WO2023171757A1 - Composition polymère, matériau à différence de phase monocouche et agent d'alignement de cristaux liquides - Google Patents

Composition polymère, matériau à différence de phase monocouche et agent d'alignement de cristaux liquides Download PDF

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WO2023171757A1
WO2023171757A1 PCT/JP2023/009098 JP2023009098W WO2023171757A1 WO 2023171757 A1 WO2023171757 A1 WO 2023171757A1 JP 2023009098 W JP2023009098 W JP 2023009098W WO 2023171757 A1 WO2023171757 A1 WO 2023171757A1
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carbon atoms
atoms
liquid crystal
side chain
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PCT/JP2023/009098
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Japanese (ja)
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ダニエルアントニオ 櫻葉汀
司 藤枝
隆之 根木
友基 玉井
大貴 古賀
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日産化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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

Definitions

  • the present invention relates to a polymer composition, a single-layer retardation material, and a liquid crystal alignment agent.
  • materials with optical properties suitable for uses such as display devices and recording materials, in particular optical compensation films such as polarizing plates and retardation plates for liquid crystal displays, optical alignment films for liquid crystal displays, organic electroluminescence (
  • the present invention relates to a liquid crystalline polymer that can be suitably used in a circularly polarizing plate (EL), a composition containing the polymer, a single-layer retardation material and a liquid crystal alignment agent obtained from the composition.
  • EL circularly polarizing plate
  • the polymerizable liquid crystal compound used here generally has a polymerizable group and a liquid crystal structural site (a structural site having a spacer part and a mesogen part), and an acrylic group is widely used as this polymerizable group. ing.
  • Such polymerizable liquid crystal compounds are generally made into polymers (films) by polymerizing them by irradiating them with radiation such as ultraviolet rays.
  • radiation such as ultraviolet rays.
  • a method of obtaining a polymer by supporting a specific polymerizable liquid crystal compound having an acrylic group on an alignment-treated support and irradiating the compound with radiation while maintaining the compound in a liquid crystal state Patent Document 1
  • a method in which a photopolymerization initiator is added to a mixture of two types of polymerizable liquid crystal compounds having an acrylic group or a composition in which a chiral liquid crystal is mixed with this mixture, and a polymer is obtained by irradiating ultraviolet rays
  • Patent Document 2 are known.
  • the present invention was made in view of the above-mentioned problems, and provides a polymer composition that enables the production of a single-layer retardation layer having a high retardation value through thin film firing at a low temperature, and a monolayer retardation layer obtained from the composition.
  • the purpose of the present invention is to provide a retardation material and a liquid crystal aligning agent.
  • the present invention provides the following polymer composition and single-layer retardation material.
  • each W 2 may be the same or different from each other.
  • R' represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Q is an alkylene group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms of the alkylene group may be substituted with halogen atoms.
  • Q 1 is a single bond, a phenylene group, a naphthylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some or all of the hydrogen atoms of the phenylene group and naphthylene group are a cyano group, It may be substituted with a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. When the number of Q 1 is 2 or more, each Q 1 may be the same or different from each other.
  • the hydrogen atom on the benzene ring is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a cyano group, and a nitro group. It may be substituted with a substituent selected from.
  • the benzene ring may be a naphthalene ring
  • the hydrogen atom on the naphthalene ring is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms.
  • 6 may be substituted with a substituent selected from a haloalkoxy group, a cyano group, and a nitro group.
  • n 1 is 0, 1, 2 or 3.
  • the dashed lines are bonds.
  • T 1 is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms of the alkylene group may be substituted with halogen atoms.
  • T 1 is a single bond
  • a 2 is also a single bond.
  • Y 1 and Y 2 are a phenylene group or a naphthylene group, and some or all of the hydrogen atoms of the phenylene group and naphthylene group are cyano groups, halogen atoms, alkyl groups having 1 to 5 carbon atoms, or 2 to 5 carbon atoms.
  • P 1 , Q 1 and Q 2 are each independently a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some or all of the hydrogen atoms of the phenylene group are , a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
  • each Q 1 may be the same or different from each other, and when the number of Q 2 is 2 or more, each Q 2 may be the same or different from each other.
  • R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or a cycloalkyl group having 1 to 5 carbon atoms. It is an alkoxy group.
  • each X 1 may be the same or different from each other, and when the number of X 2 is 2 or more, each X 2 may be the same or different from each other.
  • G 1 and G 2 are each independently N or CH.
  • the broken lines are bonds.
  • each A 4 may be the same or different from each other.
  • R 1 is -NO 2 , -CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon It is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
  • R 2 is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some of the hydrogen atoms of these groups Alternatively, all may be substituted with -NO 2 , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
  • R 3 is a hydrogen atom, -NO 2 , -CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon having 5 to 8 carbon atoms. group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • k1 to k5 are each independently an integer of 0 to 2, but the total of k1 to k5 is 2 or more.
  • k6 and k7 are each independently an integer of 0 to 2, but the sum of k6 and k7 is 1 or more.
  • m1, m2 and m3 are each independently an integer of 1 to 3.
  • n is 0 or 1.
  • Some or all of the hydrogen atoms on the benzene ring or naphthalene ring are a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. May be replaced.
  • the broken lines are bonds.
  • ⁇ 5> [I] A step of applying any of the compositions of ⁇ 1> to ⁇ 4> above on a substrate to form a coating film; [II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] A step of heating the coating film obtained in [II] to obtain a retardation material. Method for manufacturing retardation material.
