Classifications

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  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
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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
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  • 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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  • C09K19/10—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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  • C09K19/10—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
  • C09K19/30—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
• • 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
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Definitions

• the present invention relates to a compound, a liquid crystal composition and a liquid crystal display device. More specifically, a compound having a plurality of polymerizable groups such as methacryloyloxy and having a substituent lateral to the mesogenic structure, a liquid crystal composition containing this compound and having a positive or negative dielectric anisotropy, and The present invention relates to a liquid crystal display device containing a composition or a cured product of a part thereof.
• 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 ( In-plane switching, VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment) and other modes can be classified. Further, based on the driving method of the element, it can be classified into PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film transistor), MIM (metal insulator metal), and the like.
• 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. Classification based on a light source can be classified into a reflective type that uses natural light, a transmissive type that uses a backlight, and a transflective type that uses both natural light and a backlight.
• a liquid crystal composition having a nematic phase has appropriate properties. By improving the properties of this composition, an AM device having good properties 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 characteristics of the composition will be further described based on a commercially available AM device.
• the temperature range of the nematic phase (the temperature range in which the nematic phase is exhibited) is related to the temperature range in which the device can be used.
• the preferred maximum temperature of the nematic phase is about 70° C. or higher, and the preferred minimum 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 preferable for displaying a moving image on the device. Response times as short as 1 millisecond are desirable. Therefore, the viscosity of the composition is preferably low, and more preferably low even at low temperature.
• the optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, large optical anisotropy or small optical anisotropy, that is, 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 mode of operation. This value is about 0.45 ⁇ m in a device having a mode such as TN. This value is in the range of about 0.30 ⁇ m to about 0.40 ⁇ m for the VA mode device and about 0.20 ⁇ m to about 0.30 ⁇ m for the IPS mode or FFS mode device.
• 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 a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, positive or negative large dielectric anisotropy is preferable.
• the large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, in the initial stage, a composition having a large specific resistance at room temperature as well as at a temperature close to the maximum temperature of the nematic phase is preferable.
• a composition having a large specific resistance not only at room temperature but also at a temperature close to the maximum temperature of the nematic phase after being used for a long time is preferable.
• the stability of the composition against UV and heat is related to the lifetime of the device. When this stability is high, the life of the device is long. Such characteristics are preferable for an AM element used in a liquid crystal projector, a liquid crystal television, or the like.
• a liquid crystal composition containing a polymer is used.
• a composition containing a small amount of a polymerizable compound 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 polymer network in the composition.
• the orientation of liquid crystal molecules can be controlled by the polymer, so that the response time of the device is shortened and image sticking is improved.
• Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
• a polar compound is added to a liquid crystal composition to align liquid crystal molecules.
• a device containing a small amount of a polar compound and a small amount of a 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 aligned 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 is polymerized to stabilize the alignment of liquid crystal molecules.
• this composition it becomes possible to control the alignment of the liquid crystal molecules by the polar compound and the polymer, so that the response time of the device is shortened and the image sticking is improved.
• the step of forming the alignment film is unnecessary. Since there is no alignment film, the electrical resistance of the device does not decrease due to the interaction between the alignment film and the composition.
• Such an effect of the combination of the polar compound and the polymer can be expected in a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
• Patent Document 1 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 to provide high chemical stability, high ability to align liquid crystal molecules, high polymerization reactivity by UV irradiation, large voltage holding ratio when used in a liquid crystal display device, suppression of afterimage, stable stability. It is to provide compounds having at least one of the formation of pretilt angles and having high solubility in liquid crystal compositions.
• the second problem includes this compound, and includes a high upper temperature limit of the nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, a suitable optical anisotropy, a large positive or negative dielectric anisotropy, and a large specific resistance.
• a liquid crystal composition satisfying at least one of properties such as high stability against ultraviolet rays, high stability against heat, and large elastic constant.
• the third problem is that at least one of characteristics such as a wide temperature range in which the device can be used, a short response time, a high transmittance, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a long lifetime, and a good orientation property. It is to provide a liquid crystal display device having two.
• the present invention relates to a compound represented by formula (1), a liquid crystal composition containing the compound, and a liquid crystal display device containing the composition and/or a polymer obtained by polymerizing at least a part of the composition.
• R 1 , R 2 and R 3 are independently hydrogen, —Sp—P, or alkyl having 1 to 15 carbons, and in this R 1 , R 2 and R 3 , at least one —CH 2 — is , —O— or —S—, at least one —(CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and at least one hydrogen is , May be replaced by fluorine or chlorine; Ring A 1 , ring A 2 , ring A 3 and ring A 4 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
• Alkenyloxy, or -Sp-P at least one hydrogen may be replaced by fluorine or chlorine, and a plurality of ring A 1 , ring A 2 and ring A 3 are present in the structure.
• Each may be different, if a and b are independently 0, 1, 2 or 3 and c is 1, 2, 3 or 4;
• Z 1 , Z 2 and Z 3 are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this Z 1 , Z 2 and Z 3 , at least one —CH 2 — is —O—, May be replaced by —CO—, —COO—, —OCO—, or —OCOO—, where at least one —(CH 2 ) 2 — is replaced by —CH ⁇ CH— or —C ⁇ C—.
• At least one hydrogen may be replaced by fluorine or chlorine, and when there are multiple Z 1 , Z 2 and Z 3 in the structure, each may be different;
• Sp is a single bond or alkylene having 1 to 10 carbon atoms, and in this Sp, at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, Or —OCOO—, at least one —(CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, and at least one hydrogen is fluorine or chlorine.
• P is a group represented by any one of formula (1b) to formula (1h), and when a plurality of P are present in the structure, each may be different, but at least One P is a group in which R 4 in formula (1b) is —CH 2 OCH 3 or —CH 2 OH;
• R 4 in formula (1b) is —CH 2 OCH 3 or —CH 2 OH;
• M 1 , M 2 , M 3 and M 4 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen has been replaced by halogen;
• R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently hydrogen or alkyl having 1 to 15 carbons, and R 4 , R 5 , R 6 , R 7 , R 8 and R 8 In R 9 , at least one —CH 2 — may be replaced by —O— or —S—, and at least one —(CH 2 ) 2
• the first advantage of the present invention is chemically high stability, high ability to align liquid crystal molecules, high polymerization reactivity by ultraviolet irradiation, large voltage holding ratio when used in a liquid crystal display device, suppression of afterimage, stable stability. It is to provide compounds having at least one of the formation of pretilt angles and having high solubility in liquid crystal compositions.
• the second advantage is that it contains this compound, and has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a low viscosity, a suitable optical anisotropy, a large positive or negative dielectric anisotropy, a large specific resistance.
• a liquid crystal composition satisfying at least one of properties such as high stability against ultraviolet rays, high stability against heat, and large elastic constant.
• the third advantage is that at least one of characteristics such as a wide temperature range in which the device can be used, a short response time, a high transmittance, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a long lifetime, and a good orientation property. It is to provide a liquid crystal display device having two.
• liquid crystal compound liquid crystal composition
• liquid crystal display device may be abbreviated as “compound”, “composition”, and “device”, respectively.
• liquid crystalline compound is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and has no liquid crystal phase, but controls the physical properties of the composition such as the maximum temperature, the minimum temperature, the viscosity, and the dielectric anisotropy. It is a general term for compounds added for the purpose. This compound usually has a 6-membered ring such as 1,4-cyclohexylene and 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” assists the alignment of liquid crystal molecules by the interaction of polar groups with the surface of the substrate.
• “Liquid crystal display element” is a generic term for liquid crystal display panels, liquid crystal display modules, and the like.
• the liquid crystal composition is usually prepared by mixing a plurality of liquid crystal compounds.
• This composition contains a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and a depolymerizing agent for the purpose of further adjusting physical properties.
• Additives such as foaming agents are added as needed.
