbon fiber, molecular sieve carbon, silica gel, alumina, zeolite, or the like can be used. As the chemical substitution method of the chlorine atom, a method of inducing a chlorine atom to a hydrogen atom, a method of inducing a hydroxyl group, a method of inducing a nitro group, a method of inducing a cyano group, or a method of inducing an amino group are preferable A method of deriving to a hydrogen atom is more preferable. The hydrogen atom can be formed by hydrogenation using a metal hydride reducing agent typified by lithium aluminum hydride or the like or a metal catalyst such as palladium.
一般式（ＩＩ）で表される化合物の含有量を測定する手段としては、ガスクロマトグラフィーにより試料を分離した後、水素炎イオン化検出器、又は電子捕獲型検出器、又は原子発光検出器、又は質量分析計により検出する手段、あるいは液体クロマトグラフィーにより試料を分離した後、屈折率検出器、又は紫外・可視吸光度検出器、又は蛍光検出器、又は蒸発光散乱検出器、又は電気化学検出器、又は荷電化粒子検出器、又は質量分析計により検出する手段、あるいは試料を分離せずに誘導結合プラズマ−発光分光、又は誘導結合プラズマ−質量分析計、又は蛍光Ｘ線にて塩素として検出する手段、さらには液体クロマトグラフィーと誘導結合プラズマ−発光分光、又は液体クロマトグラフィーと誘導結合プラズマ−質量分析計を組み合わせて検出する手段が好ましい。これらのうちガスクロマトグラフィー、又は液体クロマトグラフィーにより試料を分離した後、種々の検出器で検出する手段が、共存物の影響を排除して一般式（ＩＩ）で表される化合物の含有量を正しく測定できるため更に好ましい。このうちガスクロマトグラフィーにより試料を分離した後、水素炎イオン化検出器、又は電子捕獲型検出器、又は原子発光検出器、又は質量分析計により検出する手段、あるいは液体クロマトグラフィーにより試料を分離した後、紫外・可視吸光度検出器、又は蛍光検出器、又は電気化学検出器、又は荷電化粒子検出器、又は質量分析計、又は誘導結合プラズマ−質量分析計で検出する手段は一般式（ＩＩ）で表される化合物を高感度で検出できるため更に好ましい。中でもガスクロマトグラフィーにより試料を分離した後質量分析計で分析する手段、あるいは液体クロマトグラフィーにより試料を分離した後質量分析計で分析する手段は高感度である上に、一般式（ＩＩ）で表される化合物の構造を確認できるため最も好ましい。 As a means for measuring the content of the compound represented by the general formula (II), after separating a sample by gas chromatography, a flame ionization detector, an electron capture detector, an atomic emission detector, or After the sample is separated by means of mass spectrometry, or by liquid chromatography, a refractive index detector, an ultraviolet / visible absorbance detector, a fluorescence detector, an evaporative light scattering detector, or an electrochemical detector, Or means for detecting by charged particle detector or mass spectrometer, or means for detecting as chlorine by inductively coupled plasma-emission spectroscopy, inductively coupled plasma-mass spectrometer, or fluorescent X-ray without separating the sample In addition, liquid chromatography and inductively coupled plasma-emission spectroscopy, or liquid chromatography and inductively coupled plasma-mass spectrometer are combined. It means for detecting by are preferred. Among these, after separating the sample by gas chromatography or liquid chromatography, the means for detection by various detectors eliminates the influence of coexisting substances and reduces the content of the compound represented by the general formula (II). It is more preferable because it can be measured correctly. After separating the sample by gas chromatography, after separating the sample by flame ionization detector, electron capture detector, atomic emission detector, means for detection by mass spectrometer, or liquid chromatography , UV / visible absorbance detector, fluorescence detector, electrochemical detector, charged particle detector, mass spectrometer, or inductively coupled plasma-mass spectrometer means of general formula (II) The compound represented is more preferable because it can be detected with high sensitivity. Among them, the means for analyzing with a mass spectrometer after separating a sample by gas chromatography or the means for analyzing with a mass spectrometer after separating a sample by liquid chromatography is highly sensitive and is represented by the general formula (II). This is most preferable because the structure of the compound can be confirmed.