  • ⁇ 6> A single-layer retardation material obtained from the polymer composition according to any one of ⁇ 1> to ⁇ 4> above.
  • ⁇ 7> A liquid crystal aligning agent obtained from the polymer composition according to any one of ⁇ 1> to ⁇ 4> above.
  • the present invention it is possible to provide a single-layer retardation material and a liquid crystal aligning agent that are thin and have a high retardation value even in a low-temperature firing process.
  • the polymer composition of the present invention has a photosensitive side chain type polymer (hereinafter also simply referred to as a side chain type polymer) capable of exhibiting liquid crystallinity, and can be obtained using the polymer composition.
  • the coating film is a film containing a photosensitive side-chain type polymer capable of exhibiting liquid crystallinity. This coating film is subjected to orientation treatment by polarized light irradiation without performing rubbing treatment. After irradiation with polarized light, the side chain type polymer film is heated to become a film imparted with optical anisotropy (hereinafter also referred to as a single-layer retardation material).
  • the slight anisotropy developed by polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is efficiently reoriented by self-organization.
  • a highly efficient alignment process can be realized as a single-layer coated horizontally oriented film, and a single-layer coated horizontally oriented film imparted with high optical anisotropy can be obtained.
  • the side chain type polymer serving as the component (A) contains the side chain (a2) represented by the above formula (b) together with the side chain (a1) having a photoalignable site. ), the aggregation of the polymer is suppressed.
  • the retardation material obtained from the polymer composition of the present invention exhibits high retardation even in the form of a thin film under low-temperature firing conditions of 100° C. to 120° C. Note that these include the inventor's opinion regarding the mechanism of the present invention, and do not constrain the present invention. Embodiments of the present invention will be described in detail below.
  • the polymer composition of the present invention comprises (A) a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, comprising a side chain (a1) having a photoreactive site and the above formula (b ); and (B) an organic solvent.
  • Component (A) is a photosensitive side chain type polymer that exhibits liquid crystallinity in a predetermined temperature range, and has a side chain (a1) having a photoreactive site and a site represented by the above formula (b). It is a side chain type polymer having a side chain (a2).
  • the side chain type polymer preferably reacts with light in a wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in a temperature range of 80° C. to 300° C.
  • the side chain type polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
  • a side chain (a3) that exhibits only liquid crystallinity, other than the structure represented by the above formula (b), may be used. It is preferable to have.
  • the side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction or an isomerization reaction in response to light.
  • the structure of the photosensitive side chain type polymer capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the side chain structure has a rigid mesogenic component. In this case, stable optical anisotropy can be obtained when the side chain type polymer is used as a single layer retardation material.
  • More specific examples of structures of photosensitive side-chain polymers that can exhibit liquid crystallinity include (meth)acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, It is preferable that the structure has a main chain composed of at least one member selected from the group consisting of a radically polymerizable group such as norbornene and siloxane, and a side chain (a1) having a photoreactive site.
  • the side chain (a1) is preferably one represented by any of the following formulas (a1-1) to (a1-6).
  • the number of benzene rings that one side chain (a1) has is preferably three or less.
  • n1 and n2 are each independently 0, 1, 2 or 3.
  • T 1 is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms of the alkylene group may be substituted with halogen atoms.
  • a 2 is also a single bond.
  • Y 1 and Y 2 are a phenylene group or a naphthylene group, and some or all of the hydrogen atoms of the phenylene group and naphthylene group are cyano groups, halogen atoms, alkyl groups having 1 to 5 carbon atoms, or 2 to 5 carbon atoms. It may be substituted with an alkylcarbonyl group having 6 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • P 1 , Q 1 and Q 2 are each independently a single bond, a phenylene group, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and some or all of the hydrogen atoms of the phenylene group are , a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
  • each Q 1 may be the same or different from each other
  • each Q 2 may be the same or different from each other.
  • R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or a cycloalkyl group having 1 to 5 carbon atoms. It is an alkoxy group.
  • each X 1 may be the same or different from each other, and when the number of X 2 is 2 or more, each X 2 may be the same or different from each other.
  • G 1 and G 2 are each independently N or CH.
  • the broken lines are bonds.
  • the alkylene group having 1 to 12 carbon atoms may be linear, branched, or cyclic, and specific examples include a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group.
  • -diyl group pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane -1,10-diyl group and the like.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • the alkyl group having 1 to 5 carbon atoms may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and tert-butyl group. group, n-pentyl group, etc.
  • alkylcarbonyl group having 2 to 6 carbon atoms examples include methylcarbonyl (acetyl) group, ethylcarbonyl group, n-propylcarbonyl group, n-butylcarbonyl group, n-pentylcarbonyl group, and the like.
  • alkoxy group having 1 to 5 carbon atoms examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-pentyloxy group, and the like.
  • divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms examples include a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, and a cyclooctanediyl group.
  • cycloalkyl group having 3 to 7 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
  • the side chain (a1) As the side chain (a1), the following formulas (a1-1-1), (a1-1-2), (a1-2-1), (a1-3-1), (a1-4-1), Those represented by (a1-5-1) or (a1-6-1) are more preferred.
  • L, A 1 , A 2 , Y 1 , Y 2 , Q 1 , T 1 , R, X 1 , Cou, E, G 1 , G 2 , n1 and the broken line are the same as above.
  • the side chain represented by the formula (a1-1-1) is preferably a side chain represented by the following formula (a1-1-1-1), and a side chain represented by the formula (a1-1-2) is preferable.
