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WO2017018153A1 - Composé stabilisant, composition de cristaux liquides et élément d'affichage - Google Patents

Composé stabilisant, composition de cristaux liquides et élément d'affichage Download PDF

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Publication number
WO2017018153A1
WO2017018153A1 PCT/JP2016/070105 JP2016070105W WO2017018153A1 WO 2017018153 A1 WO2017018153 A1 WO 2017018153A1 JP 2016070105 W JP2016070105 W JP 2016070105W WO 2017018153 A1 WO2017018153 A1 WO 2017018153A1
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group
general formula
compound
hydrogen atom
carbon atoms
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Japanese (ja)
Inventor
清香 野瀬
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2017523015A priority Critical patent/JP6255633B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C07D491/113—Spiro-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

  • the present invention relates to a stabilizer compound.
  • Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators.
  • Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, VA (vertical alignment) type using TFT (thin film transistor), and IPS (in-plane Switching) type or FFS (fringe field switching) type.
  • the main characteristics required for the liquid crystal composition are (1) being stable against external stimuli such as moisture, air, heat, light, etc. There are four examples: (3) low viscosity, and (4) low driving voltage.
  • dielectric anisotropy ( ⁇ ) and refractive index anisotropy ( ⁇ n) In general, the liquid crystal composition is composed of several to several tens of kinds of compounds in order to obtain an optimal value.
  • a positive value composition and a negative value composition are used separately.
  • examples of a display method using a liquid crystal material in which ⁇ has a positive value include TN type, STN type, IPS type, and FFS type.
  • examples of the display method using a liquid crystal material in which ⁇ has a negative value include ECB type, VA type, and FFS type.
  • low voltage driving, high-speed response, and a wide operating temperature range are required in all driving systems. That is, the absolute value of ⁇ is large, the viscosity ( ⁇ ) is small, and a high nematic phase-isotropic liquid phase transition temperature (T ni ) is required.
  • ⁇ n ⁇ d which is the product of ⁇ n and the cell gap (d)
  • ⁇ n of the liquid crystal composition it is necessary to adjust ⁇ n of the liquid crystal composition to an appropriate range according to the cell gap.
  • a liquid crystal composition having a small ⁇ 1 is required.
  • the problem to be solved by the present invention is to prevent deterioration of the liquid crystal composition by adding it to the liquid crystal composition, high compatibility with the liquid crystal composition, without impairing the storage stability of the liquid crystal composition, and It is to provide a stabilizer compound that can be easily produced.
  • R a0 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 3 to 12 carbon atoms
  • R a1 , R a2 , R a3 and R a4 each independently represents an alkyl group having 1 to 8 carbon atoms, or R a1 and R a2 and / or R a3 and R a4 together form a ring structure.
  • R a5 and R a6 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents 0 or 1, t represents 1 to 4; U represents a 2 ⁇ t-valent organic group forming a ring structure, and when a plurality of R a0 , R a1 , R a2 , R a3 , R a4 , R a5 , R a6 and n are present, they are the same. Or different. ) And a liquid crystal composition containing the compound and a display element are provided.
  • the stabilizer compound according to the present invention prevents the liquid crystal composition from being deteriorated by light, has high compatibility with the liquid crystal composition, and can be easily produced without impairing the storage stability of the liquid crystal composition.
  • a fast response liquid crystal display element can be provided.
  • R a0 is preferably a hydrogen atom or a hydroxyl group, and particularly preferably a hydrogen atom, in order to enhance the ability to prevent photodegradation.
  • an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 12 carbon atoms is preferable.
  • R a1 , R a2 , R a3 and R a4 are each independently preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
  • R a1 and R a2 and / or R a3 and R a4 are preferably combined to form a ring structure.
  • R a5 and R a6 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom for ease of production.
  • n is preferably 1.
  • t is preferably 1 or 2 and particularly preferably 1 in order to increase the storage stability of the liquid crystal composition.
  • the number is preferably 3 or 4 because the number of hindered amine structures per unit weight increases.
  • U represents the general formula (Ia)
  • each broken line represents a bond to an oxygen atom
  • R a7 and R a8 each independently represents a hydrogen atom or a monovalent organic group, or R a7 and R a8 together form a ring structure.
  • m is 0 or 1.
  • R a7 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms Is particularly preferred
  • m is particularly preferably 1.
