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  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
  • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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  • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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  • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D309/06—Radicals substituted by oxygen atoms
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  • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
  • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
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  • 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
  • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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  • 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
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  • 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
  • C09K19/16—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon double bonds, e.g. stilbenes
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  • 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
  • C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
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  • 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
  • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
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  • 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
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  • C09K19/00—Liquid crystal materials
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  • C09K19/56—Aligning agents
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

• the present invention relates to compounds, liquid crystal compositions and liquid crystal display devices. More specifically, a compound having a polymerizable group such as methoxymethacryloyloxy and a polar group such as a ⁇ OH group, a liquid crystal composition containing this compound and having a positive or negative dielectric anisotropy, and this composition or its composition.
• the present invention relates to a liquid crystal display element containing a part of a cured product.
• liquid crystal display elements When liquid crystal display elements are classified based on the operation mode of liquid crystal molecules, PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS ( It can be classified into modes such as in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). Further, it can be classified into PM (passive matrix) and AM (active matrix) based on the drive method of the element. PM is classified into static, multiplex and the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal) and the like.
• PC phase change
• TN twisted nematic
• STN super twisted nematic
• ECB electrically controlled birefringence
• OCB optical compensated bend
• IPS It can be classified into modes such as in-plane switching), VA (vertical alignment
• TFTs can be classified into amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. When classified based on the light source, it can be classified into a reflective type that uses natural light, a transmissive type that uses a backlight, and a semi-transmissive type that uses both natural light and a backlight.
• the liquid crystal composition having a nematic phase has appropriate properties. By improving the characteristics of this composition, an AM element having good characteristics can be obtained.
• the relationship between the characteristics of the composition and the characteristics of the AM device is summarized in Table 1 below.
• the properties of the composition will be further described based on commercially available AM devices.
• the temperature range of the nematic phase (the temperature range exhibiting the nematic phase) is related to the temperature range in which the device can be used.
• the preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about ⁇ 10 ° C. or lower.
• the viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time of even 1 millisecond is desirable. Therefore, the viscosity of the composition is preferably low, and more preferably low even at low temperatures.
• the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required.
• the product ( ⁇ n ⁇ d) of the optical anisotropy ( ⁇ n) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio.
• the appropriate product value depends on the type of operating mode. This value is about 0.45 ⁇ m for devices in modes such as TN. This value ranges from about 0.30 ⁇ m to about 0.40 ⁇ m for VA mode devices and from about 0.20 ⁇ m to about 0.30 ⁇ m for IPS or FFS mode devices.
• a composition having a large optical anisotropy is preferable for a device having a small cell gap.
• the large dielectric anisotropy in the composition contributes to the low threshold voltage, low power consumption and large contrast ratio in the device. Therefore, a large positive or negative dielectric anisotropy is preferable.
• a large resistivity in the composition contributes to a large voltage retention and a large contrast ratio in the device. Therefore, a composition having a large resistivity at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long-term use, a composition having a large resistivity not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable.
• the stability of the composition against UV and heat is related to the life of the device. When this stability is high, the life of the device is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.
• a liquid crystal composition containing a polymer is used.
• the composition to which a small amount of the polymerizable compound is added is injected into the device.
• a polymerizable compound having a plurality of polymerizable groups is generally used.
• the composition is irradiated with ultraviolet rays while applying a voltage between the substrates sandwiching this element.
• the polymerizable compound polymerizes to form a network structure of the polymer in the composition.
• the orientation of the liquid crystal molecules can be controlled by the polymer, so that the response time of the device is shortened and the burn-in of the image is improved.
• Such effects of the polymer can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, FPA.
• a liquid crystal display element having no alignment film a mode in which a polar compound is added to a liquid crystal composition to orient liquid crystal molecules has been proposed.
• a composition containing a small amount of polar compound and a small amount of polymerizable compound is injected into the device.
• the polymerizable compound a polymerizable compound having a plurality of polymerizable groups is generally used.
• the liquid crystal molecules are oriented by the action of the polar compound.
• the composition is irradiated with ultraviolet rays while applying a voltage between the substrates sandwiching this element.
• the polymerizable compound polymerizes and stabilizes the orientation of the liquid crystal molecules.
• the orientation of the liquid crystal molecules can be controlled by the polar compound and the polymer, so that the response time of the device is shortened and the image burn-in is improved.
• the step of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not reduce the electrical resistance of the device.
• Such effects due to the combination of the polar compound and the polymer can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
• Patent Document 2 describes a polymerizable compound (S-1) having a plurality of polar groups and a plurality of polymerizable groups.
• the first object of the present invention is high stability against heat, high chemical stability, high ability to orient liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, high monomer consumption rate, and liquid crystal display. It is to provide a compound which has at least one of the large voltage retention when used in an element and has high solubility in a liquid crystal composition.
• the second challenge is to include this compound and have a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, low viscosity, suitable optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance.
• the third challenge is the wide temperature range in which the device can be used, short response time, high transmittance, large voltage retention, low threshold voltage, large contrast ratio, long life, good vertical orientation, and pretilt angle.
• the present invention relates to a liquid crystal display element containing a compound represented by the formula (1), a liquid crystal composition containing this compound, and a polymer obtained by polymerizing at least a part of this composition and / or this composition.
• Rings A 1 and A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4.
• R 2 are independently alkyl of 1 to 5 carbon atoms
• R 3 is independently a cyclic alkyl branched chain alkyl or C 3-8, straight chain alkyl or C 3 to 10 1 to 10 carbons
• Y 1 is independently chlorine, fluorine, or bromine
• Sp 2 is a single bond or an alkylene having 1 to 10 carbon atoms, and in this Sp 2 , at least one -CH 2- is -O-, -CO-, -COO-, -OCO-, -OCOO-.
• One hydrogen is replaced with fluorine, chlorine, a group represented by the formula (1-p1), the formula (1-p2), the formula (1-p3), the formula (1-p4) or the formula (1-p5). May be;
• X 1 is a polar group with a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon;
• P 1 and P 2 has at least one of the groups represented by the formulas (1-p1), formula (1-p2), and formula (1-p3).
• Sp 2 is a single bond or an alkylene having 1 to 10 carbon atoms, and in this Sp 2 , at least one -CH 2- is -O-, -CO-, -COO-, -OCO-, -OCOO.
• At least one hydrogen is fluorine, chlorine, a group represented by the formula (1-p1), the formula (1-p2), the formula (1-p3), the formula (1-p4) or the formula (1-p5). May be replaced; If neither P 1 nor P 2 has a group represented by the formulas (1-p1), formula (1-p2), and formula (1-p3), Sp 2 starts from 1 carbon number. It is 10 alkylene, and in this Sp 2 , at least one -CH 2- is replaced with a group represented by the formula (1-a), and at least one -CH 2- is -O-, -CO.
• At least one hydrogen is fluorine, chlorine, a group represented by the formula (1-p1), the formula (1-p2), the formula (1-p3), the formula (1-p4) or the formula (1-p5). May be replaced with.
• the first advantages of the present invention are high stability to heat, high chemical stability, high ability to orient liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, high monomer consumption rate, and liquid crystal display. It is to provide a compound which has at least one of the large voltage retention when used in an element and has high solubility in a liquid crystal composition.
• the second advantage is that it contains this compound and has a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, low viscosity, suitable optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance.
• the third advantage is the wide temperature range in which the device can be used, short response time, high transmittance, large voltage retention, low threshold voltage, large contrast ratio, long life, good vertical orientation, and pretilt angle. It is an object of the present invention to provide a liquid crystal display element having at least one of characteristics such as a small change in brightness with time.
• liquid crystal compound liquid crystal composition
• liquid crystal display element may be abbreviated as “compound”, “composition”, and “element”, respectively.
• the “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase but adjusting the physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, and dielectric constant anisotropy. It is a general term for compounds added for the purpose. This compound usually has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like.
• the "polymerizable compound” is a compound added for the purpose of forming a polymer in the composition.
• a liquid crystal compound having an alkenyl is not a polymerizable compound in that sense.
• the "polar compound” helps the liquid crystal molecules to be arranged by the polar groups interacting with the surface of the substrate or the like.
• Liquid crystal display element is a general term for a liquid crystal display panel, a liquid crystal display module, and the like.
• the liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds.
• This composition contains polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and defoamers for the purpose of further adjusting the physical properties.