  • side chains represented by formulas (a1-1-2-1), (a1-1-2-2) and (a1-1-2-3) are preferred.
  • Me means a methyl group
  • L, R and the broken line are the same as above.
  • the side chain represented by the formula (a1-2-1) is preferably a side chain represented by the following formula (a1-2-1-1). (In the formula, L, A 2 , Q 1 , T 1 , R and the broken line are the same as above.)
  • the side chain represented by the formula (a1-3-1) is represented by the following formula (a1-3-1-1), (a1-3-1-2) or (a1-3-1-3).
  • the side chain is (In the formula, L, Cou and the broken line are the same as above.)
  • the side chain represented by formula (a1-4-1) is the following formula (a1-4-1-1), (a1-4-1-2), (a1-4-1-3) or ( The side chain represented by a1-4-1-4) is preferred. (In the formula, L, R and the broken line are the same as above.)
  • the side chain represented by the formula (a1-5-1) is preferably a side chain represented by the following formula (a1-5-1-1) or (a1-5-1-2). (In the formula, L, R and the broken line are the same as above.)
  • the side chain represented by the formula (a1-6-1) is represented by the following formula (a1-6-1-1), (a1-6-1-2) or (a1-6-1-3).
  • the side chain is (In the formula, L, R and the broken line are the same as above.)
  • the side chain type polymer (A) contains a side chain (a2) having a photoreactive site represented by the above formula (b).
  • the side chain type polymer (A) exhibits liquid crystallinity in the temperature range of 80 to 300°C, it is preferable to use one of the above formulas (a3-1) to (a3-11). It is preferable to have a side chain (a3) that exhibits only liquid crystallinity.
  • "expressing only liquid crystallinity” here means that the polymer having only the side chain (a3) is used during the production process of the retardation material of the present invention (i.e., steps [I] to [III] described later). This means that it does not exhibit photosensitivity and only exhibits liquid crystallinity.
  • the photosensitive side chain type polymer capable of exhibiting the above-mentioned liquid crystallinity includes a monomer (MA) containing a side chain (a1) having a photoreactive site, a monomer (MA) having a site represented by formula (b) ( MB) and a monomer (MC) having a site that exhibits liquid crystallinity.
  • Monomers containing a side chain (a1) having a photoreactive site include the following formulas (M1), (M2), (M3), (M4), (M5) or ( Examples include compounds represented by M6).
  • PG is a polymerizable group, A 1 , A 2 , D 1 , L, T 1 , Y 1 , Y 2 , P 1 , Q 1 , Q 2 , R, Cou, E, X 1 . _ _ may be substituted with a substituent selected from an alkylcarbonyl group and an alkoxy group having 1 to 5 carbon atoms.
  • PG is a polymerizable group, and groups represented by any of the following formulas (PG1) to (PG7) are preferable.
  • an acrylic group or a methacrylic group represented by formula (PG1) is preferred from the viewpoint of easy control of the polymerization reaction and stability of the polymer.
  • R A and R B are each independently a hydrogen atom or a methyl group, and the broken line is a bond with L.
  • the compound represented by formula (M1) is preferably one represented by the following formula (M1-1), (M1-2), (M1-3) or (M1-4).
  • Me means a methyl group
  • PG, L, Y 1 , P 1' and R are the same as above.
  • the compound represented by formula (M2) is preferably one represented by formula (M2-1) below. (In the formula, PG, A 2 , L, T 1 , Y 1 , P 1 , Q 1 and R are the same as above.)
  • the compound represented by formula (M3) is preferably one represented by formula (M3-1) below. (In the formula, PG, A 1 , L, X 1 , Q 1 , Cou and n1 are the same as above.)
  • the compound represented by formula (M4) is preferably one represented by formula (M4-1) below. (In the formula, PG, A 1 , L, X 1 , Y 1 , Y 2 , Q 1 , E, R and n1 are the same as above.)
  • the compound represented by formula (M5) is preferably one represented by formula (M5-1) below. (In the formula, PG, A 1 , L, X 1 , Y 1 , Y 2 , Q 1 , R and n1 are the same as above.)
  • the compound represented by formula (M6) is preferably one represented by formula (M6-1) below. (In the formula, PG, A 1 , L, X 1 , Y 1 , Y 2 , Q 1 , G 1 , G 2 , R and n1 are the same as above.)
  • the compound represented by formula (M1-1) is preferably one represented by the following formula (M1-1-1), and the compound represented by formula (M1-2) is preferably one represented by the following formula (M1-1-1). 2-1) is preferable, and as a compound represented by formula (M1-3), a compound represented by the following formula (M1-3-1) is preferable, and a compound represented by formula (M1-4) is preferable. As the compound represented, a compound represented by the following formula (M1-4-1) is preferable. (In the formula, Me means a methyl group, and PG, L and R are the same as above.)
  • the compound represented by formula (M2-1) is preferably one represented by formula (M2-2) below. (In the formula, PG, A 2 , L, T 1 , Q 1 and R are the same as above.)
  • the compound represented by the formula (M3-1) is preferably one represented by the following formula (M3-2), (M3-3) or (M3-4). (In the formula, PG, L and Cou are the same as above.)
  • the compound represented by the formula (M4-1) is preferably one represented by the following formula (M4-2), (M4-3), (M4-4) or (M4-5). (In the formula, PG, L and R are the same as above.)
  • the compound represented by formula (M5-1) is preferably one represented by formula (M5-2) or (M5-3) below. (In the formula, PG, L and R are the same as above.)