  • R a8 represents the general formula (Ic)
  • Sp a1 and Sp a2 each independently represent a single bond or an alkylene group having 1 to 12 carbon atoms. , more preferably a single bond or an alkylene group having 1 to 8 carbon atoms, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O- , —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C— are preferred, and a single bond is particularly preferred.
  • a a1 and A a2 each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - is -O- May be replaced by.) (B) a 1,4-phenylene group (one —CH ⁇ present in the group or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ ) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH ⁇ or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ .
  • a group selected from the group consisting of the above groups is preferable, and the groups (a), (b) and (c) are each independently a cyano group, fluorine More preferably, it is substituted with an atom, a chlorine atom, a methyl group or a methoxy group.
  • R a9 preferably represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and one — CH 2 — or two or more non-adjacent —CH 2 — are replaced by —O—, —S—, —COO—, —OCO—, —CO—, —CH ⁇ CH— or —C ⁇ C—. And is preferably replaced by —O— or —CH ⁇ CH—.
  • R a9 represents the general formula ( Id )
  • R d0 , R d1 , R d2 , R d3 , R d4 , R d5 and R d6 are R a0 , R a1 , R a2 , R a3 , R a4 , R a5 and R in the general formula (I)).
  • R a10 represents a hydrogen atom or a monovalent organic group
  • Sp a3 represents the same meaning as Sp a1 or Sp a2
  • s and v each independently represent 0 or 1.
  • a structure represented by R d0 is preferably a hydrogen atom or a hydroxyl group for enhancing the ability to prevent photodegradation, and particularly preferably a hydrogen atom for ease of production.
  • an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 3 to 12 carbon atoms is preferable.
  • R d1 , R d2 , R d3 and R d4 are each independently preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group. In order to facilitate removal of polar impurities mixed during production, it is preferable that R d1 and R d2 and / or R d3 and R d4 together form a ring structure.
  • R d5 and R d6 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom from the standpoint of ease of production.
  • Sp a3 is preferably each independently a single bond or an alkylene group having 1 to 8 carbon atoms, and one —CH 2 — present in the alkyl group or two or more —CH 2 — not adjacent to each other. Is preferably replaced by —O—, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C—, and particularly preferably a single bond.
  • R a10 is particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • s and v are each preferably 1.
  • p and q are each preferably 0 or 1.
  • each broken line represents a bond to an oxygen atom, and l and o each independently represents 0 or 1.
  • each broken line represents a bond to an oxygen atom
  • le and oe each independently represent 0 or 1
  • R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group
  • V e represents a divalent organic group.
  • a structure represented by l, o, le and oe are each preferably 1 in order to improve the storage stability of the liquid crystal composition.
  • R e1 and R e2 are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 3 is preferable, and a hydrogen atom, a methyl group, and an ethyl group are more preferable.
  • the general formula (Ie) is preferably a structure represented by the general formula (Ie1).
  • each broken line represents a bond to an oxygen atom
  • le and oe each independently represent 0 or 1
  • R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group
  • sp ae represents a single bond or an alkylene group having a carbon number of from 12
  • the alkylene group in present in one -CH 2 - or nonadjacent two or more -CH 2 - is -O-
  • Sp ae is more preferably a single bond or an alkylene group having 1 to 8 carbon atoms.
  • the general formula (Ie) is preferably a structure represented by the general formula (Ie2).
  • each broken line represents a bond to an oxygen atom
  • le and oe each independently represent 0 or 1
  • R e1 and R e2 each independently represent a hydrogen atom or a monovalent organic group
  • Sp ae1 and Sp ae2 each independently represent the same meaning as Sp a1 in the general formula (Ic)
  • a ad1 represents the same meaning as A a1 in the general formula (Ic)
  • pe is 1 or 2
  • U represents the general formula (If)
  • a broken line represents a bond to an oxygen atom
  • lf represents 0 or 1
  • R f7 represents a hydrogen atom or a monovalent organic group
  • Sp af1 and Sp af2 are each independently represented by the general formula (I -A ) represents the same meaning as Sp a1 in -c)
  • a afl represents the same meaning as A a1 in the general formula (Ic)
  • pf represents 0, 1 or 2
  • tf represents 3 or 4
  • V f represents a trivalent or tetravalent group, but the valence of V f is the same as the number represented by tf, and when there are a plurality of Sp af1 , Sp af2 and A af1 , they may be the same May be different.