• the proportion (content) of the liquid crystal compound in the liquid crystal composition is expressed as a percentage by weight (% 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. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Weight parts per million (ppm) may be used.
• the ratio of the polymerization initiator and the polymerization inhibitor in the liquid crystal composition is exceptionally expressed based on the weight of the polymerizable compound.
• “Clearing point” is the transition temperature between the liquid crystal phase and the isotropic phase in a liquid crystal compound.
• the “minimum 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 “maximum temperature of the nematic phase” is a transition temperature of a nematic phase-isotropic phase in a mixture of a liquid crystal compound and a mother liquid crystal or a liquid crystal composition, and may be abbreviated as “maximum temperature”.
• the “minimum temperature of the nematic phase” may be abbreviated as “minimum temperature”.
• the expressions “increase dielectric anisotropy” and “large dielectric anisotropy” mean that the absolute value of the value increases or increases.
• “High voltage holding ratio” means that the device has a large voltage holding ratio not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature, and even after using the device for a long time, not only at room temperature but also at the upper limit temperature. It means having a large voltage holding ratio even at a temperature close to.
• the characteristics of the composition or device may be examined before and after the aging test (including the accelerated deterioration test).
• the expression “highly soluble in a liquid crystal composition” means that it has a high solubility in any of the compositions containing a liquid crystalline compound at room temperature.
• the composition used to evaluate the solubility can be the standard.
• the compound represented by the formula (1) may be abbreviated as “compound (1)”.
• the 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 formula (2). Symbols such as A 1 , B 1 and C 1 surrounded by hexagons correspond to ring A 1 , ring B 1 and ring C 1 , respectively.
• the hexagon represents a 6-membered ring such as a cyclohexane ring or a benzene ring or a condensed ring such as a naphthalene ring.
• a straight line across one side of this hexagon represents that any hydrogen on the ring may be replaced with a group such as -Sp 1 -P 1 .
• Subscripts such as f, g, and h indicate the number of replaced groups. When the subscript is 0, there is no such replacement.
• ring A and ring C are independently X, Y, or Z,”"independently” is used because the subject is plural. When the subject is “ring A is”, “independently” is not used because the subject is singular.
• the symbol of the terminal group R 11 is used for a plurality of compounds, and 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.
• compound (8) when i is 2, two rings D 1 are present. The two groups represented by the two rings D 1 in this compound may be the same or different. When i is greater than 2, it also applies to any two rings D 1 . This rule also applies to other symbols.
• At least one'A' means that the number of'A's is arbitrary.
• the expression "at least one'A' may be replaced by'B'” means that if'A' itself is not replaced by'B', then one'A' is replaced by'B'. In this case, two or more'A's are replaced with'B', and in these, the position of'A' replaced with'B' is arbitrary.
• the rule that the substitution position is arbitrary also applies to the expression "at least one'A' is replaced by'B'".
• the expression "at least one A may be replaced by B, C, or D" means that when A is not replaced, when at least one A is replaced by B, at least one A is replaced by C.
• alkyl in which at least one —CH 2 — (or —CH 2 CH 2 —) may be replaced by —O— includes alkyl, alkenyl, alkoxy, alkoxyalkyl. , Alkoxyalkenyl, and alkenyloxyalkyl.
• —CH 2 — of the methyl moiety (—CH 2 —H) is replaced with —O— to give —O—H.
• R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH 2 — is replaced with —O— Of course, in these groups, at least one hydrogen may be replaced by fluorine".
• in these groups may be interpreted literally.
• “these groups” means alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, “these groups” refers to all of the groups listed before the term “in these groups”. This common sense interpretation applies to other terms as well.
• Halogen means fluorine, chlorine, bromine, or iodine.
• the preferred halogen is fluorine or chlorine.
• a more preferred halogen is fluorine.
• alkyl is linear or branched and does not include cyclic alkyl. Straight chain alkyls are generally preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl.
• trans is preferable to cis for increasing the maximum temperature of the nematic phase.
• 2-Fluoro-1,4-phenylene means the following two divalent groups.
• fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric bivalent groups formed by removing two hydrogens from a ring, such as tetrahydropyran-2,5-diyl.
• the present invention includes the following items.
• R 1 , R 2 and R 3 are independently hydrogen, —Sp—P, or alkyl having 1 to 15 carbons, and in this R 1 , R 2 and R 3 , at least one —CH 2 — is , —O— or —S—, at least one —(CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and at least one hydrogen is , May be replaced by fluorine or chlorine;
• Ring A 1 , ring A 2 , ring A 3 and ring A 4 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
• Alkenyloxy, or -Sp-P at least one hydrogen may be replaced by fluorine or chlorine, and a plurality of ring A 1 , ring A 2 and ring A 3 are present in the structure.
• Each may be different, if a and b are independently 0, 1, 2 or 3 and c is 1, 2, 3 or 4;
• Z 1 , Z 2 and Z 3 are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this Z 1 , Z 2 and Z 3 , at least one —CH 2 — is —O—, May be replaced by —CO—, —COO—, —OCO—, or —OCOO—, where at least one —(CH 2 ) 2 — is replaced by —CH ⁇ CH— or —C ⁇ C—.
• At least one hydrogen may be replaced by fluorine or chlorine, and when there are multiple Z 1 , Z 2 and Z 3 in the structure, each may be different;
• Sp is a single bond or alkylene having 1 to 10 carbon atoms, and in this Sp, at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, Or —OCOO—, at least one —(CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, and at least one hydrogen is fluorine or chlorine.
• P is a group represented by any one of formula (1b) to formula (1h), and when a plurality of P are present in the structure, each may be different, but at least One P is a group in which R 4 in formula (1b) is —CH 2 OCH 3 or —CH 2 OH;
• R 4 in formula (1b) is —CH 2 OCH 3 or —CH 2 OH;
• M 1 , M 2 , M 3 and M 4 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen has been replaced by halogen;
• R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are independently hydrogen or alkyl having 1 to 15 carbons, and R 4 , R 5 , R 6 , R 7 , R 8 and R 8 In R 9 , at least one —CH 2 — may be replaced by —O— or —S—, and at least one —(CH 2 ) 2
• Ring A 1 , Ring A 2 , Ring A 3 and Ring A 4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydro Pyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, wherein ring A 1 , ring A 2 , ring A 3 And in ring A 4 , at least one hydrogen is fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons.
• P is the formula (1b-1), (1b-2), (1b-3), (1b-4), formula (1b-5), (1c-1), (1d-1), (1d-2) ) Or (1e-1), and when a plurality of Ps are present in the structure, each may be different, provided that at least one P is represented by the formula (1b-4) or (1b- The compound according to any one of [1] to [4] which is 5).
• a and b are independently 0, 1 or 2, provided that a+b is 3 or less, c is 1, 2 or 3, and ring A 1 , ring A 2 , ring A 3 and ring A 4 are independent.
• R 3 is alkyl having 1 to 10 carbons, hydrogen or —Sp 3 —P 3
• Sp 1 , Sp 2 and Sp 3 are independently , A single bond or alkylene having 1 to 10 carbons, wherein in Sp 1 , Sp 2 and Sp 3 , at least one —CH 2 — is replaced with —O—, —COO—, or —OCO—
• at least one —(CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—
• P 1 , P 2 and P 3 are independently of the formula (1b- 1), (1b-2), (1b-3), (1b-4), formula (1b-5), (1c-1), (1d-1), (1d-2) or (1e-1)
• each of them may be different, provided that at least one
• R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this R 11 and R 12 , at least one —CH 2 — is replaced with —O— And at least one hydrogen may be replaced by fluorine;
• Ring B 1 , Ring B 2 , Ring B 3 , and Ring B 4 are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
• Z 11 , Z 12 and Z 13 are independently a single bond, —COO—, —CH 2 CH 2 —, —CH ⁇ CH—, or —C ⁇ C—.