  • the compound represented by the formula (M6-1) is preferably one represented by the following formula (M6-2), (M6-3), or (M6-4). (In the formula, PG, L and R are the same as above.)
  • Examples of the compound represented by formula (M1) include those represented by any of the following formulas (A-1-1-1) to (A-1-1-12).
  • PG is a polymerizable group
  • s1 represents the number of methylene groups and is an integer from 2 to 9.
  • R 12 is -H, -CH 3 , - CN or -F.
  • examples of the compound represented by formula (M1) include those represented by any of the following formulas (A-1-2-1) to (A-1-2-6).
  • PG is a polymerizable group
  • s1 is the same as above.
  • Me means a methyl group.
  • Specific examples of the compound represented by formula (M1) include 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, -(3-methacryloxypropyl-1-oxy)cinnamic acid, 4-[4-(6-methacryloxyhexyl-1-oxy)benzoyloxy]cinnamic acid, and the like.
  • Examples of the compound represented by formula (M2) include those represented by any of the following formulas (A-2-1) to (A-2-9).
  • PG is a polymerizable group
  • s1 and s2 represent the number of methylene groups, and are each independently an integer of 2 to 9. be.
  • Examples of the compound represented by formula (M3) include those represented by any of the following formulas (A-3-1) to (A-3-5).
  • PG is a polymerizable group
  • s1 is the same as above.
  • Examples of the compound represented by formula (M4) include those represented by any of the following formulas (A-4-1) to (A-4-4).
  • PG is a polymerizable group
  • s1 is the same as above.
  • Examples of the compound represented by formula (M5) include those represented by any of the following formulas (A-5-1) to (A-5-3).
  • PG is a polymerizable group
  • s1 is the same as above.
  • Examples of the compound represented by formula (M6) include those represented by any of the following formulas (A-6-1) to (A-6-3).
  • PG is a polymerizable group
  • s1 is the same as above.
  • Examples of the monomer having a moiety represented by formula (b) include a compound represented by the following formula (bm1-1).
  • formula (bm1-1) the definitions of each substituent are the same as those in formula (b) above, and PG is the same as the definition of PG above.
  • Preferred examples of the monomer MB having a moiety represented by formula (b) include the following formulas MB-1 to MB-10. (In the formula, s1 represents the number of methylene groups and is an integer from 2 to 9.)
  • the mesogenic group may be a group that forms a mesogenic structure by itself, such as biphenyl or phenylbenzoate, or a group that forms a mesogenic structure by hydrogen bonding between side chains, such as benzoic acid.
  • the mesogenic group possessed by the side chain preferably has a structure represented by any of the following formulas (b1) to (b11).
  • the monomer MC include hydrocarbons, radically polymerizable groups such as (meth)acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane. It is preferable that the structure has a polymerizable group derived from at least one of the above formulas (b1) to (b11). In particular, the monomer MC preferably has a polymerizable group derived from (meth)acrylate.
  • Preferred examples of monomer MC include those represented by the following formulas (MC-1) to (MC-10).
  • PG is a polymerizable group
  • p represents the number of methylene groups, and is an integer from 2 to 9.
  • monomers include unsaturated carboxylic acids, acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
  • acrylic ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-butyl acrylate.
  • methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and tert-butyl.
  • Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.
  • Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • the content of the side chain (a1) in the side chain type polymer of the present invention is preferably 5 to 99.9 mol%, more preferably 5 to 50 mol%, from the viewpoint of photoreactivity, and from the viewpoint of photostability. 5 to 20 mol% is even more preferable.
  • the content of the side chain (a2) in the side chain type polymer of the present invention is preferably 5 to 95 mol%, more preferably 5 to 80 mol%, and still more preferably 5 to 50 mol%, from the viewpoint of retardation value. preferable.
  • the side chain type polymer used in the present invention preferably has a side chain (a3) that exhibits only liquid crystallinity. It may also contain other side chains.
  • the content of side chains (a3) and other side chains is the remaining portion when the total content of side chains (a1) and side chains (a2) is less than 100 mol%.
  • the method for producing the polymer that is component (A) is not particularly limited, and any industrially-used general-purpose method can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using the above-mentioned monomer MA, monomer MB, optionally monomer MC, and optionally the vinyl group of other monomers. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control.
  • radical polymerization initiator for radical polymerization
  • known compounds such as radical polymerization initiators and reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used.
  • RAFT reversible addition-fragmentation chain transfer
  • a radical thermal polymerization initiator is a compound that generates radicals when heated above the decomposition temperature.
  • radical thermal polymerization initiators include, for example, ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxy, cyclohexane, etc.) etc.), alkyl peresters (peroxyneodecanoic acid tert-butyl ester, peroxypivalic acid tert-butyl ester, peroxy 2-eth
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • Such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(
  • the radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, etc. can be used.
  • the organic solvent used in the polymerization reaction is not particularly limited as long as it dissolves the produced polymer. Specific examples are listed below.
  • organic solvents may be used alone or in combination. Furthermore, even a solvent that does not dissolve the produced polymer may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate. Further, in radical polymerization, oxygen in an organic solvent becomes a cause of inhibiting the polymerization reaction, so it is preferable to use an organic solvent that has been degassed to the extent possible.
  • the polymerization temperature during radical polymerization can be any temperature in the range of 30 to 150°C, but is preferably in the range of 50 to 100°C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution will become too high, making it difficult to stir uniformly. Therefore, the monomer concentration is preferably 1 to 50% by weight, more preferably 5 to 30% by weight.