本発明の液晶組成物では、不純物である一般式（ＩＩ）で表される化合物の含有量が少ないほど好ましいため、この含有量を検出下限値未満とするのが最も好ましいが、用いる測定手段の検出下限値が充分に低くなければその意味がない。本発明で言う検出下限値とはシグナル／ノイズ比が３倍となる含有量のことである。そこで本発明において液晶組成物中の一般式（ＩＩ）で表される化合物の含有量を求めるにあたっては、検出下限値が液晶組成物中１ｐｐｍ以下となる測定手段を用いることが好ましく、検出下限値が液晶組成物中１００ｐｐｂ以下となる測定手段を用いることが更に好ましく、検出下限値が液晶組成物中１０ｐｐｂ以下となる測定手段を用いることが更に好ましく、検出下限値が液晶組成物中１ｐｐｂ以下となる測定手段を用いることが更に好ましい。このような検出下限値は例えばガスクロマトグラフィー質量分析計でスプリットレス注入を行い、選択イオン検出法を用いることで達成できるし、液体クロマトグラフィー質量分析計で大気圧化学イオン化法又は大気圧光イオン化法を用いることでも達成できる。 In the liquid crystal composition of the present invention, since the content of the compound represented by the general formula (II) which is an impurity is preferably as small as possible, it is most preferable to set this content below the lower limit of detection. If the lower limit of detection is not low enough, it is meaningless. The detection lower limit referred to in the present invention is the content at which the signal / noise ratio is tripled. Therefore, in obtaining the content of the compound represented by the general formula (II) in the liquid crystal composition in the present invention, it is preferable to use a measuring means having a detection lower limit value of 1 ppm or less in the liquid crystal composition. It is more preferable to use a measuring means in which the liquid crystal composition is 100 ppb or less, more preferably a measuring means in which the detection lower limit is 10 ppb or less in the liquid crystal composition, and the detection lower limit is 1 ppb or less in the liquid crystal composition. It is more preferable to use the measurement means. Such a lower limit of detection can be achieved, for example, by performing splitless injection with a gas chromatography mass spectrometer and using a selected ion detection method, or with atmospheric pressure chemical ionization or atmospheric pressure photoionization with a liquid chromatography mass spectrometer. It can also be achieved by using the method.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。化合物の構造は、核磁気共鳴スペクトル(NMR)、質量スペクトル(MS)等により確認した。なお含有量を表す「％」は「質量％」を意味する。不純物の含有量はガスクロマトグラフィーにより確認した。ガスクロマトグラフィーは、ｐ−キシレンに１０％の濃度となるよう試料を溶解させてガスクロマトグラフに注入し、気化させた後ポリジメチルシロキサンを液相とするキャピラリーカラムで分離して水素炎イオン化検出器、あるいは質量分析計で検出することで分析した。 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), mass spectrum (MS) and the like. “%” Representing the content means “% by mass”. Impurity content was confirmed by gas chromatography. In gas chromatography, a sample is dissolved in p-xylene so as to have a concentration of 10%, injected into a gas chromatograph, vaporized and then separated by a capillary column using polydimethylsiloxane as a liquid phase, and a flame ionization detector, Or it analyzed by detecting with a mass spectrometer.
液晶組成物の評価は以下の項目について行った。
ＴN-I：ネマチック相−等方相液体相転移温度（℃）を液晶相上限温度として評価。
Ｔ→N：固体相またはスメクチック相−ネマチック相転移温度（℃）を液晶相下限温度として評価。
Δｎ：２５℃における屈折率異方性。
η：２０℃における粘性（ｍＰａ・ｓ）。
ＶＨＲ：７０℃における電圧保持率（％）。
（セル厚３．５μｍのセルに液晶組成物を注入し、５Ｖ印加、フレームタイム２００ｍｓ、パルス幅６４μｓの条件で測定した時の測定電圧と初期印加電圧との比を％で表した値）
耐ＵＶ性試験：上記ＶＨＲ測定用セルに液晶組成物を注入し、ウシオ電機製スポットキュアＳＰ７にて３６５ｎｍにおける照射量が３Ｊ／ｃｍ２のＵＶ光を照射し、照射前後のＶＨＲを測定。
The liquid crystal composition was evaluated for the following items.
T NI : Nematic phase-isotropic liquid phase transition temperature (° C.) is evaluated as a liquid crystal phase upper limit temperature.
T → N : Evaluation as a liquid crystal phase lower limit temperature using a solid phase or smectic phase-nematic phase transition temperature (° C.).
Δn: refractive index anisotropy at 25 ° C.
η: Viscosity at 20 ° C. (mPa · s).
VHR: Voltage holding ratio (%) at 70 ° C.
(The ratio of the measured voltage to the initial applied voltage in% when the liquid crystal composition was injected into a cell having a cell thickness of 3.5 μm and measured under the conditions of 5 V applied, frame time 200 ms, and pulse width 64 μs)
UV resistance test: A liquid crystal composition was injected into the above VHR measurement cell, and irradiated with UV light having an irradiation amount of 3 J / cm 2 at 365 nm by Spot Cure SP7 manufactured by Ushio Electric Co., Ltd., and VHR before and after irradiation was measured.
（精製例１） １−フルオロ−２−（３，４−ジフルオロフェニル）−６−プロピルナフタレン（化合物１）の精製 (Purification Example 1) Purification of 1-fluoro-2- (3,4-difluorophenyl) -6-propylnaphthalene (Compound 1)
ヘキサン４００ｍＬに、０．０１７％の１−クロロ−２−（３，４−ジフルオロフェニル）−６−プロピルナフタレンを含有する１−フルオロ−２−（３，４−ジフルオロフェニル）−６−プロピルナフタレン（特開２００４−５１６４６号公報（実施例１２）記載）を１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して１−クロロ−２−（３，４−ジフルオロフェニル）−６−プロピルナフタレンを１６ｐｐｍに減少させた（１回目の再結晶後：１０８ｐｐｍ、２回目の再結晶後：５４ｐｐｍ）。得られた混合物は８５ｇであった。 1-fluoro-2- (3,4-difluorophenyl) -6-propylnaphthalene containing 0.017% 1-chloro-2- (3,4-difluorophenyl) -6-propylnaphthalene in 400 mL of hexane 100 g of JP-A-2004-51646 (described in Example 12) was dissolved and purified by column chromatography (using 300 g of silica gel), and then recrystallized three times from 300 mL of acetone to give 1-chloro-2- (3 , 4-Difluorophenyl) -6-propylnaphthalene was reduced to 16 ppm (after the first recrystallization: 108 ppm, after the second recrystallization: 54 ppm). The resulting mixture was 85 g.