• Ring C 1 , Ring C 2 , and Ring C 3 are independently 1,4-cyclohexylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl.
• Z 14 , Z 15 and Z 16 are independently a single bond, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CH ⁇ CH—, —C ⁇ C—, or —(CH 2 ) 4 —;
• L 11 and L 12 are independently hydrogen or 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 1,4-phenylene with one hydrogen replaced by fluorine
• Z 17 is a single bond, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, or —C ⁇ C—.
• L 13 and L 14 are independently hydrogen or fluorine; i is 1, 2, 3, or 4.
• Ring E 5 and ring E 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6.
• Z 18 , Z 19 , Z 20 and Z 21 are independently a single bond, —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, —CF 2 OCH 2 CH 2 —, or —OCF 2 CH 2 CH 2 —;
• L 15 and L 16 are independently fluorine or chlorine;
• S 11 is hydrogen or methyl;
• X is —CHF— or —CF 2 —;
• j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and the sum of s is 0, 1, 2, or 3, t is 1, 2, or 3.
• 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-diyl
• At least one hydrogen may be replaced by 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 1 or more.
• R 51 is a group represented by —OH, —NH 2 , —OR 53 , —N(R 53 ) 2 , or —Si(R 53 ) 3 , where R 53 is hydrogen or the number of carbon atoms. 1 to 7 alkyl, in which R 53 , at least one —CH 2 — may be replaced by —O—, and at least one —CH 2 CH 2 — may be replaced by —CH ⁇ CH—.
• At least one hydrogen may be replaced by fluorine;
• R 52 is hydrogen, fluorine, or alkyl having 1 to 5 carbons, and in this R 52 , at least one —CH 2 — may be replaced by —O—, and at least one hydrogen is fluorine or May be replaced by chlorine;
• Ring A 50 and ring B 50 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3 -Dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, wherein in ring A 50 and ring B 50 , at least one hydrogen is fluorine, carbon number 1 to 12 alkyl, 1-12 alkoxy, or at least one hydrogen may be replaced by 1-12 alkyl in which fluorine is replaced;
• Sp 51 , Sp 52 , Sp 53 and Sp 54 are a single bond or an alkylene having 1 to 7 carbon atoms, and in this Sp 51 , Sp 52 , Sp 53 and Sp 54 , at least one —CH 2 — is — May be replaced by O—, —COO—, or —OCO—, at least one —CH 2 CH 2 — may be replaced by —CH ⁇ CH—, and at least one hydrogen may be replaced by fluorine.
• a 50 is 0, 1, 2, 3, or 4; a 51 is 1 or 2; l is 0, 1, 2, 3, 4, 5, or 6, and at least one —CH 2 — of —(CH 2 ) l — is —O—, —CO—, —COO—, —OCO—, or —OCOO—, at least one —CH 2 CH 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and at least one hydrogen is It may be replaced by fluorine.
• P 11 , P 12 , and P 13 are each independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5). Liquid crystal composition.
• M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons or alkyl having 1 to 5 carbons in which at least one hydrogen has been replaced by halogen.
• the polymerizable compound represented by the formula (20) is at least one compound selected from the group of polymerizable compounds represented by the formula (20-1) to the formula (20-7), 14] The liquid crystal composition according to any one of [16].
• L 31 , L 32 , L 33 , L 34 , L 35 , L 36 , L 37 , and L 38 are independently hydrogen, fluorine, or methyl;
• Sp 11 , Sp 12 and Sp 13 are independently a single bond or an alkylene having 1 to 10 carbons, and in this Sp 11 , Sp 12 and Sp 13 , at least one —CH 2 — is —O.
• P 11 , P 12 , and P 13 are independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3), In formula (P-1) to formula (P-3), M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons or alkyl having 1 to 5 carbons in which at least one hydrogen has been replaced by halogen.
• a liquid crystal display device containing at least one selected from the group consisting of:
• the present invention also includes the following items.
• A Further, at least two additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye and an antifoaming agent.
• the above-mentioned liquid crystal composition containing.
• B A polymerizable composition prepared by adding a polymerizable compound different from compound (1) or compound (20) to the above liquid crystal composition.
• C A polymerizable composition prepared by adding the compound (1) and the 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 the liquid crystal composite.
• (F) Use of a polymerizable composition prepared by adding the compound (1), the compound (20), and a polymerizable compound different from the compound (1) or the compound (20) to the liquid crystal composition.
• the compound (1) of the present invention is characterized by having a mesogenic moiety composed of at least one ring, at least one polar group, and one or more polymerizable groups, and in particular, a mesogen. It is characterized by having a substituent on the side of the site.
• the compound (1) is useful because the polar group interacts non-covalently with the substrate surface such as glass (or metal oxide).
• One of the uses is an additive for a liquid crystal composition used in a liquid crystal display device, and in this use, the compound (1) is added for the purpose of controlling the alignment of liquid crystal molecules.
• Such an additive is chemically stable under the condition of being sealed in the device, has a high ability to align liquid crystal molecules, has a large voltage holding ratio when used in a liquid crystal display device, and suppresses an afterimage, It is preferable that the pretilt angle is formed stably and the solubility in the liquid crystal composition is large.
• the compound (1) having a ring in the lateral direction satisfies such characteristics to a considerable extent and has extremely high solubility in a liquid crystal composition, which cannot be achieved by conventional compounds, and thus the compound (1) is used.
• a preferred example of the compound (1) will be described. Preferred examples of symbols such as R 1 , A 1 and Sp in the compound (1) also apply to the subordinate formula of the compound (1).
• the properties can be adjusted arbitrarily by appropriately combining the types of these groups.
• Compound (1) may contain isotopes such as 2 H (deuterium) and 13 C in a larger amount than the natural abundance, since there is no large difference in the properties of the compounds.
• R 1 , R 2 and R 3 are independently hydrogen, —Sp—P, or alkyl having 1 to 15 carbons, and in this R 1 , R 2 and R 3 , at least one —CH 2 — is , —O— or —S—, at least one —(CH 2 ) 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and at least one hydrogen is , May be replaced by fluorine or chlorine.
• R 1 and R 2 are -Sp-P
• preferred R 3 is -Sp-P, alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons, or Alkenyloxy having 2 to 14 carbon atoms, in which at least one hydrogen may be replaced by fluorine. More desirable R 3 is —Sp—P, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons. Particularly preferred R 3 is alkyl having 1 to 10 carbons.
• the compound in which R 3 is alkyl having 1 to 15 carbons or alkoxy having 1 to 14 carbons has high chemical stability.
• a compound in which R 3 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, or alkenyloxy having 2 to 14 carbons has high solubility in a liquid crystal composition.
• R 3 is —Sp—P
• the polymerization reaction rate is high.
• the compound in which R 1 is alkyl having 1 to 15 carbons has high ability to align liquid crystal molecules.
• Ring A 1 , ring A 2 , ring A 3 and ring A 4 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, wherein ring A 1 , ring In A 2 , ring A 3 and ring A 4 , at least one hydrogen is fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl
• Preferred ring A 1 , ring A 2 , ring A 3 and ring A 4 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran- 2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, wherein ring A 1 , ring A 2 , ring A 3 and In ring A 4 , at least one hydrogen is replaced with fluorine, chlorine, alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyloxy having 2 to 9 carbons. And at least one hydrogen may be replaced by fluorine or chlorine.
• More preferred ring A 1 , ring A 2 , ring A 3 and ring A 4 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl and tetrahydropyran. -2,5-diyl or 1,3-dioxane-2,5-diyl, wherein at least one hydrogen in the ring A 1 , ring A 2 , ring A 3 and ring A 4 is fluorine, carbon number It may be replaced by 1-10 alkyl, C2-C10 alkenyl, C1-C9 alkoxy, or C2-C9 alkenyloxy and at least one hydrogen may be replaced by fluorine. Good.