  • a structure represented by R f7 is preferably an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon
  • V f preferably represents a hydrocarbon group having 1 to 15 carbon atoms, One or two or more non-adjacent —CH 2 — present in the carbon atom in the group are each independently —O—, —S—, —CO—, —COO—, —OCO—, — CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO— It may be substituted with CH ⁇ CH—, —OCO—CH ⁇ CH—, —CH ⁇ CH—, —CF ⁇ CF—, —OCF 2 —, —CF 2 O—, or —C ⁇ C—.
  • V f is more preferably a group selected from the groups represented by formulas (V3-1) to (V3-12).
  • R v31 and R v32 represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, and one or two or more —CH 2 — present in the alkyl group are each independently May be substituted with —O—, —S—, —CH ⁇ CH—, —C ⁇ C—, —CO—O—, —O—CO—, and the hydrogen atom in the cyclic structure is fluorine.
  • Atom chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group , A trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 12 carbon atoms may be substituted, and one or not present in the alkyl group Two or more —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—.
  • R V31 and R V32 preferably represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and are preferably linear.
  • the formulas (V3-4) to (V3-12) are preferably each independently unsubstituted, and the hydrogen atoms in the formulas (V3-4) to (V3-12) are cyano groups , Fluorine atom, chlorine atom, methyl group or methoxy group may be substituted.
  • Vf preferably represents a hydrocarbon group having 1 to 15 carbon atoms.
  • One or two or more non-adjacent —CH 2 — present in the carbon atom in the group are each independently —O—, —S—, —CO—, —COO—, —OCO—, — CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO— It may be substituted with CH ⁇ CH—, —OCO—CH ⁇ CH—, —CH ⁇ CH—, —CF ⁇ CF—, —OCF 2 —, —CF 2 O—, or —C ⁇ C—.
  • V f is more preferably a group selected from the groups represented by formulas (V4-1) to (V4-21).
  • the hydrogen atom in the cyclic structure is fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, cyano group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino.
  • —CH 2 — Two or more —CH 2 — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—.
  • the compound represented by the general formula (I) is preferably a compound represented by the general formula (I-1).
  • R a01 represents a hydrogen atom or a hydroxyl group
  • R a71 represents a hydrogen atom or a monovalent organic group
  • Sp a11 and Sp a21 represent the same meaning as Sp a1 and Sp a2 in formula (Ic)
  • a a11 and A a21 represent the same meaning as A a1 and A a2 in formula (Ic)
  • R a91 represents the same meaning as R a9 in formula (Ic)
  • m1, p1 and q1 each independently represents 0 or 1.
  • R a01 is preferably a hydrogen atom.
  • R a71 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Sp a11 and Sp a21 are preferably each independently a single bond or an alkylene group having 1 to 6 carbon atoms, and one —CH 2 — present in the alkyl group or two or more non-adjacent — CH 2 — is preferably replaced by —O—, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C—, and particularly preferably a single bond.
  • a a11 and A a21 each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH 2 - or nonadjacent two or more -CH 2 - is -O- May be replaced by.) (B) a 1,4-phenylene group (one —CH ⁇ present in the group or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ ) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 3,4-tetrahydronaphthalene-2,6-diyl group, one —CH ⁇ or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ .
  • R a91 is a hydrogen atom or preferably from 1 carbon atoms is 6 alkyl group, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O It is also preferred that it is replaced by — or —CH ⁇ CH—.
  • R a91 represents the general formula (I-d1)
  • R d01 represents a hydrogen atom or a hydroxyl group
  • Sp a31 represents the same meaning as Sp a3 in formula ( Id )
  • R a101 represents a hydrogen atom or a monovalent organic group
  • s1 represents 0 Or a structure represented by 1
  • R a101 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R d01 is preferably a hydrogen atom.
  • Sp a31 is preferably an alkylene group of a single bond or a C 1 -C 6, one -CH 2 present in the alkyl group - or nonadjacent two or more -CH 2 - is -O It is preferably replaced by —, —COO—, —OCO—, —CH ⁇ CH— or —C ⁇ C—, and particularly preferably a single bond.
  • s1 is preferably 1.
  • m1 and p1 are preferably 1.
  • q1 is preferably 0.
  • R a02 and R a03 are the same meaning as R a01 in the general formula (I-1)
  • R a72 and R a102 has the same meaning as R a71 in the general formula (I-1)
  • R a92 represents the same meaning as R a91 in the general formula (I-1)
  • Sp a12 , Sp a13 and Sp a14 represent the same meaning as Sp a11 or Sp a21 in the general formula (I-1).