• Additives such as foaming agents are added as needed.
• the ratio (content) of the liquid crystal compound in the liquid crystal composition is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive even when the additive is added.
• the ratio (addition amount) of the additive in the liquid crystal composition is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive.
• the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Parts per million (ppm) by weight may also be used.
• the proportion of polymerization initiator and polymerization inhibitor in the liquid crystal composition is exceptionally expressed based on the weight of the polymerizable compound.
• the “transparency point” is the transition temperature between the liquid crystal phase and the isotropic phase in the liquid crystal compound.
• the “lower limit temperature of the liquid crystal phase” is the transition temperature of the solid-liquid crystal phase (smectic phase, nematic phase, etc.) in the liquid crystal compound.
• the “upper limit temperature of the nematic phase” is the transition temperature of the nematic phase-isotropic phase in the mixture of the liquid crystal compound and the mother liquid crystal or the liquid crystal composition, and may be abbreviated as the “upper limit temperature”.
• the “lower limit temperature of the nematic phase” may be abbreviated as the "lower limit temperature”.
• high solubility in a liquid crystal composition means that the composition has high solubility in any of the compositions containing the liquid crystal compound at room temperature, and the composition is dissolved in the following examples.
• the composition used to assess the sex can be used as a reference.
• the compound represented by the formula (1) may be abbreviated as "compound (1)".
• Compound (1) means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. This rule also applies to at least one compound selected from the group of compounds represented by the formula (2). Symbols such as A 1 , B 1 , and C 1 enclosed in hexagons correspond to ring A 1 , ring B 1 , and ring C 1 , respectively.
• the hexagon represents a six-membered ring such as a cyclohexane ring or a benzene ring, or a condensed ring such as a naphthalene ring.
• the symbol of the terminal group R 11 is used for a plurality of compounds, but the groups represented by R 11 in these compounds may be the same or different.
• R 11 of Compound (2) when R 11 of Compound (2) is ethyl, R 11 of compound (3) may be ethyl, it may be other groups, such as propyl.
• This rule also applies to other symbols.
• i when i is 2, two rings D 1 are present.
• the two groups represented by two rings D 1 in the compound may be the same or different.
• i is greater than 2 also apply to any two rings D 1. This rule also applies to other symbols.
• the expression "at least one'A'” means that the number of'A's is arbitrary.
• the expression “at least one'A'may be replaced by'B'” is not replaced by'B'in the case of'A'itself, one'A'is replaced by'B'. In this case, including the case where two or more'A's are replaced with'B', the position of'A' replaced with'B' is arbitrary in these cases.
• the rule that the replacement position is arbitrary also applies to the expression "at least one'A'has been replaced by a'B'".
• the expression "at least one A may be replaced by B, C, or D" is that if A is not replaced, if at least one A is replaced by B, then at least one A is replaced by C.
• alkyl, alkoxyalkenyl, alkenyloxyalkyl It is not preferable that two consecutive -CH 2- are replaced with -O- to become -O-O-.
• Alkyl such as in, -CH 2 methyl moiety (-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.
• R 11 and R 12 are independently alkyls with 1 to 10 carbons or alkenyl with 2 to 10 carbons, in which at least one -CH 2- is replaced with -O-. Often, in these groups, at least one hydrogen may be replaced by fluorine. " In this expression, “in these groups” may be interpreted literally. In this expression, “these groups” means alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, “these groups” refers to all of the groups described prior to the term “in these groups”. This common-sense interpretation applies to other terms as well.
• Halogen means fluorine, chlorine, bromine, or iodine. Preferred halogens are fluorine or chlorine. A more preferred halogen is fluorine.
• the alkyl is a linear alkyl or a branched chain alkyl and does not contain a cyclic alkyl. Straight chain alkyls are generally preferred over branched chain alkyls. The same applies to terminal groups such as alkoxy and alkenyl.
• the configuration for 1,4-cyclohexylene is preferably trans over cis in order to raise the upper temperature limit of the nematic phase.
• 2-Fluoro-1,4-phenylene means the following two divalent groups.
• fluorine may be left-facing (L) or right-facing (R). This rule also applies to asymmetric divalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.
• the present invention includes the following items and the like.
• Item 1 A compound represented by the formula (1).
• Rings A 1 and A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4.
• R 2 are independently alkyl of 1 to 5 carbon atoms
• R 3 is independently a cyclic alkyl branched chain alkyl or C 3-8, straight chain alkyl or C 3 to 10 1 to 10 carbons
• Y 1 is independently chlorine, fluorine, or bromine
• Sp 2 is a single bond or an alkylene having 1 to 10 carbon atoms, and in this Sp 2 , at least one -CH 2- is -O-, -CO-, -COO-, -OCO-, -OCOO-.
• One hydrogen is replaced with fluorine, chlorine, a group represented by the formula (1-p1), the formula (1-p2), the formula (1-p3), the formula (1-p4) or the formula (1-p5). May be;
• X 1 is a polar group with a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon;
• P 1 and P 2 has at least one of the groups represented by the formulas (1-p1), formula (1-p2), and formula (1-p3).
• Sp 2 is a single bond or an alkylene having 1 to 10 carbon atoms, and in this Sp 2 , at least one -CH 2- is -O-, -CO-, -COO-, -OCO-, -OCOO.
• At least one hydrogen is fluorine, chlorine, a group represented by the formula (1-p1), the formula (1-p2), the formula (1-p3), the formula (1-p4) or the formula (1-p5). May be replaced; If neither P 1 nor P 2 has a group represented by the formulas (1-p1), formula (1-p2), and formula (1-p3), Sp 2 starts from 1 carbon number. It is 10 alkylene, and in this Sp 2 , at least one -CH 2- is replaced with a group represented by the formula (1-a), and at least one -CH 2- is -O-, -CO.
• At least one hydrogen is fluorine, chlorine, a group represented by the formula (1-p1), the formula (1-p2), the formula (1-p3), the formula (1-p4) or the formula (1-p5). May be replaced with.
• Item 2 The compound according to Item 1, wherein the polar group is represented by any one of the formulas (X-1) to (X-27).
• J 1 and J 2 are independently hydrogen, or a linear alkyl having 1 to 5 carbon atoms or a branched chain alkyl having 3 to 5 carbon atoms, and in these J 1 and J 2 , at least one -CH 2- May be replaced with -O-; J 3 is hydrogen, or a linear alkyl having 1 to 20 carbon atoms or a branched chain alkyl having 3 to 20 carbon atoms. In this J 3 , at least one -CH 2- is -O-, -COO-.
• J 4 and J 5 are independently hydrogen or alkyl having from 1 to 8 carbon atoms;
• Q 1 is methine or nitrogen, where the hydrogen of methine may be replaced by an alkyl having 1 to 6 carbon atoms;
• U 1 and U 2 are independently -CH 2- , -O-, -CO- or -S-;
• V 1 , V 2 and V 3 are independently methine or nitrogen, and at least one of V 1 , V 2 and V 3 contains nitrogen;
• W 1 is -O- or -S-;
• W 2 is carbon, sulfur or silicon.
• Q 1 is methine in the formula (X-14)
• at least one of U 1 and U 2 is -O-, -CO- or -S-.
• Item 3. The compound according to Item 1 or 2, which is represented by any one of formulas (1-1) to (1-8).
• Ring A 5 from ring A 1 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in ring a 5 from the ring a 1, at least one of hydrogen, fluorine, chlorine, alkyl of 1 to 10 carbons, alkenyl having 2 to 10 carbon atoms , 1 to 9 carbon alkoxy, or 2 to 9 carbon alkenyloxy
• Sp 1 is independently a single bond or an alkylene with 1 to 7 carbon atoms, even if at least one -CH 2- is replaced with -O-, -CO- or -COO- in this Sp 1 .
• R 2 are independently alkyl of 1 to 5 carbon atoms;
• R 3 is independently a cyclic alkyl branched chain alkyl or C 3-8, straight chain alkyl or C 3 to 10 1 to 10 carbons;
• Y 1 is independently chlorine, fluorine, or bromine;
• Sp 2 is a single bond or an alkylene having 1 to 7 carbon atoms, and in this Sp 2 , at least one -CH 2- is of -O-, -CO-, -COO- or formula (1-a).