（精製例２） １−フルオロ−２−（３，４，５−トリフルオロフェニル）−６−プロピルナフタレン（化合物２）の精製 (Purification Example 2) Purification of 1-fluoro-2- (3,4,5-trifluorophenyl) -6-propylnaphthalene (Compound 2)
ヘキサン４００ｍＬに、０．０２４％の１−クロロ−２−（３，４，５−トリフルオロフェニル）−６−プロピルナフタレンを含有する１−フルオロ−２−（３，４，５−トリフルオロフェニル）−６−プロピルナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して１−クロロ−２−（３，４，５−トリフルオロフェニル）−６−プロピルナフタレンを１９ｐｐｍに減少させた。得られた混合物は８６ｇであった。 1-fluoro-2- (3,4,5-trifluorophenyl) containing 0.024% 1-chloro-2- (3,4,5-trifluorophenyl) -6-propylnaphthalene in 400 mL of hexane ) 100 g of 6-propylnaphthalene was dissolved and purified by column chromatography (using 300 g of silica gel), and then recrystallized 3 times from 300 mL of acetone to give 1-chloro-2- (3,4,5-trifluorophenyl) -6-propylnaphthalene was reduced to 19 ppm. The resulting mixture was 86 g.
（精製例３） １−フルオロ−２−（３，４，５−トリフルオロフェニル）−６−（トランス−４−エチルシクロヘキシル）ナフタレン（化合物３）の精製 (Purification Example 3) Purification of 1-fluoro-2- (3,4,5-trifluorophenyl) -6- (trans-4-ethylcyclohexyl) naphthalene (Compound 3)
ヘキサン４００ｍＬに、０．０３３％の１−クロロ−２−（３，４，５−トリフルオロフェニル）−６−（トランス−４−エチルシクロヘキシル）ナフタレンを含有する１−フルオロ−２−（３，４，５−トリフルオロフェニル）−６−（トランス−４−エチルシクロヘキシル）ナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから２回再結晶して１−クロロ−２−（３，４，５−トリフルオロフェニル）−６−（トランス−４−エチルシクロヘキシル）ナフタレンを３９ｐｐｍに減少させた（１回目の再結晶後：１１２ｐｐｍ）。得られた混合物は８９ｇであった。 1-Fluoro-2- (3, containing 0.033% 1-chloro-2- (3,4,5-trifluorophenyl) -6- (trans-4-ethylcyclohexyl) naphthalene in 400 mL of hexane 100 g of 4,5-trifluorophenyl) -6- (trans-4-ethylcyclohexyl) naphthalene was dissolved and purified by column chromatography (using 300 g of silica gel), then recrystallized twice from 300 mL of acetone to give 1-chloro -2- (3,4,5-trifluorophenyl) -6- (trans-4-ethylcyclohexyl) naphthalene was reduced to 39 ppm (after the first recrystallization: 112 ppm). The obtained mixture was 89 g.
（精製例４） １−フルオロ−２−（３，４，５−トリフルオロフェニル）−６−（トランス−４−プロピルシクロヘキシル）ナフタレン（化合物４）の精製 (Purification Example 4) Purification of 1-fluoro-2- (3,4,5-trifluorophenyl) -6- (trans-4-propylcyclohexyl) naphthalene (Compound 4)
ヘキサン４００ｍＬに、０．０３４％の１−クロロ−２−（３，４，５−トリフルオロフェニル）−６−（トランス−４−プロピルシクロヘキシル）ナフタレンを含有する１−フルオロ−２−（３，４，５−トリフルオロフェニル）−６−（トランス−４−プロピルシクロヘキシル）ナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して１−クロロ−２−（３，４，５−トリフルオロフェニル）−６−（トランス−４−プロピルシクロヘキシル）ナフタレンを１４ｐｐｍに減少させた。得られた混合物は８８ｇであった。 1-Fluoro-2- (3, containing 0.034% 1-chloro-2- (3,4,5-trifluorophenyl) -6- (trans-4-propylcyclohexyl) naphthalene in 400 mL of hexane 100 g of 4,5-trifluorophenyl) -6- (trans-4-propylcyclohexyl) naphthalene is dissolved and purified by column chromatography (using 300 g of silica gel), and then recrystallized three times from 300 mL of acetone to give 1-chloro -2- (3,4,5-trifluorophenyl) -6- (trans-4-propylcyclohexyl) naphthalene was reduced to 14 ppm. The resulting mixture was 88 g.