  • a a12 and A a13 represent the same meaning as A a11 or A a21 in formula (I-1).
  • the composition containing one or more compounds represented by general formula (I) preferably has a liquid crystal phase at room temperature.
  • the compound represented by the general formula (I) is preferably contained in the composition at a lower limit of 0.01% or more, preferably 0.02% or more, and 0.03% or more.
  • it contains 0.05% or more, preferably 0.07% or more, preferably 0.1% or more, preferably 0.15% or more, 0.2 % Or more, preferably 0.25% or more, preferably 0.3% or more, preferably 0.5% or more, and preferably 1% or more.
  • the upper limit is preferably 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and 0.45% or less. It is preferable to contain 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less. 2% or less, preferably 0.15% or less, preferably 0.1% or less, preferably 0.07% or less, preferably 0.05% or less It is preferable to contain 0.03% or less.
  • the content is preferably 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.3% by mass, Particularly preferred is 0.05 to 0.25% by mass. More specifically, when emphasizing the suppression of precipitation at low temperatures, the content is preferably 0.01 to 0.1% by mass.
  • composition containing the compound represented by the general formula (I) may contain a compound having a liquid crystal phase in addition to the compound represented by the general formula (I), or a compound having no liquid crystal phase. It may contain.
  • a compound represented by general formula (I) can be obtained by reacting a compound represented by general formula (S-1) with a compound represented by general formula (S-2).
  • Examples of the reaction include a method in which the compound represented by the general formula (S-1) and the compound represented by the general formula (S-2) are heated in the presence of an acid catalyst to cause a dehydration reaction.
  • the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and potassium bisulfate, Lewis acids such as boron trifluoride, organic acids such as fumaric acid, phthalic acid, oxalyl acid, camphorsulfonic acid, and p-toluenesulfonic acid, And solid acids such as Amberlyst-15.
  • the acid catalyst can be added in an amount exceeding 1 equivalent, if necessary.
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1a), (I-1b), (I-1k) or (I-1l), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), A s1 has the same meaning as A a12 or A a13 in formula (I-1b) or (I-1l), and Y s1 has the same formula as in formula (I-1b).
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1c), (I-1j), (I-1m) or (I-1t), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), and A s1 represents A a12 or A a13 in formula (I-1c), (I-1j), (I-1m) or (I-1t).
  • Y s1 has the same meaning as R a92 in formula (I-1c) or (I-1j), or the same as Sp a13 in formula (I-1m) or (I-1t).
  • Sp s1 represents the same meaning as Sp a12 or Sp a14 in the general formula (I-1c), (I-1j), (I-1m) or (I-1t), and m s1 and p s1 represents 0 or 1 each independently is, t s1 is 1 or 2 Represent.
  • a compound represented by general formula (S-6) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-5).
  • a reaction example for example, a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-5) are dehydrated by heating in the presence of an acid catalyst in the same manner as in Production Method 1. Can be mentioned.
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1d), (I-1i), (I-1n) or (I-1s), and R s7 represents the general formula R a71 has the same meaning as in formula (I-1), and A s1 represents A a12 or A a13 in formula (I-1d), (I-1i), (I-1n) or (I-1s).
  • Y s1 has the same meaning as R a92 in the general formula (I-1d) or (I-1i), or the same as Sp a13 in the general formula (I-1n) or (I-1s).
  • Sp s1 represents the same meaning as Sp a12 or Sp a14 in the general formula (I-1d), (I-1i), (I-1n) or (I-1s), and m s1 and p s1 represents 0 or 1 each independently is, t s1 is 1 or 2 Represent.
  • the compound represented by the general formula (S-9) can be obtained by reacting the compound represented by the general formula (S-3) with the compound represented by the general formula (S-8).
  • a reaction example for example, in the same manner as in production method 1, there is a method in which a compound represented by general formula (S-3) and a compound represented by general formula (S-8) are heated in the presence of an acid catalyst to cause a dehydration reaction. Can be mentioned.
  • the general formula (I-1d), (I-1i), (I-1n) or A compound represented by (I-1s) can be obtained.
  • the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-9) to form an acid halide and then reacted with the compound represented by the general formula (S-7). It is done.
  • the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like.
  • Mitsunobu reaction in which the hydroxyl group of the general formula (S-7) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-9) can be mentioned.