  • the initial stage of the reaction can be carried out at a high concentration, and then an organic solvent can be added.
  • the molecular weight of the obtained polymer will be small, and if it is small, the molecular weight of the obtained polymer will be large.
  • the amount is preferably 0.1 to 15 mol % based on the monomer to be polymerized.
  • various monomer components, solvents, initiators, etc. can be added during polymerization.
  • the reaction solution may be poured into a poor solvent to precipitate the polymers.
  • the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, and the like.
  • the polymer precipitated in a poor solvent can be collected by filtration and then dried under normal pressure or reduced pressure, at room temperature or by heating.
  • the amount of impurities in the polymer can be reduced.
  • the poor solvent in this case include alcohols, ketones, hydrocarbons, etc. It is preferable to use three or more types of poor solvents selected from these, since the efficiency of purification will further increase.
  • the molecular weight of the side chain type polymer (A) of the present invention is determined by the GPC (Gel Permeation Chromatography) method, taking into consideration the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film.
  • the weight average molecular weight is preferably 2,000 to 2,000,000, more preferably 5,000 to 150,000.
  • the weight average molecular weight is preferably 2,000 to 1,000,000, more preferably 5,000 to 200,000.
  • the organic solvent used in the polymer composition used in the present invention is not particularly limited as long as it can dissolve the resin component. Specific examples are listed below. N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl- ⁇ -caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, Dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, ⁇ -butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy- N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, cyclohexanone, cyclopentanone, ethylene carbonate, propylene carbonate, diglyme,
  • the polymer composition used in the present invention may contain components other than the above-mentioned components (A) and (B).
  • examples include solvents and compounds that improve film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the retardation material and the substrate. , but not limited to.
  • solvent it is preferably 1 to 60% by mass of the total solvent, more preferably 1% by mass, so as not to significantly reduce the solubility of the entire solvent contained in the polymer composition. ⁇ 40% by mass.
  • Examples of compounds that improve the uniformity of film thickness and surface smoothness include fluorosurfactants, silicone surfactants, and nonionic surfactants. More specifically, for example, FTOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafac (registered trademark) F171, F173, F560, F563, R-30, R-40, R -41 (manufactured by DIC), Florado FC430, FC431 (manufactured by 3M Japan), Asahi Guard (registered trademark) AG710 (manufactured by AGC), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105 , SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and the like.
  • the proportion of these surfactants used is preferably 0.01 parts by mass to 2 parts by mass, more preferably 0.01 parts by mass to 1 part by mass, based on
  • compounds that improve the adhesion between the retardation material and the substrate include the following functional silane-containing compounds.
  • the following additives such as phenoplast-based and epoxy group-containing compounds are used to prevent deterioration of characteristics due to backlight when forming a polarizing plate.
  • the following additives such as phenoplast-based and epoxy group-containing compounds are used to prevent deterioration of characteristics due to backlight when forming a polarizing plate.
  • Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane,
  • the amount used is preferably 0.1 parts by mass to 30 parts by mass based on 100 parts by mass of the resin component contained in the polymer composition. , more preferably 1 part by mass to 20 parts by mass. If the amount used is less than 0.1 part by mass, no effect of improving adhesion can be expected, and if it is more than 30 parts by mass, the alignment of the liquid crystal may deteriorate.
  • a photosensitizer can also be used as an additive. Colorless sensitizers and triplet sensitizers are preferred. Photosensitizers include aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy 4-methylcoumarin), ketocoumarins, carbonylbiscoumarins, aromatic 2-hydroxyketones, and amino-substituted , aromatic 2-hydroxyketone (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2-( ⁇ -naphthoylmethylene)-3-methylbenzothiazoline, 2-( ⁇ -naphthoylmethylene)-3-methylbenzothiazoline, 2-( ⁇ -n
  • aromatic 2-hydroxyketones (benzophenone), coumarins, ketocoumarins, carbonylbiscoumarins, acetophenones, anthraquinones, xanthone, thioxanthone, and acetophenone ketal.
  • the polymer composition may contain dielectrics, conductive substances, Furthermore, a crosslinkable compound may be added for the purpose of increasing the hardness and density of the film when used as a retardation material.
  • the polymer composition used in the present invention is preferably prepared as a coating liquid so as to be suitable for forming a retardation film. That is, the polymer composition used in the present invention includes the above-mentioned component (A), the above-mentioned solvent or compound that improves the film thickness uniformity and surface smoothness, and the compound that improves the adhesion between the liquid crystal alignment film and the substrate.
  • the compound is prepared as a solution in which the compound is dissolved in an organic solvent.
  • the content of component (A) is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, particularly preferably 3 to 20% by weight.
  • other polymers may be mixed in addition to component (A) within a range that does not impair liquid crystal expression ability and photosensitivity.
  • the content of other polymers in the resin component is 0.5 to 80% by mass, preferably 1 to 50% by mass.
  • examples of such other polymers include polymers made of poly(meth)acrylate, polyamic acid, polyimide, etc., which are not photosensitive side chain polymers capable of exhibiting liquid crystallinity.
  • the retardation material of the present invention can be manufactured by a method including the following [I] to [III]. [I] Step of applying the composition of the present invention onto a substrate to form a coating film; [II] A step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] A step of heating the coating film obtained in [II] to obtain a retardation material.
  • Step [I] is a process of applying the composition of the present invention onto a substrate. More specifically, the composition of the present invention is applied to a substrate (for example, a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, Bar coating, spin coating, flow coating, roll coating, Coating is performed by a method such as slit coating, slit coating followed by spin coating, an inkjet method, or a printing method. After coating, the solvent can be evaporated at 30 to 200° C., preferably 30 to 150° C., using a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven, to obtain a coating film.