（精製例５） １，２，３−トリフルオロ−６−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］ナフタレン（化合物２２）の精製 (Purification Example 5) Purification of 1,2,3-trifluoro-6- [2-fluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene (Compound 22)
ヘキサン４００ｍＬに、０．０１８％の１−クロロ−２，３−ジフルオロ−６−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］ナフタレン及び０．００２％の２−クロロ−１，３−ジフルオロ−６−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］ナフタレンを含有する１，２，３−トリフルオロ−６−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］ナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して１−クロロ−２，３−ジフルオロ−６−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］ナフタレンを１７ｐｐｍ（１回目の再結晶後：１２２ｐｐｍ、２回目の再結晶後：５７ｐｐｍ）及び２−クロロ−１，３−ジフルオロ−６−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］ナフタレンを１ｐｐｍ（１回目の再結晶後：２ｐｐｍ、２回目の再結晶後：１ｐｐｍ）に減少させた。得られた混合物は８８ｇであった。 To 400 mL of hexane, 0.018% 1-chloro-2,3-difluoro-6- [2-fluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene and 0.002% 2-chloro-1 1,2,3-trifluoro-6- [2-fluoro-4- (trans-4) containing 1,3-difluoro-6- [2-fluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene -Propylcyclohexyl) phenyl] naphthalene was dissolved in 100 g, purified by column chromatography (using 300 g of silica gel), and recrystallized three times from 300 mL of acetone to give 1-chloro-2,3-difluoro-6- [2-fluoro -4- (trans-4-propylcyclohexyl) phenyl] naphthalene at 17 ppm (first time After crystallization: 122 ppm, after second recrystallization: 57 ppm) and 2-chloro-1,3-difluoro-6- [2-fluoro-4- (trans-4-propylcyclohexyl) phenyl] naphthalene at 1 ppm (first time) After recrystallization: 2 ppm, after second recrystallization: 1 ppm). The resulting mixture was 88 g.
（精製例６） ３−（トランス−４−プロピルシクロヘキシルメトキシ）−１，２，８−トリフルオロ−７−ブトキシナフタレン（化合物３０）の精製 (Purification Example 6) Purification of 3- (trans-4-propylcyclohexylmethoxy) -1,2,8-trifluoro-7-butoxynaphthalene (Compound 30)
ヘキサン４００ｍＬに、０．０１６％の８−クロロ−３−（トランス−４−プロピルシクロヘキシルメトキシ）−１，２−ジフルオロ−７−ブトキシナフタレン及び３ｐｐｍの１−クロロ−３−（トランス−４−プロピルシクロヘキシルメトキシ）−２，８−ジフルオロ−７−ブトキシナフタレンを含有する３−（トランス−４−プロピルシクロヘキシルメトキシ）−１，２，８−トリフルオロ−７−ブトキシナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して８−クロロ−３−（トランス−４−プロピルシクロヘキシルメトキシ）−１，２−ジフルオロ−７−ブトキシナフタレンを７ｐｐｍ（１回目の再結晶後：８８ｐｐｍ、２回目の再結晶後：５４ｐｐｍ）及び１−クロロ−３−（トランス−４−プロピルシクロヘキシルメトキシ）−２，８−ジフルオロ−７−ブトキシナフタレンを０．０６ｐｐｍ（１回目の再結晶後：０．６２ｐｐｍ、２回目の再結晶後：０．３１ｐｐｍ）に減少させた。得られた混合物は８１ｇであった。 To 400 mL of hexane, 0.016% 8-chloro-3- (trans-4-propylcyclohexylmethoxy) -1,2-difluoro-7-butoxynaphthalene and 3 ppm 1-chloro-3- (trans-4-propyl) 100 g of 3- (trans-4-propylcyclohexylmethoxy) -1,2,8-trifluoro-7-butoxynaphthalene containing cyclohexylmethoxy) -2,8-difluoro-7-butoxynaphthalene is dissolved and subjected to column chromatography. After purification by using 300 g of silica gel, it was recrystallized three times from 300 mL of acetone to obtain 7 ppm (first time) of 8-chloro-3- (trans-4-propylcyclohexylmethoxy) -1,2-difluoro-7-butoxynaphthalene. After recrystallization: 88 ppm, after second recrystallization 54 ppm) and 1-chloro-3- (trans-4-propylcyclohexylmethoxy) -2,8-difluoro-7-butoxynaphthalene 0.06 ppm (after the first recrystallization: 0.62 ppm, the second recrystallization) After: 0.31 ppm). The obtained mixture was 81 g.