  • the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1e) or (I-1o), and R s7 represents the same meaning as R a71 in the general formula (I-1).
  • a s1 represents the same meaning as A a12 or A a13 in the general formula (I-1e) or (I-1o)
  • Y s1 has the same meaning as R a92 in the general formula (I-1e)
  • it represents the same meaning as Sp a13 in the general formula (I-1o)
  • p s1 represents 0 or 1
  • t s1 represents 1 or 2.
  • a compound represented by the general formula (S-11) can be obtained by reacting the compound represented by the general formula (S-3) with a compound represented by the general formula (S-10).
  • reaction example for example, in the same manner as in Production Method 1, there is a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-10) are heated in the presence of an acid catalyst to cause a dehydration reaction. Can be mentioned.
  • a compound represented by general formula (I-1e) or (I-1o) is obtained by reacting a compound represented by general formula (S-11) with a compound represented by general formula (S-12). be able to.
  • reaction example for example, p-toluenesulfonyl chloride, methylsulfonyl chloride and the like are reacted with the hydroxyl group of the general formula (S-12) to form a leaving group, and then reacted with (S-11) in the presence of a base.
  • the Williamson reaction is mentioned.
  • the base include sodium hydride.
  • the Mitsunobu reaction which activates a hydroxyl group with azocarboxylic acid ester and triphenylphosphine and reacts with alcohol is mentioned.
  • the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
  • R s1 represents the same meaning as R a02 or R a03 in the general formula (I-1f) or (I-1p), and R s7 has the same meaning as R a71 in the general formula (I-1).
  • a s1 represents the same meaning as A a12 or A a13 in the general formula (I-1f) or (I-1p)
  • Y s1 has the same meaning as R a92 in the general formula (I-1f)
  • it represents the same meaning as Sp a13 in the general formula (I-1p)
  • p s1 represents 0 or 1
  • t s1 represents 1 or 2.
  • Examples of the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-13) to form an acid halide and then reacted with the compound represented by the general formula (S-11). It is done.
  • Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like.
  • Mitsunobu reaction in which the hydroxyl group of the general formula (S-11) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-13) can be mentioned.
  • the azocarboxylic acid ester include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
  • R s1 represents the same meaning as R a02 or R a03 in formula (I-1g), (I-1q), (I-1h) or (I-1r), and R s2 represents an alkyl group
  • R s7 represents the same meaning as R a71 in the general formula (I-1)
  • a s1 represents the general formula (I-1g), (I-1q), (I-1h) or (I ⁇ 1r) has the same meaning as A a12 or A a13
  • Y s1 has the same meaning as R a92 in General Formula (I-1g) or (I-1h), or General Formula (I-1q) or (I -1r) represents the same meaning as Sp a13
  • X represents chlorine, bromine or iodine
  • p s1 represents 0 or 1
  • t s1 represents 1 or 2.
  • a compound represented by general formula (S-14) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-17).
  • a reaction example for example, a method of heating and dehydrating the compound represented by the general formula (S-3) and the compound represented by the general formula (S-13) in the presence of an acid catalyst in the same manner as in Production Method 1. Can be mentioned.
  • a compound represented by the general formula (S-15) can be obtained by reducing the compound represented by the general formula (S-14).
  • the reducing agent include diisobutylaluminum hydride.
  • the compound represented by the general formula (S-15) can be obtained by reducing the compound represented by the general formula (S-14) to an alcohol and then oxidizing the compound to obtain an aldehyde.
  • the reducing agent include lithium aluminum hydride, diisobutylaluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, and the like.
  • the oxidizing agent include pyridinium chlorochromate and oxalyl chloride.
  • a compound represented by general formula (I-1g) or (I-1q) is obtained by reacting a compound represented by general formula (S-15) with a compound represented by general formula (S-16).
  • Examples of the reaction include a Wittig reaction in which a compound represented by the general formula (S-16) is reacted with a base to form phosphorus ylide and then reacted with a compound represented by the general formula (S-15). .
  • examples of the base include t-butoxypotassium.
  • a compound represented by the general formula (I-1h) or (I-1r) can be obtained by reducing the compound represented by the general formula (I-1g) or (I-1q).
  • Examples of the reaction include a method in which a compound represented by the general formula (I-1g) or (I-1q) and a catalyst coexist in a hydrogen atmosphere. In this case, examples of the catalyst include palladium carbon.
  • a compound represented by general formula (S-6) can be obtained by reacting a compound represented by general formula (S-3) with a compound represented by general formula (S-5).