• X 1 is a polar group with a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon;
• P 1 and P 2 has at least one of the groups represented by the formulas (1-p1), formula (1-p2), and formula (1-p3).
• -P1), formula (1-p2), formula (1-p3), formula (1-p4) or the group represented by formula (1-p5) may be replaced.
• Item 4 The compound according to any one of Items 1 to 3, which is represented by any one of the formulas (1-9) to (1-16).
• Ring A 5 from ring A 1 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in ring a 5 from the ring a 1, at least one hydrogen, fluorine, alkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms, or, It may be replaced with alkoxy having 1 to 4 carbon atoms; b and c are independently 0, 1, or 2; Z 1
• R 2 are independently alkyl of 1 to 5 carbon atoms;
• R 3 is independently a cyclic alkyl branched chain alkyl or C 3-8, straight chain alkyl or C 3 to 10 1 to 10 carbons;
• Y 1 is independently chlorine, fluorine, or bromine;
• Sp 2 is a single bond or alkylene of 1 to 7 carbon atoms, in the sp 2, at least one of -CH 2 -, -O- or replaced with a group represented by the formula (1-a)
• at least one hydrogen may be replaced with fluorine or chlorine;
• X 1 is a polar group with a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon;
• the compounds represented by formulas (1-9) to (1-16) are at least one of the groups represented by formulas (1-p1), formula (1-p2), and formula (1-p3). It has one or more groups.
• Item 5. The compound according to any one of Items 1 to 4, which is represented by any one of the formulas (1-17) to (1-145).
• R 1 is an alkyl having 1 to 10 carbon atoms
• Z 1 to Z 3 are independently single bonds or-(CH 2 ) 2-
• Sp 1 is independently alkylene of 5 a single bond or 1 carbon atoms, in the Sp 1, at least one -CH 2 - may be replaced by -O-
• R 2 are independently alkyl of 1 to 5 carbon atoms
• R 3 is independently a cyclic alkyl branched chain alkyl or C 3-8, straight chain alkyl or C 3 to 10 1 to 10 carbons
• Y 1 is independently chlorine, fluorine, or bromine
• Y 11 to Y 21 are independently hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, alkenyl with 2 to 5 carbon atoms, or alkoxy with 1 to 4 carbon atoms
• Sp 2 is a single bond or alkylene of 1 to 7 carbon atoms, in the sp 2, at least one of -CH 2 -, -O- or replaced
• Sp 3 and Sp 4 are independently single bonds or alkylenes having 1 to 5 carbon atoms, and in Sp 3 and Sp 4 , at least one -CH 2- may be replaced with -O-;
• X 1 is a polar group having a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon.
• Item 6 A liquid crystal composition containing at least one of the compounds according to any one of Items 1 to 5.
• Item 7. The liquid crystal composition according to Item 6, which contains at least one compound selected from the group of compounds represented by the formulas (2) to (4).
• R 11 and R 12 are independently alkenyl alkyl carbon atoms or 2 to 10 1 to 10 carbons, and in the R 11 and R 12, at least one -CH 2 - is replaced by -O- At least one hydrogen may be replaced with fluorine;
• Ring B 1 , Ring B 2 , Ring B 3 , and Ring B 4 are independent, 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
• Item 8. The liquid crystal composition according to Item 6 or 7, which contains at least one compound selected from the group of compounds represented by the formulas (5) to (7).
• R 13 is alkenyl alkyl carbon atoms or 2 to 10 1 to 10 carbons, and in this R 13, at least one -CH 2 - may be replaced by -O-, at least one hydrogen May be replaced with fluorine;
• X 11 is fluorine, chlorine, -OCF 3 , -OCHF 2 , -CF 3 , -CHF 2 , -CH 2 F, -OCF 2 CHF 2 , or -OCF 2 CHFCF 3 ;
• Ring C 1 , Ring C 2 , and Ring C 3 are independent, 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl.
• L 11 and L 12 are independently hydrogen or fluorine.
• Item 9 The liquid crystal composition according to any one of Items 6 to 8, which contains at least one compound selected from the group of compounds represented by the formula (8).
• R 14 is an alkenyl alkyl carbon atoms or 2 to 10 1 to 10 carbons, and in this R 14, at least one -CH 2 - may be replaced by -O-, at least one hydrogen May be replaced with fluorine;
• X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N;
• Ring D 1 is 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or at least 1
• One hydrogen is 1,4-phenylene replaced by fluorine;
• Z 17 is a single bond, -COO-, -OCO-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2 -,-(CH 2 ) 2- , or -C ⁇ C.
• -And L 13 and L 14 are independently hydrogen
• Item 10. The liquid crystal composition according to any one of Items 6 to 9, which contains at least one compound selected from the group of compounds represented by the formulas (11) to (19).
• R 15 , R 16 and R 17 are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, and at least one -CH 2 in these R 15 , R 16 and R 17 - May be replaced by -O-, at least one hydrogen may be replaced by fluorine, and R 17 may be hydrogen or fluorine; Ring E 1 , Ring E 2 , Ring E 3 , and Ring E 4 are independent, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl.
• Ring E 5 and ring E 6 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Jeil;
• Z 18 , Z 19 , Z 20 and Z 21 are independently single-bonded, -COO-, -OCO-, -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2- , -(CH 2 ) 2- , -CF 2 O- (CH 2 ) 2- , or -OCF 2- (CH 2 ) 2- ;
• L 15 and L 16 are independently fluorine or chlorine;
• S 11 is hydrogen or methyl;
• X is -CHF- or -CF 2- ;
• Item 11 The liquid crystal composition according to any one of Items 6 to 10, which contains at least one polymerizable compound represented by the formula (20) other than the compound represented by the formula (1).
• Rings F and I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl, or pyridine.
• ⁇ 2-Il, in rings F and I, at least one hydrogen is halogen, alkyl with 1 to 12 carbon atoms, alkoxy with 1 to 12 carbon atoms, or at least one hydrogen is replaced with halogen.
• Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, Naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene- 2,7-Diyl, phenanthrene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-di
• Z 22 and Z 23 are independently single-bonded or alkylene with 1 to 10 carbon atoms, and in these Z 22 and Z 23 , at least one -CH 2- is -O-, -CO-, -COO.
• P 11, P 12, and P 13 are independently a polymerizable group;
• Sp 11 , Sp 12 , and Sp 13 are independently single-bonded or alkylenes having 1 to 10 carbon atoms, and in these Sp 11 , Sp 12 , and Sp 13 , at least one -CH 2- is -O.
• At least one hydrogen may be replaced with fluorine or chlorine; u is 0, 1, or 2; f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is greater than or equal to 1.
• Item 12 In equation (20) Item 2.
• M 11 , M 12 , and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with a halogen.
• Item 13 Item 11 or 12 that the polymerizable compound represented by the formula (20) is at least one compound selected from the group of the polymerizable compounds represented by the formulas (20-1) to (20-7).
• L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 , and L 38 are independently hydrogen, fluorine, or methyl;
• P 11 , P 12 , and P 13 are independently selected groups from the group of polymerizable groups represented by formulas (P-1) to (P-3).
• M 11 , M 12 , and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms in which at least one hydrogen is replaced with a halogen.
• Item 14 A polymerizable compound different from the compound represented by the formula (1) or the formula (20), a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, and a dye.
• Item 15 At least one selected from the group consisting of the liquid crystal composition according to any one of items 6 to 14 and at least a part of the liquid crystal composition according to any one of items 6 to 14 polymerized. Liquid crystal display element containing.
• the present invention also includes the following sections.
• A) Add at least two additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, defoamers, etc.
• the above-mentioned liquid crystal composition contained.
• B) A polymerizable composition prepared by adding a polymerizable compound different from the compound (1) or the compound (20) to the liquid crystal composition.
• C A polymerizable composition prepared by adding compound (1) and compound (20) to the above liquid crystal composition.
• D) A liquid crystal composite prepared by polymerizing the polymerizable composition.
• E) A polymer-supported orientation type device containing this liquid crystal composite.
• F) A polymerizable composition prepared by adding a compound (1), a compound (20), and a polymerizable compound different from the compound (1) or the compound (20) to the liquid crystal composition is used.
• the compound (1) of the present invention is characterized by having a mesogen moiety composed of at least one ring, a polymerizable group such as methoxymethacryloyloxy, and a polar group such as an ⁇ OH group. ..