（精製例７） ３−（トランス−４−ペンチルシクロヘキシルメトキシ）−１，２，８−トリフルオロ−７−エトキシナフタレン（化合物３１）の精製 (Purification Example 7) Purification of 3- (trans-4-pentylcyclohexylmethoxy) -1,2,8-trifluoro-7-ethoxynaphthalene (Compound 31)
ヘキサン４００ｍＬに、０．０１２％の８−クロロ−３−（トランス−４−ペンチルシクロヘキシルメトキシ）−１，２−ジフルオロ−７−エトキシナフタレンを含有する３−（トランス−４−ペンチルシクロヘキシルメトキシ）−１，２，８−トリフルオロ−７−エトキシナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して８−クロロ−３−（トランス−４−ペンチルシクロヘキシルメトキシ）−１，２−ジフルオロ−７−エトキシナフタレンを９ｐｐｍに減少させた（１回目の再結晶後：７６ｐｐｍ、２回目の再結晶後：３１ｐｐｍ）。得られた混合物は７８ｇであった。 3- (trans-4-pentylcyclohexylmethoxy)-containing 0.012% 8-chloro-3- (trans-4-pentylcyclohexylmethoxy) -1,2-difluoro-7-ethoxynaphthalene in 400 mL of hexane- 100 g of 1,2,8-trifluoro-7-ethoxynaphthalene was dissolved and purified by column chromatography (using 300 g of silica gel), and then recrystallized three times from 300 mL of acetone to give 8-chloro-3- (trans-4 -Pentylcyclohexylmethoxy) -1,2-difluoro-7-ethoxynaphthalene was reduced to 9 ppm (after the first recrystallization: 76 ppm, after the second recrystallization: 31 ppm). The resulting mixture was 78 g.
（精製例８） ３−（トランス−４−ペンチルシクロヘキシルメトキシ）−１，２，８−トリフルオロ−７−プロポキシナフタレン（化合物３２）の精製 (Purification Example 8) Purification of 3- (trans-4-pentylcyclohexylmethoxy) -1,2,8-trifluoro-7-propoxynaphthalene (Compound 32)
ヘキサン４００ｍＬに、０．０１７％の８−クロロ−３−（トランス−４−ペンチルシクロヘキシルメトキシ）−１，２−ジフルオロ−７−プロポキシナフタレンを含有する３−（トランス−４−ペンチルシクロヘキシルメトキシ）−１，２，８−トリフルオロ−７−プロポキシナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して８−クロロ−３−（トランス−４−ペンチルシクロヘキシルメトキシ）−１，２−ジフルオロ−７−プロポキシナフタレンを１６ｐｐｍに減少させた。得られた混合物は８０ｇであった。 3- (trans-4-pentylcyclohexylmethoxy)-containing 0.017% 8-chloro-3- (trans-4-pentylcyclohexylmethoxy) -1,2-difluoro-7-propoxynaphthalene in 400 mL of hexane- 100 g of 1,2,8-trifluoro-7-propoxynaphthalene was dissolved and purified by column chromatography (using 300 g of silica gel), and then recrystallized from 300 mL of acetone three times to give 8-chloro-3- (trans-4 -Pentylcyclohexylmethoxy) -1,2-difluoro-7-propoxynaphthalene was reduced to 16 ppm. The resulting mixture was 80 g.
（精製例９） ３−［トランス−４−［２−（トランス−４−プロピルシクロヘキシル）エチル］シクロヘキシルメトキシ］−１，２，８−トリフルオロ−７−エトキシナフタレン（化合物３３）の精製 (Purification Example 9) Purification of 3- [trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexylmethoxy] -1,2,8-trifluoro-7-ethoxynaphthalene (Compound 33)
ヘキサン４００ｍＬに、０．０２５％の８−クロロ−３−［トランス−４−［２−（トランス−４−プロピルシクロヘキシル）エチル］シクロヘキシルメトキシ］−１，２−ジフルオロ−７−エトキシナフタレンを含有する３−［トランス−４−［２−（トランス−４−プロピルシクロヘキシル）エチル］シクロヘキシルメトキシ］−１，２，８−トリフルオロ−７−エトキシナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して８−クロロ−３−［トランス−４−［２−（トランス−４−プロピルシクロヘキシル）エチル］シクロヘキシルメトキシ］−１，２−ジフルオロ−７−エトキシナフタレンを２９ｐｐｍに減少させた（１回目の再結晶後：１９３ｐｐｍ、２回目の再結晶後：７３ｐｐｍ）。得られた混合物は８９ｇであった。 In 400 mL of hexane, 0.025% of 8-chloro-3- [trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexylmethoxy] -1,2-difluoro-7-ethoxynaphthalene is contained. 100 g of 3- [trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexylmethoxy] -1,2,8-trifluoro-7-ethoxynaphthalene was dissolved, and column chromatography (using 300 g of silica gel) And then recrystallized three times from 300 mL of acetone to give 8-chloro-3- [trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexylmethoxy] -1,2-difluoro-7- Ethoxynaphthalene was reduced to 29 ppm (after the first recrystallization 193ppm, 2 nd after recrystallization: 73ppm). The obtained mixture was 89 g.