• More preferred ring A 1 , ring A 2 , ring A 3 and ring A 4 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl and tetrahydropyran. -2,5-diyl, or 1,3-dioxane-2,5-diyl, in which at least one hydrogen is fluorine, alkyl having 1 to 5 carbons or alkenyl having 2 to 5 carbons. Or may be replaced with an alkoxy having 1 to 4 carbon atoms.
• Particularly preferred ring A 1 , ring A 2 , ring A 3 and ring A 4 are 1,4-cyclohexylene and 1,4-phenylene.
• Ring A 1 and ring A 2 are independently 1,3-cyclopentylene, 1,4-cyclohexylene, 1,4-cycloheptylene, 1,4-phenylene, at least one hydrogen being replaced by fluorine 1.
• 4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 5 carbons, decahydronaphthalene-2,6-diyl, or tetrahydropyran-2,5-diyl is , High chemical stability.
• Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, at least 1,4-phenylene in which one hydrogen is replaced by alkyl having 1 to 5 carbons or 1,4-phenylene in which at least one hydrogen is replaced by alkenyl having 2 to 5 carbons has a liquid crystal composition It has a high solubility 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 by alkyl having 1 to 2 carbons are , High ability to align liquid crystal molecules.
• Ring A 1 and ring A 2 are independently 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by alkyl having 1 to 5 carbons, at least one hydrogen is 1 to 4 carbons
• the 1,4-phenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl substituted with the above alkoxy have high polymerization reactivity upon irradiation with ultraviolet rays.
• a and b are independently 0, 1, 2 or 3
• c is 1, 2, 3 or 4, more preferably a and b are independently 0, 1 or 2.
• A+b is 3 or less
• c is 1, 2 or 3.
• a compound in which a+b is 1 has a high solubility in the liquid crystal composition.
• the compound in which c is 2 or 3 has a high ability to align liquid crystal molecules.
• Z 1 , Z 2 and Z 3 are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this Z 1 , Z 2 and Z 3 , at least one —CH 2 — is —O—, May be replaced by —CO—, —COO—, —OCO—, or —OCOO—, where at least one —(CH 2 ) 2 — is replaced by —CH ⁇ CH— or —C ⁇ C—.
• at least one hydrogen may be replaced by fluorine or chlorine.
• the 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.
• a compound in which Z 1 is a single bond or —(CH 2 ) 2 — has a high ability to align liquid crystal molecules.
• a compound in which Z 1 is a single bond, —CH ⁇ CH—, —C ⁇ C—, —COO—, —OCO—, —CH 2 O—, —OCH 2 — has a high polymerization reactivity upon irradiation with ultraviolet rays.
• Sp is independently a single bond or alkylene having 1 to 10 carbons, and in this Sp, at least one —CH 2 — is —O—, —CO—, —COO—, —OCO—, or —. OCOO—, at least one —(CH 2 ) 2 — may be replaced by —CH ⁇ CH— or —C ⁇ C—, and at least one hydrogen is replaced by fluorine or chlorine. May be
• Preferred Sp is independently a single bond or alkylene having 1 to 7 carbons, and in this Sp, at least one —CH 2 — may be replaced by —O—, —COO—, or —OCO—.
• at least one —(CH 2 ) 2 — may be replaced by —CH ⁇ CH— and at least one hydrogen may be replaced by fluorine.
• a compound in which Sp is independently a single bond or alkylene having 1 to 7 carbons has high chemical stability.
• Sp 1 , Sp 2 , Sp 3 , Sp 4 , and Sp 5 are independently alkylene having 1 to 7 carbon atoms, or at least one —CH 2 — of alkylene having 1 to 7 carbon atoms is replaced by —O—.
• the compound that is the obtained group has high solubility in the liquid crystal composition.
• P is independently a group represented by any one of formula (1b) to formula (1h).
• Preferred P is independently a group represented by any one of formulas (1b), (1c), (1d), and (1e).
• M 1 , M 2 , M 3 and M 4 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced by halogen. It is an alkyl having 1 to 5 carbon atoms.
• Preferred M 1 , M 2 , M 3 and M 4 are independently hydrogen, fluorine, methyl, ethyl or trifluoromethyl. More preferably, it is hydrogen.
• R 4 is hydrogen, halogen, or alkyl having 1 to 5 carbons, and in this R 4 , at least one hydrogen may be replaced with halogen, and at least one —CH 2 — is replaced with —O—. May be.
• Preferred R 4 is hydrogen, fluorine, methyl, ethyl, methoxymethyl, or trifluoromethyl. More preferably, it is hydrogen.
• R 5 , R 6 , R 7 , R 8 and R 9 are independently hydrogen or linear, branched or cyclic alkyl having 1 to 15 carbons, and R 5 , R 6 , R 8 In 7 , R 8 and R 9 , at least one —CH 2 — may be replaced by —O— or —S—, and at least one —(CH 2 ) 2 — is —CH ⁇ CH—. Or it may be replaced by —C ⁇ C— and at least one hydrogen may be replaced by halogen.
• R 5 , R 6 , R 7 , R 8 and R 9 are independently hydrogen, linear alkyl having 1 to 10 carbons, linear alkenyl having 2 to 10 carbons, and 1 to 10 carbons. Is a straight-chain alkoxy or a C3-C6 cyclic alkyl. More preferably, it is hydrogen, linear alkyl having 2 to 6 carbons, linear alkenyl having 2 to 6 carbons, linear alkoxy having 1 to 5 carbons, or cyclic alkyl having 4 to 6 carbons. ..
• P 1 and P 2 More preferred P is P 1 and P 2 , and P 1 and P 2 are represented by formulas (1b-1), (1b-2), (1b-3), (1b-4) and formula (1b-5). , (1c-1), (1d-1), (1d-2) or (1e-1).
• Preferred compounds (1) are compounds (1-1) to (1-10) and compounds (1-101) to (1-141) described in item 7.
• More desirable compound (1) are the following compounds (1-33) to (1-49) and compounds (1-142) to (1-309).
• MSG 1 is a monovalent organic group having at least one ring.
• the monovalent organic groups represented by a plurality of MSG 1 (or MSG 2 ) may be the same or different.
• Compounds (1A) to (1J) correspond to compound (1) or an intermediate of compound (1).
• Rings A 1 , A 2 , A 3 and A 4 1,4-Cyclohexylene, 1,4-Cyclohexenylene, 1,4-Phenylene, 2-Fluoro-1,4-phenylene, 2-Methyl-1 ,4-phenylene, 2-ethyl-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, perhydrocyclopenta[a]phenanthrene-3,17- For rings such as diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16,17-t
• Preferred examples of the polymerizable group P include acryloyloxy (1b), maleimide (1c), itaconic acid ester (1d), vinyl ester (1e), oxiranyl (1g), or It is vinyloxy (1h).
• An example of the method for synthesizing the compound in which the polymerizable group is bonded to the ring by the linking group Sp 1 or Sp 2 is as follows. First, an example in which the linking group Sp 1 or Sp 2 is a single bond is shown.
• MSG 1 is a monovalent organic group having at least one ring.
• Compounds (1S) to (1X) correspond to compound (1).
• the polymerizable group is an acrylate derivative, it is synthesized by esterification of HO-MSG1 with the corresponding acrylic acid.
• Vinyloxy is synthesized by etherification of HO-MSG1 and vinyl bromide.
• Oxiranyl is synthesized by the oxidation of the terminal double bond.
• the maleimide group is synthesized by reacting an amino group with maleic anhydride.
• Itaconic acid esters are synthesized by esterification of the corresponding itaconic acid with HO-MSG1.
• Vinyl ester is synthesized by transesterification reaction between vinyl acetate and HOOC-MSG1.
• the synthetic method of the compound in which the linking group Sp is a single bond has been described above.