• Compound (1) is useful because the polar group interacts non-covalently with the surface of a substrate such as glass (or metal oxide).
• a substrate such as glass (or metal oxide).
• One of the uses is an additive for a liquid crystal composition used in a liquid crystal display element, and in this use, compound (1) is added for the purpose of controlling the orientation of liquid crystal molecules.
• Such additives are chemically stable under the conditions sealed in the device, have high heat stability, have a high ability to orient liquid crystal molecules, and hold voltage when used in a liquid crystal display device. It is preferable that the ratio is high and the solubility in the liquid crystal composition is high.
• the compound (1) satisfies such properties to a considerable extent and has extremely high solubility in a liquid crystal composition, which cannot be achieved by the conventional compound.
• the conventional compound can be used. It is possible to easily obtain an element having excellent long-term stability while maintaining the same or higher orientation and voltage retention rate as compared with the case of using.
• a preferred example of compound (1) will be described. Preferred examples of symbols such as R 1 , A 1 , Sp 2 in compound (1) also apply to sub-formulas of compound (1), such as formula (1-1).
• the properties can be arbitrarily adjusted by appropriately combining the types of these groups.
• Compound (1) may contain more isotopes such as 2 H (deuterium) and 13 C than the natural abundance ratio, as there are no significant differences in the properties of the compounds.
• a more preferred R 1 is an alkyl having 1 to 10 carbon atoms.
• R 1 is an alkyl having 1 to 15 carbon atoms
• a compound in which R 1 is an alkyl having 1 to 15 carbon atoms has a high solubility in a liquid crystal composition.
• Compounds in which R 1 is an alkyl having 1 to 15 carbon atoms have a high ability to orient liquid crystal molecules.
• Rings A 1 and A 2 are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4. -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2 , 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in which ring a 1 and ring a 2, at least one hydrogen May be replaced with fluorine, chlorine, alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms,
• Preferred rings A 1 and A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or 1 , 3-dioxane-2,5-diyl, in which ring a 1 and ring a 2, at least one of hydrogen, fluorine, chlorine, alkyl of 1 to 10 carbons, alkenyl having 2 to 10 carbon atoms, carbon It may be replaced with an alkoxy of number 1 to 9 or an alkenyloxy having 2 to 9 carbon atoms, in which at least one hydrogen may be replaced by fluorine or chlorine.
• rings A 1 and A 2 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, or It is 1,3-dioxane-2,5-diyl, and in rings A 1 and A 2 , at least one hydrogen is fluorine, an alkyl having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms, or carbon. It may be replaced with alkoxy of numbers 1 to 4.
• Particularly preferred rings A 1 and A 2 are 1,4-cyclohexylene, 1,4-phenylene, 2- and 3-position substituted, or 2- and 3-position substituted 1,4-phenylene, said substituents. It is preferably hydrogen, fluorine, an alkyl having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms, or an alkoxy having 1 to 4 carbon atoms, and more preferably hydrogen, fluorine, methyl, or ethyl. ..
• Ring A 1 and Ring A 2 are independent, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-phenylene, at least one hydrogen replaced with fluorine 1 , 4-Phenylene, 1,4-phenylene in which at least one hydrogen is replaced by an alkyl having 1 to 5 carbon atoms, decahydronaphthalene-2,6-diyl, or tetrahydropyran-2,5-diyl , High in chemical stability.
• Ring A 1 and Ring A 2 are independent, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with fluorine, at least A compound in which one hydrogen is replaced with an alkyl having 1 to 5 carbon atoms is 1,4-phenylene, or at least one hydrogen is replaced with an alkenyl having 2 to 5 carbon atoms is 1,4-phenylene. Highly soluble in substances.
• a compound in which ring A 1 and ring A 2 are independently 1,4-cyclohexylene, 1,4-phenylene, and 1,4-phenylene in which at least one hydrogen is replaced with an alkyl having 1 to 2 carbon atoms.
• Rings A 1 and A 2 are independent, 1,4-phenylene, at least one hydrogen is replaced with an alkyl having 1 to 5 carbon atoms, 1,4-phenylene, and at least one hydrogen is 1 to 4 carbon atoms.
• Compounds such as 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl replaced by the alkoxy in the above have high polymerization reactivity by ultraviolet irradiation.
• a is 0, 1, 2, 3, or 4, preferably 0, 1, 2, or 3, more preferably 1, 2, or 3, and particularly preferably 1 or. It is 2.
• the compound in which a is 0 has a high solubility in the liquid crystal composition.
• a compound in which a is 3 or 4 has a high ability to orient liquid crystal molecules.
• a compound having a of 1 or 2 has a high solubility in a liquid crystal composition, a high ability to orient liquid crystal molecules, and a high polymerization reactivity by ultraviolet irradiation.
• B and c are independently 0, 1, or 2.
• the sum of b and c is one or more. More preferably, the sum of b and c is 1, 2, 3, or 4. When the sum of b and c is 1 or 2, the solubility is high.
• a compound having a total of 1 or more of b and c will have a polymerizable group on ring A 1 or ring A 2 .
• the polymerization reactivity due to ultraviolet irradiation is high.
• a compound in which Z 1 is a single bond has high chemical stability.
• a compound in which Z 1 is a single bond,-(CH 2 ) 2- , -CF 2 O-, or -OCF 2- has high solubility in a liquid crystal composition.
• Compounds in which Z 1 is a single bond or-(CH 2 ) 2- have a high ability to orient liquid crystal molecules.
• P 1 and P 2 are independently derived from the groups represented by the formulas (1-p1), formula (1-p2), formula (1-p3), formula (1-p4) and formula (1-p5).
• the selected group preferably at least one of P 1 and P 2 , is among the groups represented by the formulas (1-p1), (1-p2), and formula (1-p3). It has at least one group.
• Preferred P 1 and P 2 are groups selected from the groups represented by the formulas (1-p1), formula (1-p2) and formula (1-p3).
• Sp 1 is independently a single bond or an alkylene having 1 to 7 carbon atoms have high chemical stability.
• Sp 1 is independently alkylene of 1 to 7 carbon atoms, or at least one -CH 2 in the alkylene from 1 to 7 carbon atoms - a compound which is is replaced by -O- groups, to a liquid crystal composition High solubility.
• R 2 is independently alkyl of 1 to 5 carbon atoms. Preferred R 2 has 1 to 3 carbon atoms. More preferably, R 2 has 1 carbon atom, and in this case, it has high reactivity and can maintain the ability to orient liquid crystal molecules and the voltage holding ratio when used in a liquid crystal display element.
• R 3 is independently a linear alkyl having 1 to 10 carbon atoms, a branched chain alkyl having 3 to 10 carbon atoms, or a cyclic alkyl having 3 to 8 carbon atoms.
• Preferred R 3 is 1 to 5 carbon atoms. More preferably, R 3 has 1 carbon atom, and in this case, it has high reactivity and can maintain the ability to orient liquid crystal molecules and the voltage holding ratio when used in a liquid crystal display element.
• Y 1 is independently chlorine, fluorine, or bromine. Preferred Y 1 is fluorine. When Y 1 is fluorine, the solubility is high.
• One hydrogen may be replaced with fluorine, chlorine, a group represented by the formula (1-p1), the formula (1-p2), the formula (1-p3) or the formula (1-p4).
• P 1 and P 2 has at least one of the groups represented by the formulas (1-p1), formula (1-p2), and formula (1-p3).
• At least one hydrogen is fluorine, chlorine, a group represented by the formula (1-p1), the formula (1-p2), the formula (1-p3), the formula (1-p4) or the formula (1-p5). It may be replaced. However, if neither P 1 nor P 2 has a group represented by the formulas (1-p1), formula (1-p2), and formula (1-p3), Sp 2 has the number of carbon atoms. It is an alkylene of 1 to 10, and in this Sp 2 , at least one -CH 2- is replaced by a group represented by the formula (1-a), and at least one -CH 2- is -O-,.
• At least one hydrogen is represented by fluorine, chlorine, formula (1-p1), formula (1-p2), formula (1-p3), formula (1-p4) or formula (1-p5). It may be replaced with a base.
• Sp 2 is a single bond or alkylene of 1 to 7 carbon atoms, in the Sp 2, at least one -CH 2 - is replaced with a group represented by -O- or the formula (1-a) At least one hydrogen may be replaced with fluorine or chlorine. Further preferred Sp 2 is a single bond or alkylene of 1 to 7 carbon atoms, in the Sp 2, at least one -CH 2 - is replaced with a group represented by -O- or the formula (1-a) May be done.