  • a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven
  • step [II] the coating film obtained in step [I] is irradiated with polarized ultraviolet light.
  • the substrate is irradiated with polarized ultraviolet rays from a fixed direction via a polarizing plate.
  • the ultraviolet light to be used ultraviolet light with a wavelength in the range of 100 to 400 nm can be used.
  • the optimum wavelength is selected via a filter or the like depending on the type of coating film used.
  • ultraviolet light in the wavelength range of 290 to 400 nm can be selected and used so as to selectively induce a photocrosslinking reaction.
  • the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
  • the amount of polarized ultraviolet radiation depends on the coating used.
  • the amount of irradiation is the polarized ultraviolet rays that achieves the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet rays.
  • the amount is preferably within the range of 1 to 70%, and more preferably within the range of 1 to 50%.
  • step [III] the coating film irradiated with the polarized ultraviolet rays in step [II] is heated. By heating, orientation controllability can be imparted to the coating film.
  • heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven can be used.
  • the heating temperature can be determined in consideration of the temperature at which the coating film used exhibits liquid crystallinity.
  • the heating temperature is preferably within the temperature range at which the specific polymer contained in the composition of the present invention develops liquid crystallinity (hereinafter referred to as liquid crystal development temperature).
  • liquid crystal development temperature the temperature at which liquid crystals appear on the surface of the paint film is expected to be lower than the temperature at which liquid crystals appear when the specific polymer is observed in bulk. For this reason, the heating temperature is more preferably within the temperature range of the liquid crystal development temperature on the surface of the coating film.
  • the heating temperature range after irradiation with polarized ultraviolet rays has a lower limit of 10°C lower than the lower limit of the liquid crystal development temperature range of the specific polymer used, and an upper limit of 10°C lower than the upper limit of the liquid crystal temperature range. It is preferable that the temperature is within the range. If the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy due to heat in the coating film tends to be insufficient, and if the heating temperature is too high than the above temperature range, the condition of the coating film tends to be insufficient. tends to be close to an isotropic liquid state (isotropic phase), in which case it may be difficult to reorient in one direction due to self-organization.
  • isotropic liquid state isotropic phase
  • the liquid crystal development temperature is the liquid crystal transition temperature at which the polymer or coating surface undergoes a phase transition from a solid phase to a liquid crystal phase, and is an isotropic phase at which a phase transition occurs from a liquid crystal phase to an isotropic phase.
  • a temperature below the phase transition temperature (Tiso) For example, exhibiting liquid crystallinity at 130° C. or lower means that the liquid crystal transition temperature at which a phase transition from a solid phase to a liquid crystal phase occurs is 130° C. or lower.
  • the thickness of the coating film formed after heating can be appropriately selected in consideration of the level difference and optical and electrical properties of the substrate used, and is preferably 0.5 to 10 ⁇ m, for example.
  • the single-layer retardation material of the present invention thus obtained is a material having optical properties suitable for use in display devices, recording materials, etc., and is particularly suitable for use in polarizing plates and retardation plates for liquid crystal displays. It is suitable as an optical compensation film and a retardation film for circularly polarizing plates of organic EL.
  • the present invention provides a liquid crystal aligning agent having the above-mentioned polymer composition, consisting essentially of the above-mentioned polymer composition, or consisting only of the above-mentioned polymer composition, particularly for use in liquid crystal display elements, more particularly A liquid crystal aligning agent for a transverse electric field driven liquid crystal display element is provided.
  • the present invention provides a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent, particularly a liquid crystal alignment film for a liquid crystal display element, and more particularly for a horizontal electric field drive type liquid crystal display element.
  • the present invention also provides a substrate having a liquid crystal alignment film formed from the above-mentioned liquid crystal alignment agent, particularly for a liquid crystal display element, more particularly for a horizontal electric field drive type liquid crystal display element, particularly for a liquid crystal display element, and more particularly for a liquid crystal display element.
  • a substrate for a lateral electric field driven liquid crystal display element is provided.
  • the above-mentioned liquid crystal alignment film is a liquid crystal alignment film imparted with alignment control ability by having the steps [I] to [III] above, particularly for liquid crystal display elements, more particularly for transverse electric field drive type liquid crystal display elements.
  • a liquid crystal alignment film or a substrate having the liquid crystal alignment film can be obtained.
  • the substrate is not particularly limited, but if the liquid crystal display element to be manufactured is of a transmission type, it is preferable to use a highly transparent substrate. In that case, there are no particular limitations, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. Furthermore, in consideration of application to reflective liquid crystal display elements, opaque substrates such as silicon wafers can also be used.
  • the substrate When used in a lateral electric field driven liquid crystal display element, the substrate has a conductive film for lateral electric field driving.
  • the conductive film include, but are not limited to, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and the like.
  • the conductive film may be made of a material that reflects light, such as aluminum, but is not limited thereto. A conventionally known method can be used to form the conductive film on the substrate.
  • Steps [I] to [III] are the same as above.
  • the wavelength is preferably 5 to 300 nm, more preferably 10 to 150 nm.
  • the present invention provides a liquid crystal display element, particularly a transverse electric field drive type liquid crystal display element, having a substrate having the liquid crystal alignment film obtained above.
  • a transverse electric field drive type liquid crystal display element can be obtained.
  • the second substrate has a conductive film for transverse electric field drive, as in the first substrate.