• the method for producing another linking group can be synthesized with reference to the method for synthesizing the bonding groups Z 1 , Z 2 , Z 3 , Z 4 and Z 5 .
• Synthetic Example An example of the method for synthesizing the compound (1) is as follows.
• MES is a mesogenic group having at least one ring.
• the definitions of P 1 , M 1 , M 2 , Sp 1 and Sp 2 are the same as above.
• (1) Introduction of SP and P-1 Compound (51A) and compound (51B) are commercially available or can be synthesized according to a general organic synthesis method using mesogen (MES) having a suitable ring structure as a starting material.
• MES mesogen
• the compound (51A) is used as a starting material, and the compound (52) and a base such as potassium hydroxide are used for etherification to synthesize the compound.
• (53A) can be obtained.
• the compound (51B) is used as a starting material, the compound (52), a metal catalyst such as palladium, and a cross-coupling reaction using a base.
• the compound (53B) can be obtained by performing.
• the compound (53A) or (53B) may be derivatized to the compound (54A) or (54B) to which a protecting group such as TMS or THP is applied, if necessary.
• Preferred protecting groups are THP, MOM, TMS, TES, TIPS, TBS, TBDPS, Bn, t-Bu, Me, Boc, Cbz, Fmoc, CH 3 CO-(acetyl).
• Further preferred protecting groups are THP, MOM, TMS, TIPS, TBS, Bn, t-Bu.
• Compound (57A) or (57B) is obtained by subjecting compound (53A), (53B), (54A) or compound (54B) to etherification again in the presence of compound (55) and a base such as potassium hydroxide. Can be obtained. At this time, when the protecting group is reacted in the previous step, the protecting group is removed by a deprotection reaction.
• the compound (1A) in which P 2 is a group represented by the formula (1b-4) can be synthesized from the compound (57) by the following method.
• Compound (1) can be derived from compound (57) by performing an esterification reaction in the presence of compound (58), DCC and DMAP.
• Compound (58) is a known substance.
• the compound (d-2) can be obtained by reducing the commercially available compound (d-1) with lithium aluminum hydride.
• a compound (d-4) can be obtained by reacting a commercially available compound (d-3) with an appropriate protecting group such as THP and Bn.
• the compound (d-5) can be obtained by reacting the compounds (d-2) and (d-4) with p-toluenesulfonic acid which is an acid catalyst.
• the compound (e-2) can be obtained by reacting n-BuLi with a commercially available compound (e-1) as a starting material and then adding DMF.
• the compound (e-3) can be obtained by reacting the compounds (d-2) and (e-2) with p-toluenesulfonic acid which is an acid catalyst.
• the compound (f-2) can be obtained by acting an appropriate protecting group such as THP and Bn.
• the compound (f-3) can be obtained by reacting the compound (f-2) with n-BuLi and then adding trimethyl borate.
• the compound (f-5) can be obtained by brominating the compound (f-4) with a brominating agent such as N-bromosuccinimide.
• Compound (f-6) can be obtained by Suzuki coupling of compound (f-5) and compound (f-3).
• a compound (g-1) can be obtained by triflating the compound (f-6) of (6) as a starting material.
• Compound (g-2) can be obtained by Suzuki coupling of compound (g-1) and compound (f-3).
• compound (i-2) can be obtained by acting an appropriate protecting group such as THP and Bn. After reacting the compound (i-2) with n-BuLi, trimethyl borate is added to obtain the compound (i-3).
• the compound (i-4) can be obtained by Suzuki coupling the compound (i-3) and the compound (h-6).
• Compound (j-1) can be obtained by reacting n-BuLi with compound (f-5) as a starting material and then adding compound (h-4) in (8).
• the compound (j-2) can be obtained by subjecting the compound (j-1) to silane reduction.
• the compound (j-3) can be obtained by triflating the compound (j-2).
• the compound (J-4) can be obtained by Suzuki coupling the compound (j-3) and the compound (f-3).
• the compound (h-1) can be obtained by reacting the compound (h-5) as a starting material with n-BuLi and then adding the compound (h-1).
• the compound (k-2) can be obtained by subjecting the compound (k-1) to silane reduction.
• the compound (k-3) can be obtained by deprotecting the acetal group of the compound (k-2) with formic acid.
• the compound (k-4) can be obtained by adding the compound (k-3) into ethyl dimethylphosphonoacetate and t-BuOK.
• the compound (1-1) can be obtained by adding the compound (k-3) into (methoxymethyl)triphenylphosphonium chloride and t-BuOK.
• the compound (l-2) can be obtained by reacting the compound (l-1) with p-toluenesulfonic acid and methanol.
• the compound (l-3) can be obtained by adding formic acid to the compound (l-2) for deprotection.
• the compound (1-5) can be obtained by adding the compound (1-3) to the commercially available compound (1-4) and t-BuOK.
• Compound (1-6) can be obtained by reducing compound (1-5) with palladium hydroxide in a hydrogen atmosphere.
• the compound (1-7) can be obtained by deprotecting the acetal of the compound (1-6) with formic acid.
• the compound (1-8) can be obtained by reducing the compound (1-7) with sodium borohydride.
• the compound (m-2) can be obtained by adding diisobutylaluminum hydride and reducing the commercially available compound (m-1).
• the compound (m-3) can be obtained by reacting the compound (m-2) with an appropriate protecting group such as THP and Bn. After reacting the compound (m-3) with n-BuLi, trimethyl borate is added to obtain the compound (m-4).
• Compound (m-5) can be obtained by Suzuki coupling of compound (m-4) and compound (h-6).
• the compound (n-2) can be obtained by reacting a commercially available compound (n-1) with an appropriate protecting group such as THP and Bn.
• the compound (n-3) can be obtained by adding the compound (n-2) to the commercially available compound (1-4) and t-BuOK.
• the compound (n-4) can be obtained by reducing the compound (n-3) with palladium hydroxide in a hydrogen atmosphere.
• the compound (n-5) can be obtained by deprotecting the acetal of the compound (1-6) with formic acid.
• the compound (n-6) can be obtained by reducing the compound (n-5) with sodium borohydride.
• Compound (n-7) can be obtained by reacting compound (n-6) with a suitable protecting group such as THP and Bn.
• the compound (n-8) can be obtained by deprotecting the compound (n-7).
• the compound (n-9) can be obtained by triflating the compound (n-8). After reacting compound (n-9) with n-BuLi, trimethyl borate is added to obtain compound (n-10).
• the compound (n-11) can be obtained by Suzuki coupling the compound (n-10) and the compound (h-6).
• the other side chain can be deprotected, and then Sp or P can be introduced by etherification or esterification to obtain the compound (73).
• the compound (1B) in which P is a group represented by the formula (1b-4) or the formula (1b-5) is obtained by subjecting the compound (73) to an esterification reaction in the presence of the compound (74), DCC and DMAP.
• the compound (1B) can be derived by carrying out.
• Liquid crystal composition 3-1 Component Compound
• the liquid crystal composition of the present invention contains the compound (1) as the component A.
• the compound (1) can control the alignment of liquid crystal molecules by the non-covalent interaction with the substrate of the device.
• This composition preferably contains the compound (1) as the component A, and further contains at least one liquid crystal compound selected from the following components B, C, D and E.
• Ingredient B is compounds (2) to (4).
• Component C is compounds (5) to (7) other than compounds (2) to (4).
• Ingredient D is compound (8).
• Ingredient E is compounds (11) to (19). This composition may contain other liquid crystal compounds different from the compounds (2) to (8) and (11) to (19).
• a composition with properly selected components has a high maximum temperature, a low minimum temperature, a low viscosity, an appropriate optical anisotropy (that is, large optical anisotropy or small optical anisotropy), and a large positive or negative dielectric constant. It has anisotropy, large resistivity, stability to heat or ultraviolet light, 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 alignment of 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 liquid crystal molecules can be easily aligned, etc., and it is possible to further prevent defective display of the device. From the viewpoint of the above, it is preferably 10% by weight or less.