  • reaction example for example, a method in which the compound represented by the general formula (S-3) and the compound represented by the general formula (S-5) are dehydrated by heating in the presence of an acid catalyst in the same manner as in Production Method 1.
  • a compound represented by general formula (I-1u) or (I-1v) is obtained by reacting a compound represented by general formula (S-6) with a compound represented by general formula (S-18).
  • Examples of the reaction include a method in which a halogenating agent is allowed to act on the carboxyl group of the general formula (S-18) to form an acid halide and then reacted with the compound represented by the general formula (S-6). It is done.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfuryl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide and the like.
  • Mitsunobu reaction in which the hydroxyl group of the general formula (S-6) is activated with an azocarboxylic acid ester and triphenylphosphine and reacted with the carboxyl group of the general formula (S-18) can be mentioned.
  • the azocarboxylic acid ester examples include diethyl azodicarboxylate and diisopropyl azodicarboxylate.
  • reaction conditions other than those described in the above steps include, for example, Experimental Chemistry Course (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.), Organic Synthesis (A John Wiley & Sons, Inc., Publication), and Bilstein Handbook of Organic Chemistry (Chemical Chemistry). -Described by Institut Futeriter der Organischen Chemie, Springer-Verlag Berlin and Heidelberg GmbH, Co. K, Fiesers' Reagents for Organic Science. racts Service, American Chemical Society), include those listed in databases such as Reaxys (Elsevier Ltd.).
  • a reaction solvent can be appropriately used in each step.
  • the solvent include ethanol, tetrahydrofuran, toluene, dichloromethane, water and the like.
  • a phase transfer catalyst can be added.
  • the phase transfer catalyst include benzyltrimethylammonium bromide and tetrabutylammonium bromide.
  • purification can be performed as necessary.
  • the purification method include chromatography, recrystallization, distillation, sublimation, reprecipitation, adsorption, and liquid separation treatment.
  • Specific examples of the purification agent include silica gel, NH 2 silica gel, alumina, activated carbon and the like.
  • tert-butoxypotassium 13.0 g was added and suspended in tetrahydrofuran (400 mL). Diethyl malonate (18.6 g) was added followed by 1,8-dibromooctane (15.8 g). Stir at room temperature for 3 days. The solution was concentrated under reduced pressure and acidified with 10% hydrochloric acid. Extracted twice with dichloromethane (150 mL). After concentration under reduced pressure, the residue was purified by column chromatography to obtain 15.0 g of 1,1,8,8-tetra (ethoxycarbonyl) octane as a colorless liquid.
  • a lithium aluminum hydride (10.6 g) was added to a reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, and suspended in tetrahydrofuran (279 mL).
  • 1,1,8,8-Tetra (ethoxycarbonyl) octane (20.0 g) was added, and the mixture was stirred at 60 ° C. for 5 hours. Ice-cooled and water (57.0 g) was carefully added. Stir at 40 ° C. for 1 hour and filter to remove solids.
  • the tetrahydrofuran solution was concentrated to obtain 10.1 g of 1,1,8,8-tetra (hydroxymethyl) octane as a colorless solid.
  • Example 26 (Compound (I-1c-B6)) to Example 39 (Compound (I-1t-BB)) ) was manufactured.
  • Example 56 (Compound (I-1e-B6)) to Example 64 (Compound (I-1o-BEBEB)) were carried out using the same reaction as in Example 55 and, if necessary, a method based on a known method. ) was manufactured.
  • Example 66 Compound (I-1f-B6)
  • Example 74 Compound (I-1p-BEBEB)
  • Example 76 (Compound (I-1g-B6)) to Example 82 (Compound (I-1q-BEBEB)) ) was manufactured.
  • Example 84 (Compound (I-1h-B6)) to Example 90 (Compound (I-1r-BEBEB)) ) was manufactured.
  • Measured characteristics of the liquid crystal composition containing any of the compounds obtained in Examples 1 to 90 are as follows.
  • VHR A voltage holding ratio (%) at 333 K was evaluated in three stages under the conditions of a frequency of 60 Hz and an applied voltage of 1 V.
  • VHR Light resistance
  • the liquid crystal composition is irradiated with ultraviolet rays at 180 J / m 2 using an ultrahigh pressure mercury lamp through a glass having a thickness of 0.5 mm.
  • the voltage holding ratio of the liquid crystal after ultraviolet irradiation is measured by the same method as the above VHR measurement.