（精製例１０） ３−［トランス−４−［２−（トランス−４−プロピルシクロヘキシル）エチル］シクロヘキシルメトキシ］−１，２，８−トリフルオロ−７−プロポキシナフタレン（化合物３４）の精製 (Purification Example 10) Purification of 3- [trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexylmethoxy] -1,2,8-trifluoro-7-propoxynaphthalene (Compound 34)
ヘキサン４００ｍＬに、０．０３６％の８−クロロ−３−［トランス−４−［２−（トランス−４−プロピルシクロヘキシル）エチル］シクロヘキシルメトキシ］−１，２−ジフルオロ−７−プロポキシナフタレンを含有する３−［トランス−４−［２−（トランス−４−プロピルシクロヘキシル）エチル］シクロヘキシルメトキシ］−１，２，８−トリフルオロ−７−プロポキシナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して８−クロロ−３−［トランス−４−［２−（トランス−４−プロピルシクロヘキシル）エチル］シクロヘキシルメトキシ］−１，２−ジフルオロ−７−プロポキシナフタレンを３４ｐｐｍに減少させた。得られた混合物は８８ｇであった。 In 400 mL of hexane, 0.036% 8-chloro-3- [trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexylmethoxy] -1,2-difluoro-7-propoxynaphthalene is contained. 100 g of 3- [trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexylmethoxy] -1,2,8-trifluoro-7-propoxynaphthalene was dissolved, and column chromatography (using 300 g of silica gel) And then recrystallized three times from 300 mL of acetone to give 8-chloro-3- [trans-4- [2- (trans-4-propylcyclohexyl) ethyl] cyclohexylmethoxy] -1,2-difluoro-7- Propoxynaphthalene was reduced to 34 ppm. The resulting mixture was 88 g.
（精製例１１） ３−（トランス，トランス−４’−エチルビシクロヘキシル−４−イルメトキシ）−１，２，８−トリフルオロ−７−エトキシナフタレン（化合物３５）の精製 (Purification Example 11) Purification of 3- (trans, trans-4'-ethylbicyclohexyl-4-ylmethoxy) -1,2,8-trifluoro-7-ethoxynaphthalene (Compound 35)
ヘキサン４００ｍＬに、０．０１４％の８−クロロ−３−（トランス，トランス−４’−エチルビシクロヘキシル−４−イルメトキシ）−１，２−ジフルオロ−７−エトキシナフタレン、０．２ｐｐｍの２−クロロ−３−（トランス，トランス−４’−エチルビシクロヘキシル−４−イルメトキシ）−１，８−ジフルオロ−７−エトキシナフタレン及び４．３ｐｐｍの１−クロロ−３−（トランス，トランス−４’−エチルビシクロヘキシル−４−イルメトキシ）−２，８−ジフルオロ−７−エトキシナフタレンを含有する３−（トランス，トランス−４’−エチルビシクロヘキシル−４−イルメトキシ）−１，２，８−トリフルオロ−７−エトキシナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから２回再結晶して８−クロロ−３−（トランス，トランス−４’−エチルビシクロヘキシル−４−イルメトキシ）−１，２−ジフルオロ−７−エトキシナフタレンを１３ｐｐｍ（１回目の再結晶後：７３ｐｐｍ）、２−クロロ−３−（トランス，トランス−４’−エチルビシクロヘキシル−４−イルメトキシ）−１，８−ジフルオロ−７−エトキシナフタレンを２ｐｐｂ（１回目の再結晶後：８０ｐｐｂ、２回目の再結晶後：２４ｐｐｂ）及び１−クロロ−３−（トランス，トランス−４’−エチルビシクロヘキシル−４−イルメトキシ）−２，８−ジフルオロ−７−エトキシナフタレンを４ｐｐｂ（１回目の再結晶後１５２ｐｐｂ）に減少させた。得られた混合物は８９ｇであった。 To 400 mL of hexane, 0.014% of 8-chloro-3- (trans, trans-4′-ethylbicyclohexyl-4-ylmethoxy) -1,2-difluoro-7-ethoxynaphthalene, 0.2 ppm of 2-chloro -3- (trans, trans-4'-ethylbicyclohexyl-4-ylmethoxy) -1,8-difluoro-7-ethoxynaphthalene and 4.3 ppm 1-chloro-3- (trans, trans-4'-ethyl 3- (trans, trans-4′-ethylbicyclohexyl-4-ylmethoxy) -1,2,8-trifluoro-7 containing bicyclohexyl-4-ylmethoxy) -2,8-difluoro-7-ethoxynaphthalene -Dissolve 100 g of ethoxynaphthalene and use column chromatography (using 300 g of silica gel). After purification, the product was recrystallized twice from 300 mL of acetone to give 13 ppm (1 of 8-chloro-3- (trans, trans-4′-ethylbicyclohexyl-4-ylmethoxy) -1,2-difluoro-7-ethoxynaphthalene). 2 ppb of 2-chloro-3- (trans, trans-4′-ethylbicyclohexyl-4-ylmethoxy) -1,8-difluoro-7-ethoxynaphthalene (after the first recrystallization: 73 ppm) After: 80 ppb, after the second recrystallization: 24 ppb) and 1-chloro-3- (trans, trans-4′-ethylbicyclohexyl-4-ylmethoxy) -2,8-difluoro-7-ethoxynaphthalene in 4 ppb ( It was reduced to 152 ppb) after the first recrystallization. The obtained mixture was 89 g.