• a more desirable ratio is in the range of 0.1 wt% to 7 wt %, a more desirable ratio is in the range of 0.4 wt% to 5 wt %, and a particularly desirable ratio is in the range of 0.5 wt% to 5 wt %. It is in the range of% by weight. These ratios also apply to compositions containing compound (20).
• Component B is a compound in which the two end groups are alkyl and the like.
• the 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 alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, wherein at least one —CH 2 — is —O— May be replaced with and at least one hydrogen may be replaced with fluorine.
• Component B has a small absolute value of dielectric anisotropy, so it is a compound close to neutrality.
• the compound (2) is mainly effective in decreasing the viscosity or adjusting the optical anisotropy.
• the compounds (3) and (4) are effective in increasing the temperature range of the nematic phase by increasing the maximum 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 based on 100% by weight of the liquid crystal composition, and the upper limit thereof is not particularly limited, but is 99.95% by weight, for example.
• Component C is a compound having a fluorine, chlorine or fluorine-containing group at at least one end.
• the component C has a positively 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 alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—.
• At least one hydrogen may be replaced by 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 has very good stability against heat, light and the like, and therefore is preferably used when preparing a composition for modes such as IPS, FFS and OCB. ..
• the content of the component C relative to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, preferably 10% by weight to 97% by weight, more preferably 40% by weight to 95% by weight. The range is.
• the content of the component C is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
• the component D is a compound (8) in which one end group is —C ⁇ N or —C ⁇ C—C ⁇ N. Since the 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 alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, 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 has a large value, so it is mainly used when preparing a composition for modes such as TN. By adding this component D, the dielectric anisotropy of the composition can be increased.
• the component D is effective in extending 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 the component D relative to 100% by weight of the liquid crystal composition is suitably in the range of 1% by weight to 99% by weight, preferably 10% by weight to 97% by weight, more preferably 40% by weight to 95% by weight. The range is.
• the content of the component D is preferably 30% by weight or less based on 100% by weight of the liquid crystal composition.
• Ingredient E is compounds (11) to (19).
• the component E has a large negative dielectric anisotropy. These compounds have phenylene substituted in the lateral position with two halogens (fluorine or chlorine), such as 2,3-difluoro-1,4-phenylene.
• Preferred examples of the component E include compounds (11-1) to (11-9), compounds (12-1) to (12-19), compounds (13-1) and (13-2), compound (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 the compound (19-1) can be mentioned.
• R 15 , R 16 , and R 17 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, wherein at least one —CH 2 — May be replaced by —O—, in these groups at least one hydrogen may be replaced by fluorine, and R 17 may be hydrogen or fluorine.
• Component E has a large negative dielectric anisotropy.
• Ingredient E is suitably used when preparing a composition for modes such as IPS, VA, PSA.
• the content of the component E is increased, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, it is preferable that the content is small as long as the required threshold voltage of the device is satisfied.
• the content of the component E is preferably 40% by weight or more with respect to 100% by weight of the liquid crystal composition in order to drive the voltage sufficiently.
• the compound (11) of the component E is a bicyclic compound, it has the effect of lowering the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compounds (12) and (13) are tricyclic compounds and the compound (14) is a tetracyclic compound, they have the effects of increasing the maximum 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, and 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 based on 100% by weight of the liquid crystal composition.
• a liquid crystal composition satisfying at least one of properties such as specific resistance, high stability against ultraviolet rays, high stability against heat, and large elastic constant can be prepared.
• the liquid crystal composition is prepared by a known method. For example, there may be mentioned a method of mixing the above components and dissolving them by heating. Additives may be added to the composition depending on the application. Examples of additives include polymerizable compounds other than compound (1), polar compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dyes, and decolorizers. For example, a foaming agent. Such additives are well known to the person skilled 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 polymerizing the compound (1) by irradiating it with ultraviolet rays while applying a voltage between the electrodes. At this time, the compound (1) is immobilized in a state where its polar group interacts non-covalently with the surface of the glass (or metal oxide) substrate. As a result, the ability to control the alignment 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 the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are compounds with at least one acryloyloxy and compounds with at least one methacryloyloxy. Further preferred examples also include compounds having both acryloyloxy and methacryloyloxy.
• a particularly preferable example of the polymerizable compound is the compound (20).
• the compound (20) is a compound different from the compound (1).
• the compound (1) has a polar group.
• the compound (20) preferably has no polar group.
• ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine- 2-yl or pyridin-2-yl, and in the ring F and ring I, at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen. May be replaced by an alkyl having 1 to 12 carbons which is replaced by halogen.
• Preferred ring F or ring I is cyclohexyl, cyclohexenyl, phenyl, fluorophenyl, difluorophenyl, 1-naphthyl, or 2-naphthyl. More desirable ring F or ring I is cyclohexyl, cyclohexenyl, or phenyl. Particularly preferred ring F or ring I is phenyl.
• 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-diyl, or Pyridine-2,5-diyl
• Preferred ring G is 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.
• 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 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, or —OCO—. More desirable Z 22 or Z 23 is a single bond.
• P 11 , P 12 , and P 13 are independently a polymerizable group.
• Preferred P 11 to P 13 are groups selected from the group of polymerizable groups represented by formula (P-1) to formula (P-5). More desirable P 11 to P 13 are groups represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P 11 to P 13 are groups represented by formula (P-1).
• the wavy lines in the formulas (P-1) to (P-5) indicate binding sites.
• M 11 , M 12 and M 13 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is replaced with halogen. And is an alkyl having 1 to 5 carbons.
• Preferred M 11 , M 12 or M 13 is hydrogen or methyl for increasing the reactivity. More preferred M 11 is hydrogen or methyl, and more preferred M 12 or M 13 is hydrogen.
• Sp 11 , Sp 12 and Sp 13 are independently a single bond or an alkylene having 1 to 10 carbons, and in the Sp 11 , Sp 12 and Sp 13 , at least one —CH 2 — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH 2 CH 2 — is —CH ⁇ CH— or —C ⁇ C—. It may be replaced and at least one hydrogen may be replaced by fluorine or chlorine.
• Preferred Sp 11 , Sp 12 or Sp 13 is a single bond.
• u is 0, 1, or 2.
• 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 more.
• Preferred f, g, or h is 1 or 2.
• the preferred sum is 2, 3 or 4.
• a further preferred sum is 2 or 3.
• Preferred examples of the compound (20) are the compounds (20-1) to (20-7) and the following compounds (20-8) to (20-11) described in Item 15. More preferred examples are the following compounds (20-1-1) to (20-1-5), compounds (20-2-1) to (20-2-5), compound (20-4-1), A compound (20-5-1), a compound (20-6-1), and a compound (20-7-1).
• R 25 to R 31 are independently hydrogen or methyl
• v and x are independently 0 or 1
• t and u are independently integers from 1 to 10.
• t+v and x+u are each at most 10
• L 31 to L 36 are independently hydrogen or fluorine
• L 37 and L 38 are independently hydrogen, fluorine, or methyl.
• a polar compound can be mixed and used. Similar to the compound (1), the polar compound is added for the purpose of controlling the alignment of liquid crystal molecules by allowing the polar group to interact non-covalently with the substrate surface such as glass (or metal oxide). Like the compound (1), such a polar compound is chemically stable under the condition of being sealed in the device, has a high ability to align liquid crystal molecules, and has a voltage holding ratio when used in a liquid crystal display device. Is preferably high and the solubility in the liquid crystal composition is high. By mixing the polar compound, the orientation of the compound (1) and the voltage holding ratio can be further improved, an afterimage can be suppressed, and a stable pretilt angle can be formed.
• Preferred examples of the polar compound include compounds (21) to (24).