• Sp 2 is a single bond or an alkylene having 1 to 7 carbon atoms have high chemical stability.
• Sp 2 is a group in which alkylene having 1 to 7 carbon atoms or at least one -CH 2- of alkylene having 1 to 7 carbon atoms is replaced with -O- or a group represented by the formula (1-a).
• the compound has high solubility in the liquid crystal composition.
• X 1 is a polar group having a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, phosphorus and silicon.
• Preferred X 1 is a polar group represented by any one of the formulas (X-1) to (X-27).
• J 1 and J 2 are independently hydrogen, or a linear alkyl having 1 to 5 carbon atoms or a branched chain alkyl having 3 to 5 carbon atoms, and in these J 1 and J 2 , at least one -CH 2- May be replaced with —O—.
• J 3 is hydrogen, or a linear alkyl having 1 to 20 carbon atoms or a branched chain alkyl having 3 to 20 carbon atoms. In this J 3 , at least one -CH 2- is -O-, -COO-. Alternatively, it may be replaced with -OCO-.
• J 4 and J 5 are independently hydrogen or alkyl having from 1 to 8 carbon atoms;
• Q 1 is methine or nitrogen, where the hydrogen of methine may be replaced by an alkyl having 1 to 6 carbon atoms.
• U 1 and U 2 are independently -CH 2- , -O-, -CO- or -S-.
• V 1 , V 2 and V 3 are independently methine or nitrogen, and at least one of V 1 , V 2 and V 3 contains nitrogen.
• W 1 is -O- or -S-.
• W 2 is carbon, sulfur or silicon.
• Q 1 is methine in the formula (X-14)
• at least one of U 1 and U 2 is -O-, -CO- or -S-.
• More preferred X 1 is, -OH, -NH 2, -OR 4 , -N (R 4) 2, -COOH, -SH or -Si (R 4), 3. Further preferable X 1 is -OH, -NH 2 , or -SH, and particularly preferable X 1 is -OH from the viewpoint of making the compound more excellent in solubility in the liquid crystal composition.
• a compound in which X 1 is -OH, -NH 2 , or -SH have a high ability to orient liquid crystal molecules.
• a compound in which X 1 is ⁇ OH has high chemical stability, high ability to orient liquid crystal molecules, high voltage retention when used in a liquid crystal display element, and high solubility in a liquid crystal composition.
• the preferred compound (1) has at least one group among the groups represented by the formulas (1-p1), (1-p2), and (1-p3).
• Examples of the preferable compound (1) are the compounds (1-1) to (1-8) described in Item 3. Examples of the more preferable compound (1) are the compounds (1-9) to (1-16) described in Item 4. Examples of a more preferable compound (1) are the compounds (1-17) to (1-145) described in Item 5.
• MSG 1 (or MSG 2 ) is a monovalent organic group having at least one ring.
• the monovalent organic groups represented by the plurality of MSG 1 (or MSG 2 ) may be the same or different.
• Compounds (1A) to (1H) correspond to compound (1) or an intermediate of compound (1).
• the boric acid compound (21) and the compound (22) are reacted in the presence of a carbonate and a tetrakis (triphenylphosphine) palladium catalyst to synthesize the compound (1A).
• This compound (1A) can also be synthesized by reacting compound (23) with n-butyllithium and then zinc chloride, and then reacting compound (22) in the presence of a dichlorobis (triphenylphosphine) palladium catalyst.
• rings A 1 and A 2 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-cyclohexenylene , 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl , 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, etc., are commercially available starting materials or well-known synthetic methods. ..
• the compound (1-X51) in which the polar group is the formula (X-24) and the polymerizable group is fluoroacryloyloxy can be synthesized by the following method.
• Compound (51) is reacted in the presence of formaldehyde and DABCO (1,4-diazabicyclo [2.2.2] octane) to give compound (52).
• Compound (52) is reacted in the presence of pyridinium p-toluenesulfonate (PPTS) and 3,4-dihydro-2H-pyran to give compound (53).
• PPTS pyridinium p-toluenesulfonate
• Compound (54) is reacted with 2-fluoroacrylic acid, N, N-dicyclohexylcarbodiimide (DCC), N, N-dimethyl-4-aminopyridine (DMAP) to give compound (55).
• Compound (55) is reacted with tetrabutylammonium fluoride (TBAF) to give compound (56).
• Compound (56) is reacted with compound (53), N, N-dicyclohexylcarbodiimide, N, N-dimethyl-4-aminopyridine to give compound (57).
• Compound (57) can be reacted with pyridinium p-toluenesulfonate (PPTS) to lead to compound (1-X51).
• PPTS pyridinium p-toluenesulfonate
• the liquid crystal composition of the present invention contains compound (1) as component A.
• Compound (1) can control the orientation of liquid crystal molecules by non-covalent interaction with the substrate of the device.
• the composition preferably comprises compound (1) as component A and further comprises at least one liquid crystal compound selected from the following components B, C, D, and E.
• Component B is compounds (2) to (4).
• the component C is a compound (5) to (7) other than the compounds (2) to (4).
• Component D is compound (8).
• Component E is compounds (11) to (19).
• the composition may contain other liquid crystal compounds different from compounds (2) to (8) and (11) to (19).
• a composition with properly selected components has a high upper limit temperature, a lower lower limit temperature, a low viscosity, a suitable optical anisotropy (ie, large optical anisotropy or a small optical anisotropy), and a large positive or negative modulus. It has anisotropy, high specific resistance, stability against heat or ultraviolet rays, and a suitable elastic constant (ie, large elastic constant or small elastic constant).
• Compound (1) is added to the composition for the purpose of controlling the orientation of the liquid crystal molecules.
• the preferable ratio of the compound (1) to 100% by weight of the liquid crystal composition is 0.05% by weight or more from the viewpoint that the liquid crystal molecules can be easily oriented, and display defects of the element can be further prevented. From the above points, it is preferably 10% by weight or less. A more preferable ratio is in the range of 0.1% by weight to 7% by weight, and a particularly preferable ratio is in the range of 0.4% by weight to 5% by weight. These proportions also apply to compositions containing compound (20).
• Component B is a compound having two terminal groups such as alkyl.
• Component B has a small dielectric anisotropy.
• Preferred examples of the component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can.
• R 11 and R 12 are independently alkyls with 1 to 10 carbon atoms or alkenyl with 2 to 10 carbon atoms, and in these R 11 and R 12 , at least one -CH 2- is-. It may be replaced with O-, and at least one hydrogen may be replaced with fluorine.
• Component B is a compound that is close to neutral because the absolute value of dielectric anisotropy is small.
• Compound (2) is mainly effective in reducing viscosity or adjusting optical anisotropy.
• the compounds (3) and (4) are effective in widening the temperature range of the nematic phase by increasing the upper limit temperature, or in adjusting the optical anisotropy.
• the content of component B is preferably large.
• the content of the component B is preferably 30% by weight or more, more preferably 40% by weight or more, and the upper limit thereof is not particularly limited, but is, for example, 99.95% by weight, based on 100% by weight of the liquid crystal composition.
• Component C is a compound having fluorine, chlorine or a fluorine-containing group at at least one end.
• Component C has a very large dielectric anisotropy.
• Preferred examples of the component C include compounds (5-1) to (5-16), compounds (6-1) to (6-116), and compounds (7-1) to (7-59). ..
• R 13 is alkenyl having 2 to 10 carbon alkyl or C 1 to 10 carbon atoms, in the R 13, at least one -CH 2 - may be replaced by -O-, At least one hydrogen may be replaced with fluorine;
• X 11 is fluorine, chlorine, -OCF 3 , -OCHF 2 , -CF 3 , -CHF 2 , -CH 2 F, -OCF 2 CHF 2 , or- OCF 2 CHFCF 3 .
• Component C has a positive dielectric anisotropy and very good stability against heat, light, etc., and is therefore preferably used when preparing a composition for modes such as IPS, FFS, and OCB. ..
• the content of component C with respect to 100% by weight of the liquid crystal composition is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and more preferably 40% by weight to 95% by weight. Is the range of.
• the content of the component C is preferably 30% by weight or less with respect to 100% by weight of the liquid crystal composition.