  • a substrate having the following characteristics is used.
  • the second substrate has a liquid crystal alignment film, similarly to the first substrate.
  • the manufacturing method of liquid crystal display elements is as follows: [IV] Obtaining a liquid crystal display element by arranging the first and second substrates obtained above to face each other so that the liquid crystal alignment films of the first and second substrates face each other via the liquid crystal; has. Thereby, a liquid crystal display element, particularly a lateral electric field drive type liquid crystal display element, can be obtained.
  • Step is the substrate (first substrate) having a liquid crystal alignment film on the conductive film for transverse electric field driving obtained in [III], and the substrate obtained in [I'] to [III'] above.
  • the obtained substrate with a liquid crystal alignment film (second substrate) was placed facing each other with the liquid crystal interposed therebetween so that both liquid crystal alignment films faced each other, a liquid crystal cell was produced by a known method, and a transverse electric field was applied.
  • steps [I'] to [III'] can be performed in the same manner as steps [I] to [III] except for the difference in the presence or absence of a conductive film for horizontal electric field drive in step [I].
  • the only difference between steps [I] to [III] and steps [I'] to [III'] is the presence or absence of the above-mentioned conductive film, so the explanation of steps [I'] to [III'] will be omitted. do.
  • the above-mentioned first and second substrates are prepared, and spacers are sprinkled on the liquid crystal alignment film of one of the substrates, so that the liquid crystal alignment film surface is on the inside.
  • a method of bonding the other substrate and sealing by injecting liquid crystal under reduced pressure, or a method of dripping liquid crystal onto the surface of the liquid crystal alignment film on which spacers have been sprinkled, and then bonding the substrates together and sealing. , etc. can be exemplified.
  • the diameter of the spacer is preferably 1 ⁇ m to 30 ⁇ m, more preferably 2 ⁇ m to 10 ⁇ m. This spacer diameter determines the distance between the pair of substrates that sandwich the liquid crystal layer, that is, the thickness of the liquid crystal layer.
  • the polymer composition or liquid crystal aligning agent of the present invention a liquid crystal aligning film formed using the composition or liquid crystal aligning agent, or a substrate having the aligning film, and a substrate having the liquid crystal aligning film or the substrate.
  • the liquid crystal display element formed by this method can be suitably used for large-screen, high-definition liquid crystal televisions, etc.
  • MA1 to MA2 having a photoreactive group and monomers MB1 to MB4 and MC1 to MC3 having liquid crystal properties used in Examples are shown below.
  • MA1 was synthesized according to the synthesis method described in International Publication No. 2011/084546.
  • MA2 was synthesized according to the synthesis method described in JP-A-2012-27354.
  • MC1 was synthesized according to the synthesis method described in JP-A-9-118717.
  • MB1 was synthesized according to the synthesis method described in JP-A-2016-128403.
  • MB2 to MB4 are new compounds, and the synthesis method is shown below.
  • MC2 and MC3 were synthesized according to the synthesis method described in International Publication No. 2017/135130.
  • the side chain derived from MA1 corresponds to the side chain (a1)
  • the side chain derived from MB1 to MB4 corresponds to the side chain (a2)
  • the side chain derived from MC1 to MC3 corresponds to the side chain (a3). Applies to.
  • reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-1 (13.0 g).
  • the number average molecular weight of P-1 was 22,000, and the weight average molecular weight was 74,000.
  • reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-2 (13.6 g).
  • the number average molecular weight of P-2 was 23,000, and the weight average molecular weight was 84,000.
  • reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-3 (13.8 g).
  • the number average molecular weight of P-3 was 30,000, and the weight average molecular weight was 95,000.
  • P-4 had a number average molecular weight of 19,000 and a weight average molecular weight of 54,000.
  • the monomer mixed solution was added dropwise to NMP (14.2 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours.
  • reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-7 (12.1 g).
  • the number average molecular weight of P-7 was 23,000 and the weight average molecular weight was 45,000.
  • the monomer mixed solution was added dropwise to NMP (13.9 g) at 60° C. over 2 hours under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours.
  • reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-8 (12.6 g).
  • the number average molecular weight of P-8 was 24,000, and the weight average molecular weight was 52,000.
  • reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-9 (6.01 g).
  • the number average molecular weight of P-9 was 21,000, and the weight average molecular weight was 99,000.
  • the monomer mixed solution was added dropwise to NMP (6.72 g) over 2 hours at 60° C. under a nitrogen atmosphere. After the dropwise addition was completed, the reaction was carried out at 60° C. for 12 hours.
  • reaction solution was poured into a methanol/pure water mixed solvent to precipitate the polymer, which was filtered and washed with methanol to obtain polymer powder P-10 (6.12 g).
  • the number average molecular weight of P-10 was 20,000, and the weight average molecular weight was 50,000.
  • Polymer solution T-7 was obtained by adding and stirring CPN (16.38 g) and F560 (18.0 mg) to polymer powder P-2 (3.60 g) obtained in Synthesis Example 2. .
  • This polymer solution T-7 was directly used as a material for forming a retardation film.
  • Example 2 to 16 Glass substrates S-2 to S-16 with retardation films were prepared in the same manner as in Example 1, except that the polymer solution, exposure amount, and main firing temperature were changed as shown in Tables 2 and 3. did.