（精製例１２） ３−（トランス，トランス−４’−プロピルビシクロヘキシル−４−イルメトキシ）−１，２，８−トリフルオロ−７−ブトキシナフタレン（化合物３６）の精製 (Purification Example 12) Purification of 3- (trans, trans-4'-propylbicyclohexyl-4-ylmethoxy) -1,2,8-trifluoro-7-butoxynaphthalene (Compound 36)
ヘキサン４００ｍＬに、０．０２８％の８−クロロ−３−（トランス，トランス−４’−プロピルビシクロヘキシル−４−イルメトキシ）−１，２−トリフルオロ−７−ブトキシナフタレンを含有する３−（トランス，トランス−４’−プロピルビシクロヘキシル−４−イルメトキシ）−１，２，８−トリフルオロ−７−ブトキシナフタレンを１００ｇ溶解し、カラムクロマトグラフィー（シリカゲル３００ｇ使用）により精製した後、アセトン３００ｍＬから３回再結晶して８−クロロ−３−（トランス，トランス−４’−プロピルビシクロヘキシル−４−イルメトキシ）−１，２−トリフルオロ−７−ブトキシナフタレンを２６ｐｐｍに減少させた。得られた混合物は８５ｇであった。
（実施例１〜４）
上記精製例１〜５で精製したナフタレン化合物（化合物１〜４及び２２）の混合物を用いて、ｐ型液晶組成物を作製した。組成を表１に示す。
3- (trans containing 0.028% 8-chloro-3- (trans, trans-4′-propylbicyclohexyl-4-ylmethoxy) -1,2-trifluoro-7-butoxynaphthalene in 400 mL of hexane. , Trans-4′-propylbicyclohexyl-4-ylmethoxy) -1,2,8-trifluoro-7-butoxynaphthalene is dissolved in 100 g and purified by column chromatography (using 300 g of silica gel), and then 300 ml to 3 ml of acetone. Recrystallization was performed to reduce 8-chloro-3- (trans, trans-4′-propylbicyclohexyl-4-ylmethoxy) -1,2-trifluoro-7-butoxynaphthalene to 26 ppm. The resulting mixture was 85 g.
(Examples 1-4)
A p-type liquid crystal composition was prepared using the mixture of naphthalene compounds (compounds 1 to 4 and 22) purified in the purification examples 1 to 5. The composition is shown in Table 1.
（実施例５〜８）
上記精製例６〜１２で精製したナフタレン化合物（化合物３０〜３６）の混合物を用いて、ｎ型液晶組成物を作製した。組成を表２に示す。
(Examples 5 to 8)
Using the mixture of naphthalene compounds (compounds 30 to 36) purified in the above purification examples 6 to 12, n-type liquid crystal compositions were prepared. The composition is shown in Table 2.
表１〜２に記載した化合物１〜５４の化学構造を以下に示す。 The chemical structures of compounds 1 to 54 described in Tables 1 and 2 are shown below.
（比較例１）
上記精製例による精製を行っていない、ナフタレン上のフッ素原子が塩素原子に置換した化合物を含有するナフタレン化合物（精製例として示した精製法において原料として使用したナフタレン化合物の混合物）を使用して実施例１と同様な組成物を作製した。
（比較例２）
上記精製例による精製を行っていない、ナフタレン上のフッ素原子が塩素原子に置換した化合物を含有するナフタレン化合物（精製例として示した精製法において原料として使用したナフタレン化合物の混合物）を使用して実施例２と同様な組成物を作製した。
（比較例３）
上記精製例による精製を行っていない、ナフタレン上のフッ素原子が塩素原子に置換した化合物を含有するナフタレン化合物（精製例として示した精製法において原料として使用したナフタレン化合物の混合物）を使用して実施例３と同様な組成物を作製した。
（比較例４）
上記精製例による精製を行っていない、ナフタレン上のフッ素原子が塩素原子に置換した化合物を含有するナフタレン化合物（精製例として示した精製法において原料として使用したナフタレン化合物の混合物）を使用して実施例４と同様な組成物を作製した。
（比較例５）
上記精製例による精製を行っていない、ナフタレン上のフッ素原子が塩素原子に置換した化合物を含有するナフタレン化合物（精製例として示した精製法において原料として使用したナフタレン化合物の混合物）を使用して実施例５と同様な組成物を作製した。
（比較例６）
上記精製例による精製を行っていない、ナフタレン上のフッ素原子が塩素原子に置換した化合物を含有するナフタレン化合物（精製例として示した精製法において原料として使用したナフタレン化合物の混合物）を使用して実施例６と同様な組成物を作製した。
（比較例７）
上記精製例による精製を行っていない、ナフタレン上のフッ素原子が塩素原子に置換した化合物を含有するナフタレン化合物（精製例として示した精製法において原料として使用したナフタレン化合物の混合物）を使用して実施例７と同様な組成物を作製した。
（比較例８）
上記精製例による精製を行っていない、ナフタレン上のフッ素原子が塩素原子に置換した化合物を含有するナフタレン化合物（精製例として示した精製法において原料として使用したナフタレン化合物の混合物）を使用して実施例８と同様な組成物を作製した。
（評価）
実施例１〜８の液晶組成物について、ＴＮ−Ｉ、Ｔ→Ｎ、Δｎ、ηを測定した結果を表３に示す。これらの評価項目においては比較例１〜８の液晶組成物についても対応する実施例と同様の結果が得られた。
(Comparative Example 1)
Conducted using a naphthalene compound (a mixture of naphthalene compounds used as a raw material in the purification method shown in the purification example) containing a compound in which the fluorine atom on naphthalene is replaced by a chlorine atom, which has not been purified by the above purification example A composition similar to Example 1 was prepared.