• Component D is compound (8) having one end group of -C ⁇ N or -C ⁇ C-C ⁇ N. Since component D has a cyano group, it has a larger positive dielectric anisotropy. Preferred examples of the component D include compounds (8-1) to (8-64).
• R 14 is alkenyl having 2 to 10 carbon alkyl or C 1 to 10 carbon atoms, in the R 14, at least one -CH 2 - may be replaced by -O-, At least one hydrogen may be replaced by fluorine; -X 12 is -C ⁇ N or -C ⁇ C-C ⁇ N.
• Component D has a positive dielectric anisotropy and a large value, so it is mainly used when preparing a composition for a mode such as TN. By adding this component D, the dielectric anisotropy of the composition can be increased.
• the component D has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy.
• Component D is also useful for adjusting the voltage-transmittance curve of the device.
• the content of component D with respect to 100% by weight of the liquid crystal composition is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and more preferably 40% by weight to 95% by weight. Is the range of.
• the content of the component D is preferably 30% by weight or less with respect to 100% by weight of the liquid crystal composition.
• Component E is compounds (11) to (19).
• Component E has a negatively large dielectric anisotropy. These compounds have phenylene in which the lateral position is substituted with two halogens (fluorine or chlorine), such as 2,3-difluoro-1,4-phenylene.
• Preferred examples of component E are compounds (11-1) to (11-9), compounds (12-1) to (12-19), compounds (13-1) and (13-2), compounds (14-). 1) to (14-3), compounds (15-1) to (15-3), compounds (16-1) to (16-11), compounds (17-1) to (17-3), compounds ( 18-1) to (18-3), and compound (19-1) can be mentioned.
• R 15, R 16, and R 17 are independently alkenyl alkyl carbon atoms or 2 to 10 of 1 to 10 carbons, and in this R 15, R 16, and R 17, at least One -CH 2- may be replaced with -O-, at least one hydrogen may be replaced with fluorine, and R 17 may be hydrogen or fluorine.
• Component E has a large negative dielectric anisotropy.
• Component E is preferably used when preparing compositions for modes such as IPS, VA, PSA and the like. As the content of the component E is increased, the dielectric anisotropy of the composition becomes negatively large, but the viscosity becomes large. Therefore, as long as the required value of the threshold voltage of the element is satisfied, the content is preferably small. Considering that the dielectric anisotropy is about ⁇ 5, the content of the component E with respect to 100% by weight of the liquid crystal composition is preferably 40% by weight or more in order to drive the liquid crystal sufficiently.
• the compound (11) is a bicyclic compound, and therefore has the effects of lowering the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since compounds (12) and (13) are tricyclic compounds and compound (14) is a tetracyclic compound, they have the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. is there.
• the compounds (15) to (19) have the effect of increasing the dielectric anisotropy.
• the content of the component E is preferably 40% by weight or more, more preferably 50% by weight to 95% by weight, based on 100% by weight of the liquid crystal composition.
• the content of the component E is preferably 30% by weight or less with respect to 100% by weight of the liquid crystal composition.
• a liquid crystal composition can be prepared that satisfies at least one of the properties such as specific resistance, high stability against ultraviolet rays, high stability against heat, and a large elastic constant.
• Additives Liquid crystal compositions are prepared by known methods. For example, a method of mixing the components and dissolving them by heating can be mentioned. Additives may be added to this composition depending on the application. Examples of additives include polymerizable compounds other than compound (1), polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, defoamers, etc. Is. Such additives are well known to those of skill in the art and are described in the literature.
• the polymerizable compound is added for the purpose of forming a polymer in the liquid crystal composition.
• a polymer can be produced by injecting a liquid crystal composition into an element and irradiating it with ultraviolet rays while applying a voltage between the electrodes to polymerize the compound (1).
• the compound (1) is immobilized in a state in which its polar group interacts non-covalently with the surface of the glass (or metal oxide) substrate.
• the ability to control the orientation of the liquid crystal molecules is further improved, and an appropriate pretilt angle is obtained, so that the response time is shortened.
• Preferred examples of polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxylane, oxetane), and vinyl ketones. More preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. More preferred examples also include compounds having both acryloyloxy and methacryloyloxy.
• Particularly preferred examples of the polymerizable compound include compound (20).
• Compound (20) is a compound different from compound (1). Compound (1) has a polar group. On the other hand, compound (20) preferably does not have a polar group.
• ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-.
• the preferred ring F or ring I is cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl, or 2-naphthyl. More preferred ring F or ring I is cyclohexyl, cyclohexenyl, or phenyl. A particularly preferred ring F or ring I is phenyl.
• the ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-.
• Preferred ring Gs are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3.
• ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, or 2-fluoro-1,4-phenylene.
• a particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.
• the most preferred ring G is 1,4-phenylene.
• Preferred Z 22 or Z 23 are single bonds,-(CH 2 ) 2- , -CH 2 O-, -OCH 2- , -COO-, or -OCO-. A more preferred Z 22 or Z 23 is a single bond.
• P 11 , P 12 , and P 13 are independently polymerizable groups.
• Preferred P 11 to P 13 are groups selected from the group of polymerizable groups represented by the formulas (P-1) to (P-5).
• P 13 from further preferred P 11 has the formula (P-1), formula (P-2), or a group represented by the formula (P-3).
• Particularly preferable P 11 to P 13 are groups represented by the formula (P-1).
• the wavy lines of the formulas (P-1) to (P-5) indicate the sites to be combined.
• M 11 , M 12 , and M 13 are independently replaced by hydrogen, fluorine, alkyl with 1 to 5 carbon atoms, or at least one hydrogen with halogen. It is an alkyl having 1 to 5 carbon atoms.
• Preferred M 11 , M 12 , or M 13 are hydrogen or methyl to increase reactivity. The more preferred M 11 is hydrogen or methyl, and the more preferred M 12 or M 13 is hydrogen.
• Sp 11 , Sp 12 , and Sp 13 are independently single-bonded or alkylene with 1 to 10 carbon atoms, and at least one -CH in the Sp 11 , Sp 12 , and Sp 13 .
• Preferred Sp 11 , Sp 12 , and Sp 13 are single bonds.
• u is 0, 1, or 2.
• the preferred u is 0 or 1.
• f, g, and h are independently 0, 1, 2, 3, or 4, and the sum of f, g, and h is 1 or greater.
• the preferred f, g, or h is 1 or 2.
• the preferred sum is 2, 3 or 4.
• a more preferred sum is 2 or 3.
• R 25 to R 31 are independently hydrogen or methyl;
• R 32 , R 33 , and R 34 are independently hydrogen or alkyl having 1 to 5 carbon atoms, R 32 , At least one of R 33 , and R 34 is an alkyl having 1 to 5 carbon atoms;
• v and x are independently 0 or 1;
• t and u are independently integers from 1 to 10. Yes, t + v and x + u are each up to 10;
• L 31 to L 36 are independently hydrogen or fluorine, and
• L 37 and L 38 are independently hydrogen, fluorine, or methyl.
• the polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a photoradical polymerization initiator. Further, by optimizing the reaction conditions at the time of polymerization, the amount of the residual polymerizable compound can be reduced.
• a polymerization initiator such as a photoradical polymerization initiator.
• photoradical polymerization initiators include TPO, 1173, and 4265 from BASF's DaroCure series, and 184,369,500,651,784,819,907,1300,1700,1800, from the Irgacure series. 1850, and 2959 are mentioned.
• photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-Phenylaclysine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethylketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4-diethylxanthone / p-dimethylaminomethyl benzoate mixture, benzophenone / methyltriethanolamine mixture Is.
• polymerization After adding a photoradical polymerization initiator to the liquid crystal composition, polymerization can be carried out by irradiating ultraviolet rays with an electric field applied. However, unreacted polymerization initiators or decomposition products of the polymerization initiators can cause display defects such as image burn-in on the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator.
• the preferred wavelength of the emitted light is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range of 250 nm to 450 nm, and most preferred wavelengths are in the range of 300 nm to 400 nm.
• a polymerization inhibitor When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization.
• the polymerizable compound is usually added to the composition without removing the polymerization inhibitor.
• polymerization inhibitors are hydroquinone derivatives such as hydroquinone and methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine.
• the optically active compound has the effect of preventing reverse twisting by inducing a helical structure in the liquid crystal molecule to give a necessary twist angle.