  • the irradiation intensity was 366 nm and 0.1 W / m 2 . Evaluation was performed in the following three stages.
  • Example 1 To this base liquid crystal (H), 500 ppm of the compound (I-1a-5) obtained in Example 1 was added.
  • the measured properties of the composition examples in the examples are as follows.
  • VHR A Light resistant VHR: A Compatibility: A Storage stability: A
  • VHR A Light resistant VHR: A Compatibility: A Storage stability: A
  • Example 182 (Compound (I-1u-B6)) to Example 187 (Compound (I-1u-T3)) ) was manufactured.
  • VHR A Light resistant VHR: C Storage stability: A From this result, it can be seen that the compound of the present invention has an effect of preventing deterioration of the liquid crystal composition due to light without impairing the storage stability of the liquid crystal composition.
  • Comparative Example 2 500 ppm of compound (R-1) was added to the base liquid crystal (H), and the measurement results were as follows.
  • VHR A Light resistant VHR: A Compatibility: B Storage stability: C (Comparative Examples 3 and 4)
  • Comparative Examples 3 and 4 the results of measurement in Comparative Examples 3 and 4 in the same manner as in Comparative Example 2 are shown below.
  • the compound of the present invention has high compatibility with the liquid crystal composition without impairing the storage stability of the liquid crystal composition, and has an effect of preventing deterioration of the liquid crystal composition due to light.

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Abstract

La présente invention concerne un composé représenté par la formule générale (I) (dans laquelle Ra0 représente un atome d'hydrogène, un groupe hydroxy, un groupe alkyle ayant 1 à 12 atomes de carbone, ou un groupe alcényle ayant 3 à 12 atomes de carbone ; Ra1, Ra2, Ra3 et Ra4 représentent indépendamment un groupe alkyle ayant 1 à 8 atomes de carbone, ou Ra1 et Ra2 et/ou Ra3 et Ra4 peuvent former ensemble une structure cyclique ; Ra5 et Ra6 représentent indépendamment un atome d'hydrogène ou un groupe alkyle ayant 1 à 6 atomes de carbone ; n représente 0 ou 1 ; t représente 1 à 4 ; et U représente un groupe organique qui peut former une structure cyclique et a une valence de 2 × t).
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JPWO2017026271A1 (ja) * 2015-08-07 2017-08-31 Dic株式会社 液晶組成物及びそれを使用した液晶表示素子
JP2020090441A (ja) * 2018-12-03 2020-06-11 Dic株式会社 安定剤化合物、液晶組成物および表示素子
CN112852444A (zh) * 2019-11-27 2021-05-28 Dic株式会社 液晶组合物和使用其的液晶显示元件
KR20210063256A (ko) * 2019-11-21 2021-06-01 장쑤 허청 디스플레이 테크놀로지 컴퍼니, 리미티드 액정 조성물 및 이의 응용
JP2021084870A (ja) * 2019-11-27 2021-06-03 Dic株式会社 安定剤化合物、液晶組成物および表示素子

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JPWO2017026271A1 (ja) * 2015-08-07 2017-08-31 Dic株式会社 液晶組成物及びそれを使用した液晶表示素子
JP2020090441A (ja) * 2018-12-03 2020-06-11 Dic株式会社 安定剤化合物、液晶組成物および表示素子
KR20210063256A (ko) * 2019-11-21 2021-06-01 장쑤 허청 디스플레이 테크놀로지 컴퍼니, 리미티드 액정 조성물 및 이의 응용
KR102500486B1 (ko) 2019-11-21 2023-02-16 장쑤 허청 디스플레이 테크놀로지 컴퍼니, 리미티드 액정 조성물 및 이의 응용
CN112852444A (zh) * 2019-11-27 2021-05-28 Dic株式会社 液晶组合物和使用其的液晶显示元件
JP2021084870A (ja) * 2019-11-27 2021-06-03 Dic株式会社 安定剤化合物、液晶組成物および表示素子
JP2021084949A (ja) * 2019-11-27 2021-06-03 Dic株式会社 液晶組成物およびそれを用いた液晶表示素子
JP7363414B2 (ja) 2019-11-27 2023-10-18 Dic株式会社 安定剤化合物、液晶組成物および表示素子
JP7380136B2 (ja) 2019-11-27 2023-11-15 Dic株式会社 液晶組成物およびそれを用いた液晶表示素子

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