  • Example 17 Polymer solution T-9 was filtered through a filter with a pore size of 5.0 ⁇ m, and then applied onto a COP film (ZF16-100, manufactured by Nippon Zeon) using a bar coater. This substrate was dried in a thermal circulation oven at 50° C. for 3 minutes, and then 1200 mJ/cm 2 of 365 nm polarized ultraviolet light was irradiated onto this substrate from a high-pressure mercury lamp through a 365 nm bandpass filter and a polarizing plate. It was heated in an IR oven at 120° C. for 10 minutes to produce a COP film S-17 with a retardation film. Note that the thickness of the retardation layer of S-17 was 2.0 ⁇ m.
  • Example 18 Polymer solution T-10 was filtered through a filter with a pore size of 5.0 ⁇ m, and then applied onto a COP film (ZF16-100, manufactured by Nippon Zeon) using a bar coater. This substrate was dried in a thermal circulation oven at 50° C. for 3 minutes, and then 200 mJ/cm 2 of 313 nm polarized ultraviolet light was irradiated from a high-pressure mercury lamp through a 313 nm bandpass filter and a polarizing plate. It was heated in an IR oven at 120° C. for 10 minutes to produce a COP film S-18 with a retardation film. Note that the thickness of the retardation layer of S-18 was 2.0 ⁇ m.
  • Polymer solution T-8 was filtered through a filter with a pore size of 5.0 ⁇ m, and then applied onto a COP film (ZF16-100, manufactured by Nippon Zeon) using a bar coater.
  • This substrate was dried in a thermal circulation oven at 50° C. for 3 minutes, and then 200 mJ/cm 2 of 313 nm polarized ultraviolet light was irradiated from a high-pressure mercury lamp through a 313 nm bandpass filter and a polarizing plate. It was heated in an IR oven at 120° C. for 10 minutes to produce a COP film R-5 with a retardation film. Note that the thickness of the retardation layer of R-5 was 2.0 ⁇ m.
  • the film thickness, retardation value, and ⁇ n of each of the substrates S-1 to S18 and R-1 to R-5 with retardation films were evaluated by the following method.
  • the film thickness of the retardation layer of the glass substrate with a retardation film was measured using a high-precision fine shape measuring machine (ET4000M) manufactured by Kosaka Laboratory Co., Ltd.
  • the film thickness of the retardation layer of the COP film with a retardation film was measured using F20 film thickness meter manufactured by Filmetrics.
  • a single-layer retardation material obtained from a polymer composition using monomer MB showed a higher ⁇ n than a single-layer retardation material obtained from a polymer composition not using monomer MB. Since it shows a good ⁇ n when fired at a low temperature of 100 to 120°C, it is possible to form a retardation layer on a film base material.
  • a substrate for order parameter measurement was prepared using the liquid crystal aligning agent (U-1) according to the procedure shown below.
  • the substrate used was a quartz substrate measuring 40 mm x 40 mm and having a thickness of 1.0 mm. After filtering the liquid crystal aligning agent (U-1) through a 1.0 ⁇ m filter, it was spin-coated onto a quartz substrate and dried on a hot plate at 60° C. for 90 seconds to form a thin film with a thickness of 100 nm.
  • the order parameter S was calculated from the absorbance of polarized light using the following formula.
  • a para represents absorbance in a direction parallel to the direction of polarized ultraviolet rays irradiated
  • a per represents absorbance in a direction perpendicular to the direction of polarized ultraviolet rays irradiated.
  • the absolute values of the calculated order parameters (S) are shown in Table 5.
  • evaluation criteria ⁇ : 0.5 or more ⁇ : 0.4 or more and less than 0.5 ⁇ : 0.3 or more and less than 0.4 ⁇ : less than 0.3
  • the liquid crystal aligning agent obtained from the polymer composition using the monomer MB shows an order parameter value of about 0.4 to 0.5 under low temperature firing conditions of 120°C, and the liquid crystal alignment agent It was confirmed that it can function as a membrane.

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Abstract

L'invention concerne une composition polymère se présentant sous la forme d'une composition polymère qui fournit un matériau à différence de phase monocouche présentant une valeur de différence de phase élevée, même avec une cuisson à basse température et même sous la forme d'un film mince : (A) un polymère de type à chaîne latérale qui a une chaîne latérale (a1) qui a un site photoréactif et une chaîne latérale (a2) qui a un site représenté par la formule (b) ; et (B) un solvant organique. L'invention concerne également un agent d'alignement de cristaux liquides et un matériau à différence de phase monocouche obtenu à partir de ladite composition polymère. (Dans la formule, L, W1, W2, W3, Q1, n1 et Q sont tels que définis dans la description.)
PCT/JP2023/009098 2022-03-10 2023-03-09 Composition polymère, matériau à différence de phase monocouche et agent d'alignement de cristaux liquides WO2023171757A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016002691A1 (fr) * 2014-06-30 2016-01-07 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP2016128403A (ja) * 2014-12-02 2016-07-14 Jnc株式会社 液晶性化合物、液晶組成物およびその重合体
JP2019148716A (ja) * 2018-02-27 2019-09-05 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
WO2021070515A1 (fr) * 2019-10-10 2021-04-15 Jsr株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016002691A1 (fr) * 2014-06-30 2016-01-07 日産化学工業株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément d'affichage à cristaux liquides
JP2016128403A (ja) * 2014-12-02 2016-07-14 Jnc株式会社 液晶性化合物、液晶組成物およびその重合体
JP2019148716A (ja) * 2018-02-27 2019-09-05 日産化学株式会社 液晶配向剤、液晶配向膜、及び液晶表示素子
WO2021070515A1 (fr) * 2019-10-10 2021-04-15 Jsr株式会社 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides et élément à cristaux liquides

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