• the spiral pitch can be adjusted by adding an optically active compound.
• Two or more optically active compounds may be added for the purpose of adjusting the temperature dependence of the spiral pitch.
• Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18).
• ring J is 1,4-cyclohexylene or 1,4-phenylene
• R 28 is an alkyl having 1 to 10 carbon atoms. * Marks represent asymmetric carbon.
• Antioxidants are effective in maintaining a large voltage retention.
• Preferred examples of the antioxidants include the following compounds (AO-1) and (AO-2); Irganox415, Irganox565, Irganox1010, Irganox1035, Irganox3114, and Irganox1098 (trade name; BASF).
• the ultraviolet absorber is effective for preventing a decrease in the upper limit temperature.
• UV absorber is benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 328, Tinuvin 99-2 (trade name; BASF); and 1,4-diazabicyclo [2.2.2] octane (DABCO) can be mentioned.
• Light stabilizers such as amines with steric hindrance are preferred for maintaining high voltage retention.
• Preferred examples of light stabilizers are the following compounds (AO-5), (AO-6), and (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770DF (trade name; BASF); LA-77Y and LA- 77G (trade name; ADEKA Corporation) can be mentioned.
• a heat stabilizer is also effective for maintaining a large voltage holding ratio, and Irgafos 168 (trade name; BASF) can be mentioned as a preferable example.
• dichroic dyes such as azo dyes and anthraquinone dyes are added to the composition in order to adapt them to devices in GH (guest host) mode. Defoamers are effective in preventing foaming.
• Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil and the like.
• R 40 is an alkyl having 1 to 20 carbon atoms, an alkoxy having 1 to 20 carbon atoms, -COOR 41 , or-(CH 2 ) 2- COOR 41 , where R 41 is carbon. Alkoxy of numbers 1 to 20.
• R 42 is an alkyl having 1 to 20 carbon atoms.
• R 43 is hydrogen, methyl or O ⁇ be (oxygen radicals); in the compound (AO-7); ring G 1 is 1,4-cyclohexylene or 1,4-phenylene , Ring G 2 is a group in which at least one hydrogen of 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene has been replaced with fluorine; compounds (AO-5) and (AO-7). ), Z is 1, 2, or 3.
• the liquid crystal composition has an operation mode such as PC, TN, STN, OCB, PSA, and can be suitably used for a liquid crystal display element driven by an active matrix method.
• This composition has an operation mode such as PC, TN, STN, OCB, VA, and IPS, and can be suitably used for a liquid crystal display element driven by a passive matrix method.
• These elements can be applied to any type of reflective type, transmissive type, and semitransparent type.
• This composition is also suitable for NCAP (nematic curvilinear aligned phase) devices, where the composition is microencapsulated.
• This composition can also be used in a polymer dispersed liquid crystal display element (PDLCD) and a polymer network liquid crystal display element (PNLCD). In these compositions, a large amount of polymerizable compound is added.
• the proportion of the polymerizable compound is preferably 10% by weight or less with respect to 100% by weight of the liquid crystal composition, and the more preferable ratio is 0.1% by weight to 2% by weight. %, More preferably in the range of 0.2% by weight to 1.0% by weight.
• the PSA mode element can be driven by a drive system such as an active matrix system or a passive matrix system. Such an element can be applied to any type of reflective type, transmissive type, and semitransparent type.
• the polymer contained in the composition orients the liquid crystal molecules.
• Polar compounds help liquid crystal molecules to align. That is, the polar compound can be used instead of the alignment film.
• An example of a method for manufacturing such an element is as follows. An element having two substrates called an array substrate and a color filter substrate is prepared. This substrate has no alignment film. At least one of the substrates has an electrode layer. Liquid crystal compounds are mixed to prepare a liquid crystal composition. Compound (1) and, if necessary, other polymerizable compounds and polar compounds are added to this composition. Additional additives may be added as needed. This composition is injected into the device. Light is irradiated while a voltage is applied to this element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is produced, and an element having a PSA mode is produced.
• the polar compounds are arranged on the substrate because the polar groups interact with the substrate surface.
• This polar compound orients the liquid crystal molecules.
• the interaction with the substrate surface becomes stronger and the orientation can be performed at a low concentration.
• the orientation of the liquid crystal molecules is further promoted by the action of the electric field.
• the polymerizable compound is also oriented according to this orientation. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer that maintains this orientation is produced. The effect of this polymer further stabilizes the orientation of the liquid crystal molecules, thus shortening the response time of the device.
• the burn-in of the image is a malfunction of the liquid crystal molecules, the burn-in is also improved at the same time by the effect of this polymer.
• compound (1) is polymerizable, it is consumed by polymerization.
• Compound (1) is also consumed by copolymerizing with other polymerizable compounds. Therefore, although compound (1) has a polar group, it is consumed, so that a liquid crystal display element having a large voltage holding ratio can be obtained. If a polar compound having a polymerizable property is used, the effects of both the polar compound and the polymerizable compound can be achieved with one compound, so that a polymerizable compound having no polar group may not be required. is there.
• the present invention will be described in more detail by way of examples (including synthetic examples and usage examples). The present invention is not limited by these examples.
• the present invention also includes a mixture prepared by mixing at least two of the compositions of Examples.
• Example of compound (1) Unless otherwise specified, the reaction was carried out in a nitrogen atmosphere. Compound (1) was synthesized by the procedure shown in Example 1 and the like. The synthesized compound was identified by a method such as NMR analysis. The characteristics of compound (1), liquid crystal compound, composition, and device were measured by the following methods.
• NMR analysis A DRX-500 manufactured by Bruker Biospin was used for the measurement. 1 In the 1 H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl 3, and the measurement was carried out at room temperature under the conditions of 500 MHz and 16 times of integration. Tetramethylsilane was used as an internal standard. 19 In the F-NMR measurement, CFCl 3 was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sext means sextet, m means multiplet, and br means broad.
• a GC-2010 type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement.
• a capillary column DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m) manufactured by Agilent Technologies Inc. was used.
• Helium (1 ml / min) was used as the carrier gas.
• the temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) portion was set to 300 ° C.
• the sample was dissolved in acetone to prepare a 1% by weight solution, and 1 ⁇ l of the obtained solution was injected into the sample vaporization chamber.
• a GC Solution system manufactured by Shimadzu Corporation was used as the recorder.
• HPLC analysis Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for the measurement.
• YMC-Pack ODS-A length 150 mm, inner diameter 4.6 mm, particle diameter 5 ⁇ m
• the eluate used was an appropriate mixture of acetonitrile and water.
• the detector a UV detector, an RI detector, a CORONA detector and the like were appropriately used. When a UV detector was used, the detection wavelength was 254 nm.
• the sample was prepared to dissolve in acetonitrile to form a 0.1% by weight solution, and 1 ⁇ L of this solution was introduced into the sample chamber.
• C-R7Aplus manufactured by Shimadzu Corporation was used.
• Ultraviolet-visible spectroscopic analysis For the measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was 190 nm to 700 nm. The sample was prepared by dissolving it in acetonitrile to form a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length 1 cm) for measurement.
• Measurement sample When measuring the phase structure and transition temperature (transparency point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample.
• Measurement method The characteristics were measured by the following method. Most of these are methods described in the JEITA standard (JEITA ED-2521B), which is deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method. there were. A thin film transistor (TFT) was not attached to the TN element used for the measurement.
• JEITA Japan Electronics and Information Technology Industries Association
• Phase structure A sample was placed on a hot plate (FP-52 type hot stage manufactured by Mettler) of a melting point measuring device equipped with a polarizing microscope. The phase state and its change were observed with a polarizing microscope while heating this sample at a rate of 3 ° C./min to identify the type of phase.
• Transition temperature (° C)
• a scanning calorimeter manufactured by PerkinElmer Co., Ltd., a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., X-DSC7000 was used.
• the temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the start point of the endothermic peak or the exothermic peak accompanying the phase change of the sample was determined by extrapolation to determine the transition temperature.
• the melting point and polymerization initiation temperature of the compound were also measured using this device.
• the temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "lower limit temperature of the liquid crystal phase”.
• the temperature at which a compound transitions from the liquid crystal phase to a liquid may be abbreviated as "transparency point”.