• R 50 is hydrogen, fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or R 2 having 2 to 12 carbons.
• R 51 is a group represented by —OH, —CH(CH 2 OH) 2 , —NH 2 , —OR 53 , —N(R 53 ) 2 , or —Si(R 53 ) 3 , and here, , R 53 is hydrogen or alkyl having 1 to 7 carbons, and in this R 53 , at least one —CH 2 — may be replaced by —O—, and at least one —CH 2 CH 2 —.
• R 52 is hydrogen, fluorine, or alkyl having 1 to 5 carbons, and in this R 52 , at least one —CH 2 — may be replaced by —O—, and at least one hydrogen is fluorine or May be replaced by chlorine;
• R 54 is a group represented by —OH, —NH 2 , —OR 53 , —N(R 53 ) 2 , or —Si(R 53 ) 3 , where R 53 is hydrogen or the number of carbon atoms.
• Ring A 50 and ring B 50 are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3 -Dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, wherein in ring A 50 and ring B 50 , at least one hydrogen is fluorine, carbon number 1 to 12 alkyl, 1-12 alkoxy, or at least one hydrogen may be replaced by 1-12 alkyl in which fluorine is replaced; Z 50 represents a single bond, —CH
• Sp 51 , Sp 52 , Sp 53 and Sp 54 are a single bond or an alkylene having 1 to 7 carbon atoms, and in this Sp 51 , Sp 52 , Sp 53 and Sp 54 , at least one —CH 2 — is — May be replaced by O—, —COO—, or —OCO—, at least one —CH 2 CH 2 — may be replaced by —CH ⁇ CH—, and at least one hydrogen may be replaced by fluorine.
• a 50 is 0, 1, 2, 3, or 4; a 51 is 1 or 2; l is 0, 1, 2, 3, 4, 5, or 6 and at least one —CH 2 — of this alkylene is —O—, —CO—, —COO—, —OCO—, or — OCOO—, at least one —CH 2 CH 2 — may be replaced with —CH ⁇ CH— or —C ⁇ C—, and in these groups at least one hydrogen is fluorine. May be replaced with.
• More preferable examples include the following compounds.
• the polymerizable compound in the composition can be rapidly polymerized by using a polymerization initiator such as a photoradical polymerization initiator.
• a polymerization initiator such as a photoradical polymerization initiator.
• the amount of the remaining polymerizable compound can be reduced by optimizing the reaction conditions during the polymerization.
• photo-radical polymerization initiators include TPO, 1173, and 4265 from Darocur series of BASF, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800 from Irgacure series. 1850, and 2959.
• photo radical polymerization initiator examples include 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone/Michler's ketone mixture, hexaarylbiimidazole/mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, benzophenone/methyltriethanolamine mixture Is.
• polymerization After adding a photo-radical polymerization initiator to the liquid crystal composition, polymerization can be performed by irradiating with ultraviolet rays while applying an electric field. However, the unreacted polymerization initiator or the decomposition product of the polymerization initiator may cause display failure such as image sticking on the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator.
• the preferable wavelength of the light for irradiation is in the range of 150 nm to 500 nm. More preferred wavelengths are in the range 250 nm to 450 nm, and most preferred wavelengths are in the range 300 nm to 400 nm.
• a polymerization inhibitor When storing a 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, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol and phenothiazine.
• the optically active compound has an effect of preventing a reverse twist by inducing a helical structure in liquid crystal molecules and giving a necessary twist angle.
• the helical 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 helical 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 alkyl having 1 to 10 carbons. * Indicates an asymmetric carbon.
• the antioxidant is effective for maintaining a large voltage holding ratio.
• Preferred examples of the antioxidants include the following compounds (AO-1) and (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade name; BASF Corporation).
• the ultraviolet absorber is effective for preventing the lowering of the maximum temperature.
• Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Examples include Tinuvin 328, and Tinuvin 99-2 (trade name; BASF Corporation); and 1,4-diazabicyclo[2.2.2]octane (DABCO).
• Light stabilizers such as sterically hindered amines are preferred for maintaining a large voltage holding ratio.
• Preferred examples of the light stabilizer include 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 Co.).
• a heat stabilizer is also effective for maintaining a large voltage holding ratio, and Irgafos 168 (trade name; BASF Corporation) can be mentioned as a preferable example.
• a dichroic dye such as an azo dye or anthraquinone dye is added to the composition in order to adapt to a GH (guest host) mode device.
• the antifoaming agent is effective for preventing foaming.
• Preferred examples of the defoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.
• R 40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, —COOR 41 , or —CH 2 CH 2 COOR 41 , wherein R 41 is 1 To 20 alkyl.
• R 42 is alkyl having 1 to 20 carbons.
• R 43 is hydrogen, methyl or O.(oxygen radical); ring G 1 is 1,4-cyclohexylene or 1,4-phenylene; in compound (AO-7) , Ring G 2 is a group in which at least one hydrogen of 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene is 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, and PSA, and can be suitably used for a liquid crystal display device driven by an active matrix system.
• 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 device driven by a passive matrix system.
• These elements can be applied to any of reflection type, transmission type, and semi-transmission type.
• This composition is also suitable for NCAP (nematic curvilinear aligned phase) devices, where the composition is microencapsulated.
• This composition can also be used for a polymer dispersed liquid crystal display device (PDLCD) and a polymer network liquid crystal display device (PNLCD).
• PDLCD polymer dispersed liquid crystal display device
• PLCD polymer network liquid crystal display device
• the ratio of the polymerizable compound is preferably 10% by weight or less, and more preferably 0.1% to 2% by weight, based on 100% by weight of the liquid crystal composition. %, and a more preferable ratio is in the range of 0.2% by weight to 1.0% by weight.
• the PSA mode element can be driven by a driving method such as an active matrix method or a passive matrix method. Such an element can be applied to any of reflection type, transmission type, and semi-transmission type.
• the polymer contained in the composition orients the liquid crystal molecules.
• the polar compound helps the liquid crystal molecules to align. That is, the polar compound can be used instead of the alignment film.
• An example of a method of 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. A liquid crystal composition is prepared by mixing liquid crystal compounds. The compound (1) and, if necessary, other polymerizable compound and polar compound are added to the composition. You may add an additive further as needed. This composition is injected into the device. Light irradiation is performed with a voltage applied to this element. UV light is preferred. The polymerizable compound is polymerized by irradiation with light. By this polymerization, a composition containing a polymer is produced, and a device having a PSA mode is produced.
• polar compounds are arranged on the substrate because the polar groups interact with the substrate surface.
• This polar compound aligns the liquid crystal molecules.
• the interaction with the surface of the substrate becomes stronger and the alignment can be performed at a low concentration.
• the alignment of liquid crystal molecules is further promoted by the action of the electric field.
• the polymerizable compound is also oriented according to this orientation. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is produced. The effect of this polymer additionally stabilizes the alignment of the liquid crystal molecules, thus shortening the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, the effect of this polymer also improves the sticking.
• the compound (1) Since the compound (1) is polymerizable, it is consumed by the polymerization. The compound (1) is also consumed by copolymerizing with another polymerizable compound. Therefore, the compound (1) has a polar group but is consumed, so that a liquid crystal display device having a large voltage holding ratio can be obtained. If a polar compound having polymerizability is used, the effects of both the polar compound and the polymerisable compound can be achieved by a single compound, and thus the polymerizing compound having no polar group may be unnecessary. is there.
• the present invention will be described in more detail with reference to examples (including synthesis examples and use examples). The invention is not limited by these examples.
• the invention also includes mixtures prepared by mixing at least two of the composition of use examples.
• Example 1 Examples of Compound (1) Unless otherwise stated, reactions were carried out under nitrogen atmosphere. The 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 the compound (1), liquid crystal compound, composition and device were measured by the following methods.
• NMR analysis DRX-500 manufactured by Bruker BioSpin was used for the measurement.