(Comparative Example 2)
Conducted using a naphthalene compound (a mixture of naphthalene compounds used as a raw material in the purification method shown in the purification example) containing a compound in which the fluorine atom on naphthalene is replaced by a chlorine atom, which has not been purified by the above purification example A composition similar to Example 2 was prepared.
(Comparative Example 3)
Conducted using a naphthalene compound (a mixture of naphthalene compounds used as a raw material in the purification method shown in the purification example) containing a compound in which the fluorine atom on naphthalene is replaced by a chlorine atom, which has not been purified by the above purification example A composition similar to Example 3 was prepared.
(Comparative Example 4)
Conducted using a naphthalene compound (a mixture of naphthalene compounds used as a raw material in the purification method shown in the purification example) containing a compound in which the fluorine atom on naphthalene is replaced by a chlorine atom, which has not been purified by the above purification example A composition similar to Example 4 was prepared.
(Comparative Example 5)
Conducted using a naphthalene compound (a mixture of naphthalene compounds used as a raw material in the purification method shown in the purification example) containing a compound in which the fluorine atom on naphthalene is replaced by a chlorine atom, which has not been purified by the above purification example A composition similar to Example 5 was prepared.
(Comparative Example 6)
Conducted using a naphthalene compound (a mixture of naphthalene compounds used as a raw material in the purification method shown in the purification example) containing a compound in which the fluorine atom on naphthalene is replaced by a chlorine atom, which has not been purified by the above purification example A composition similar to Example 6 was prepared.
(Comparative Example 7)
Conducted using a naphthalene compound (a mixture of naphthalene compounds used as a raw material in the purification method shown in the purification example) containing a compound in which the fluorine atom on naphthalene is replaced by a chlorine atom, which has not been purified by the above purification example A composition similar to Example 7 was prepared.
(Comparative Example 8)
Conducted using a naphthalene compound (a mixture of naphthalene compounds used as a raw material in the purification method shown in the purification example) containing a compound in which the fluorine atom on naphthalene is replaced by a chlorine atom, which has not been purified by the above purification example A composition similar to Example 8 was prepared.
(Evaluation)
Table 3 shows the results of measuring T N-I , T 1 → N , Δn, and η for the liquid crystal compositions of Examples 1 to 8. In these evaluation items, the same results as in the corresponding examples were obtained for the liquid crystal compositions of Comparative Examples 1 to 8.
次に、実施例１〜８の液晶組成物について、一般式（ＩＩ）で表される化合物の含有量及び耐ＵＶ性試験を行った結果を表４に示す。 Next, Table 4 shows the results of the content of the compound represented by the general formula (II) and the UV resistance test for the liquid crystal compositions of Examples 1 to 8.
続いて、比較例１〜８の液晶組成物について、一般式（ＩＩ）で表される化合物の含有量の合計及び耐ＵＶ性試験を行った結果を表５に示す。 Then, about the liquid crystal composition of Comparative Examples 1-8, the result of having done the sum total of content of the compound represented by general formula (II), and a UV-proof test is shown in Table 5.
一般式（ＩＩ)で表される化合物の含有量が５ｐｐｍ以下である本願発明の液晶組成物は、一般式（ＩＩ）で表される化合物の含有量が５ｐｐｍを超えることを除いては本願発明の液晶組成物と同一組成である比較例の液晶組成物と同様に、ＵＶを照射する前のＶＨＲの値はほぼ等しく高い値を示すことが確認できた。その後ＵＶを照射し耐ＵＶ性試験を行ったところ比較例の液晶組成物はＶＨＲの値が９％程度低下したのに対し、本願発明の液晶組成物は４％程度以下の低下に抑えられ高い信頼性を持つことが明らかとなった。 The liquid crystal composition of the present invention in which the content of the compound represented by the general formula (II) is 5 ppm or less is the present invention except that the content of the compound represented by the general formula (II) exceeds 5 ppm. As in the liquid crystal composition of the comparative example having the same composition as the liquid crystal composition, it was confirmed that the VHR values before UV irradiation were almost equally high. Thereafter, when UV irradiation was performed by irradiating with UV, the liquid crystal composition of the comparative example had a VHR value of about 9% lower, whereas the liquid crystal composition of the present invention was suppressed to about 4% or less and was high. It became clear that it was reliable.
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| US10113115B2 (en) | 2014-09-05 | 2018-10-30 | DIC Corporation (Tokyo) | Nematic liquid crystal composition and liquid crystal display device using the same |
| US10323186B2 (en) | 2014-12-25 | 2019-06-18 | Dic Corporation | Nematic liquid crystal composition and liquid crystal display element using the same |
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| JP2003335711A (en) * | 2002-03-11 | 2003-11-28 | Dainippon Ink & Chem Inc | Method for purifying liquid crystalline compound |
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| US10351772B2 (en) | 2014-05-13 | 2019-07-16 | Dic Corporation | Nematic liquid crystal composition and liquid crystal display element using same |
| US10113115B2 (en) | 2014-09-05 | 2018-10-30 | DIC Corporation (Tokyo) | Nematic liquid crystal composition and liquid crystal display device using the same |
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