• the crystal was represented as C. When the types of crystals can be distinguished, they are represented as C 1 and C 2 , respectively.
• the smectic phase was represented as S and the nematic phase was represented as N.
• a smectic A phase, a smectic B phase if can be distinguished in the smectic C phase, or a smectic F phase, respectively S A, S B, expressed as S C or S F,.
• the liquid (isotropic) was represented as I.
• the transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C. and the transition temperature from the nematic phase to the liquid is 100.0 ° C.
• T C Minimum Temperature of a Nematic Phase
• a sample having a nematic phase was stored in a freezer at 0 ° C., ⁇ 10 ° C., ⁇ 20 ° C., ⁇ 30 ° C., and ⁇ 40 ° C. for 10 days, and then the liquid crystal phase was observed.
• TC was described as ⁇ -20 ° C when the sample remained in the nematic phase at -20 ° C and changed to a crystalline or smectic phase at -30 ° C.
• the lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature”.
• Viscosity Bulk viscosity; ⁇ ; measured at 20 ° C; mPa ⁇ s
• An E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.
• the method of measuring the characteristics may differ between a sample with a positive dielectric anisotropy and a sample with a negative dielectric anisotropy.
• the measuring method when the dielectric anisotropy is positive is described in Items (8a) to (12a).
• the dielectric anisotropy is negative, it is described in the items (8b) to (12b).
• Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C.; mPa ⁇ s) Positive Permittivity Anisotropy: Measurements were made according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degrees and a distance (cell gap) between the two glass substrates of 5 ⁇ m. A voltage was applied to this device stepwise in 0.5 V increments in the range of 16 V to 19.5 V. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds).
• Viscosity Rotational viscosity; ⁇ 1; measured at 25 ° C.; mPa ⁇ s) Negative Permittivity Anisotropy: Measurements were made according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a VA element having a distance (cell gap) of 20 ⁇ m between the two glass substrates. A voltage was applied to this element stepwise in 1 volt increments in the range of 39 to 50 volts. After no application for 0.2 seconds, application was repeated under the conditions of only one square wave (square pulse; 0.2 seconds) and no application (2 seconds).
• a sample was placed in a VA element in which the distance (cell gap) between the two glass substrates was 4 ⁇ m, and this element was sealed with an adhesive that cures with ultraviolet rays.
• a sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity ( ⁇ ) of the liquid crystal molecule in the major axis direction was measured.
• the sample was placed in a TN element in which the distance (cell gap) between the two glass substrates was 9 ⁇ m and the twist angle was 80 degrees.
• a sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the permittivity ( ⁇ ) of the liquid crystal molecule in the minor axis direction was measured.
• Threshold voltage (Vth; measured at 25 ° C; V) Positive permittivity anisotropy An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement.
• the light source was a halogen lamp.
• the sample was placed in a normally white mode TN element in which the distance (cell gap) between the two glass substrates was 0.45 / ⁇ n ( ⁇ m) and the twist angle was 80 degrees.
• the voltage (32 Hz, square wave) applied to this device was gradually increased by 0.02 V from 0 V to 10 V.
• the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured.
• a voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum.
• the threshold voltage is expressed as the voltage when the transmittance reaches 90%.
• the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured.
• a voltage-transmittance curve was created in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was minimum.
• the threshold voltage is expressed as the voltage when the transmittance reaches 10%.
• the rise time ( ⁇ r: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%.
• the fall time ( ⁇ f: fall time; millisecond) is the time required for the transmittance to change from 10% to 90%.
• the response time was expressed as the sum of the rise time and the fall time obtained in this way.
• a square wave (60 Hz, 10 V, 0.5 seconds) was applied to this device.
• the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum.
• the response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; fall time; millisecond).
• the polymerizable compound was polymerized by irradiating with ultraviolet rays using F40T10 / BL (peak wavelength 369 nm), a black light manufactured by Eye Graphics Co., Ltd.
• a pulse voltage 60 microseconds at 1 V was applied to this device at 60 ° C. to charge it.
• the decaying voltage was measured with a high-speed voltmeter for 1.67 seconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined.
• Area B is the area when there is no attenuation.
• the voltage holding ratio is expressed as a percentage of the area A with respect to the area B.
• Raw material Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (IPA) (1.1%) from Japan Alcohol Trading Co., Ltd. obtained.
• Second step A known compound (T-3) (72.1 g) and tetrahydrofuran (THF) (500 ml) are placed in a reactor, and n-butyllithium (1.6 mol / L, hexane solution) (185) at ⁇ 70 ° C. .7 ml) is added dropwise, and the mixture is stirred at ⁇ 70 ° C. for 1 hour.
• a THF solution (150 ml) of compound (T-4) (50.0 g) was added dropwise thereto, and the mixture was stirred for 5 hours while raising the temperature to room temperature.
• the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate.
• LAH lithium aluminum hydride
• THF tetrahydrofuran
• DMAP N-dimethylaminopyridine
• 2-fluoroacrylic acid 10.5 g
• PPTS pyridinium p-toluenesulfonate
• THF 200 ml
• methanol 200 ml
• PPTS pyridinium p-toluenesulfonate
• THF 100 ml
• methanol 100 ml
• PPTS pyridinium p-toluenesulfonate
• THF 100 ml
• methanol 100 ml
• the ratio of the components of the composition (i) is shown in% by weight.
• a sample was prepared by adding the compound (1-3-30) or the comparative compound (S-1) to the mother liquid crystal (i) at a ratio of 3% by weight to 0.5% by weight. After allowing this sample to stand at 25 ° C. and ⁇ 20 ° C. for 7 days, the sample was visually observed and marked with ⁇ when the nematic phase was maintained and ⁇ when the crystal or smectic phase was precipitated.
• the compound (1-3-30) maintained the nematic phase at both 25 ° C. and -20 ° C. even when 3% by weight was added to the mother liquid crystal, whereas the comparative compound (S-1) When 3% by weight was added, crystals were precipitated at ⁇ 20 ° C.
• These compounds have the same ring structure and are similar in that a plurality of polymerizable groups are bonded to each other, but their compatibility is significantly different. It can be considered that this is because the compound (1-3-30) has a lower crystallinity than the diol compound and thus has an improved affinity for the liquid crystal composition as compared with the comparative compound (S-1). .. Therefore, it can be said that the compound of the present application is an excellent compound having great compatibility.
• V-HBB-2 (3-4) 10% 1O1-HBBH-4 (4-1) 3% 1O1-HBBH-5 (4-1) 5% 3-HHB (F, F) -F (6-3) 9% 3-H2HB (F, F) -F (6-15) 10% 4-H2HB (F, F) -F (6-15) 6% 5-H2HB (F, F) -F (6-15) 8% 3-HBB (F, F) -F (6-24) 10% 5-HBB (F, F) -F (6-24) 21% 3-H2BB (F, F) -F (6-27) 10% 5-HHBB (F, F) -F (7-6) 4% 3-HH2BB (F, F) -F (7-15) 2% 5-HHEBB-F (7-17) 2% The following compound (1-3-245) was added to the above composition in a proportion of 4% by weight.
• V2-HHB-1 (3-1) 4% 3-HB-CL (5-2) 3% 5-HB-CL (5-2) 7% 3-HHB-OCF3 (6-1) 5% 5-HHB (F) -F (6-2) 7% V-HHB (F) -F (6-2) 4% 3-H2HB-OCF3 (6-13) 5% 5-H2HB (F, F) -F (6-15) 5% 5-H4HB-OCF3 (6-19) 15% 5-H4HB (F, F) -F (6-21) 7% 3-H4HB (F, F) -CF3 (6-21) 8% 5-H4HB (F, F) -CF3 (6-21) 10% 2-H2BB (F) -F (6-26) 5% 3-H2BB (F) -F (6-26) 10% 3-HBEB (F, F) -F (6-39) 5%
• the following compound (1-3-237) was added to the above composition in a proportion of 2% by weight.
• the liquid crystal composition containing the compound (1) can be used for a display element of a liquid crystal projector, a liquid crystal television, or the like.

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• 2020
  • 2020-02-20 CN CN202080006874.1A patent/CN113166035A/zh active Pending
  • 2020-02-20 JP JP2021504885A patent/JPWO2020184142A1/ja active Pending
  • 2020-02-20 WO PCT/JP2020/006863 patent/WO2020184142A1/ja active Application Filing
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