• the sample was dissolved in a deuterated solvent such as CDCl 3 and the measurement was performed at room temperature under the conditions of 500 MHz and 16 times of integration.
• Tetramethylsilane was used as an internal standard.
• CFCl 3 was used as an internal standard, and the number of times of integration was 24.
• s means a singlet, d a doublet, t a triplet, q a quartet, quin a quintet, sext a sextet, m a multiplet and br a broad.
• a GC-2010 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) part 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.
• HPLC analysis For measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used.
• YMC-Pack ODS-A manufactured by YMC Co., Ltd. length 150 mm, inner diameter 4.6 mm, particle diameter 5 ⁇ m
• eluent acetonitrile and water were appropriately mixed and used.
• the detector a UV detector, an RI detector, a CORONA detector or the like was appropriately used. When a UV detector was used, the detection wavelength was 254 nm.
• the sample was dissolved in acetonitrile to prepare 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 PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used for the measurement. The detection wavelength was 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol/L solution, which was placed in a quartz cell (optical path length 1 cm) for measurement.
• Measurement sample When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample.
• Measurement method The characteristics were measured by the following methods. Many of these are based on the method 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 method modified from this. there were. No thin film transistor (TFT) was attached to the TN device used for the measurement.
• phase Structure The sample was placed on a hot plate (FP-52 type hot stage manufactured by METTLER CORPORATION) of a melting point measuring device equipped with a polarization microscope. While heating this sample at a rate of 3° C./min, the phase state and its change were observed with a polarizing microscope to specify the type of phase.
• FP-52 type hot stage manufactured by METTLER CORPORATION
• Transition temperature (°C)
• a scanning calorimeter manufactured by Perkin Elmer, a Diamond DSC system or a high-sensitivity differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., X-DSC7000 was used.
• the sample was heated and lowered at a rate of 3° C./min, and the starting point of the endothermic peak or exothermic peak accompanying the phase change of the sample was obtained by extrapolation to determine the transition temperature.
• the melting point of the compound and the polymerization initiation temperature were also measured using this device.
• the temperature at which a compound transitions from a solid state to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "lower limit temperature of liquid crystal phase”.
• the temperature at which a compound transitions from a liquid crystal phase to a liquid is sometimes abbreviated as "clearing point”.
• the crystal was designated as C. When the types of crystals can be distinguished, they are represented as C 1 and C 2 .
• the smectic phase was represented by S and the nematic phase was represented by N.
• a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished among the smectic phases, they are represented as S A , S B , S C , or S F , respectively.
• the liquid (isotropic) was designated 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
• 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 measurement method of the characteristics may differ between the sample with positive dielectric anisotropy and the sample with negative dielectric anisotropy.
• the measurement method when the dielectric anisotropy is positive is described in items (8a) to (12a).
• Viscosity (rotary viscosity; ⁇ 1; measured at 25°C; mPa ⁇ s) Positive dielectric anisotropy: The measurement followed the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was put in a TN device in which the twist angle was 0 degree and the distance (cell gap) between the two glass substrates was 5 ⁇ m. A voltage was applied to the device stepwise in the range of 16V to 19.5V at intervals of 0.5V. After 0.2 seconds of non-application, application was repeated under the conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds).
• the peak current and the peak time of the transient current generated by this application were measured. These measurements and M.
• the value of rotational viscosity was obtained from the paper of Imai et al., Formula (8) on page 40.
• the value of the dielectric anisotropy required for this calculation was determined by the method described below using the device whose rotational viscosity was measured.
• Viscosity Rotational viscosity; ⁇ 1; measured at 25°C; mPa ⁇ s
• Negative dielectric anisotropy The measurement followed the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was put in a VA device in which the distance (cell gap) between the two glass substrates was 20 ⁇ m. A voltage was applied to the device stepwise in the range of 39 V to 50 V in steps of 1 V. After 0.2 seconds of non-application, application was repeated under the conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and the peak time of the transient current generated by this application were measured.
• Dielectric constants ( ⁇ and ⁇ ) were measured as follows. 1) Measurement of dielectric constant ( ⁇ ): A well-cleaned glass substrate was coated with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). The glass substrate was rotated with a spinner and then heated at 150° C. for 1 hour. The sample was put in a VA device having a distance (cell gap) of 4 ⁇ m between two glass substrates, and the device was sealed with an adhesive that was cured by ultraviolet rays.
• a sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant ( ⁇ ) of the liquid crystal molecule in the major axis direction was measured.
• 2) Measurement of dielectric constant ( ⁇ ) A polyimide solution was applied to a well washed glass substrate. After firing this glass substrate, the obtained alignment film was rubbed. The sample was put in a TN device 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 dielectric constant ( ⁇ ) in the short axis direction of the liquid crystal molecule was measured.
• Threshold voltage (Vth; measured at 25°C; V) Positive dielectric anisotropy: LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement.
• the light source was a halogen lamp.
• the sample was put in a normally white mode TN device 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, rectangular wave) applied to this element was increased stepwise from 0 V to 10 V by 0.02 V.
• the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
• a voltage-transmittance curve in which the transmittance is 100% when the amount of light is maximum and the transmittance is 0% when the amount of light is minimum was created.
• the threshold voltage is represented by the voltage when the transmittance reaches 90%.
• the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured.
• a voltage-transmittance curve in which the transmittance is 100% when the amount of light is maximum and the transmittance is 0% when the amount of light is minimum was created.
• the threshold voltage is represented by the voltage when the transmittance becomes 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 to change the transmittance from 10% to 90%.
• the response time was represented by the sum of the rise time and fall time thus obtained.
• a voltage slightly exceeding the threshold voltage was applied to this device for 1 minute, and then a 23.5 mW/cm 2 ultraviolet ray was irradiated for 8 minutes while applying a voltage of 5.6V.
• a rectangular wave 60 Hz, 10 V, 0.5 seconds was applied to this device.
• the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device 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 to change the transmittance 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) manufactured by Eye Graphics Co., Ltd.
• the device was charged by applying a pulse voltage (60 microseconds at 1 V) at 60°C.
• 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 cycle was obtained.
• Area B is the area when there is no attenuation.
• the voltage holding ratio was expressed as a percentage of the area A with respect to the area B.
• Pretilt angle stability Changes in the pretilt angle of the liquid crystal display device were evaluated.
• the pretilt angle Pt angle (before) before stress application was measured, and after that, a rectangular wave of 7.0 V and 60 Hz was applied to the device for 24 hours, and then the pretilt angle Pt angle (after) after stress application was measured again. From these values, the change in pretilt angle ⁇ Pt angle (deg.) was calculated using the following formula.
• ⁇ Pt angle Pt angle (after)-Pt angle (before)
• Optipro manufactured by Shintech
• Raw material Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (IPA) (1.1%), and is available from Nippon Alcohol Sales Co., Ltd. obtained.
• compound (No. 1) (6.80 g; 66%) was obtained by a method similar to the method of synthesizing compound (No. 13).
• composition examples The compounds in the examples are represented by symbols based on the definitions in Table 2 below.
• Table 2 the configuration for 1,4-cyclohexylene is trans.
• the number in parentheses after the symbol corresponds to the compound number.
• the symbol ( ⁇ ) means other liquid crystal compound.
• the ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition.
• Example 40 The compound of No. 1 as the compound (1) was added to the composition (M1) at a ratio of 1.0% by mass.
• the liquid crystal composition of the present invention to which this compound (1) was added was enclosed in a VA element of a glass substrate having no alignment film, and the vertical alignment of the composition on the substrate was confirmed. It was
• the liquid crystal composition of the present invention can control the alignment of liquid crystal molecules in an element having no alignment film.
• a liquid crystal display device containing this composition has characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long life, so that it can be used for a liquid crystal projector, a liquid crystal television and the like. ..

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