WO2018110529A1 - Sealing material composition for display element, and display element in which said composition is used - Google Patents

Sealing material composition for display element, and display element in which said composition is used Download PDF

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Publication number
WO2018110529A1
WO2018110529A1 PCT/JP2017/044504 JP2017044504W WO2018110529A1 WO 2018110529 A1 WO2018110529 A1 WO 2018110529A1 JP 2017044504 W JP2017044504 W JP 2017044504W WO 2018110529 A1 WO2018110529 A1 WO 2018110529A1
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oco
carbon atoms
general formula
coo
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PCT/JP2017/044504
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French (fr)
Japanese (ja)
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浩一 延藤
桑名　康弘
伊佐 西山
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Dic株式会社
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Priority to JP2018556675A priority Critical patent/JP6551618B2/en
Publication of WO2018110529A1 publication Critical patent/WO2018110529A1/en

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    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations

Definitions

  • the present invention relates to a sealing material composition for a display element containing a filler and a polymerizable liquid crystal compound, which is used as a sealing agent for liquid crystal display elements, organic light emitting display elements, and the like, and a sealing agent and a base material using the composition
  • the present invention relates to a sealing protective agent, a liquid crystal display element, and an organic light emitting display element.
  • a display element such as a liquid crystal display element or an organic light emitting display element
  • Organic light-emitting substances such as liquid crystal materials, organic light-emitting diodes, and quantum dots used in these display elements are easily affected by moisture and oxygen, and glass sheets and metal sheets are used to ensure stable operation over a long period of time. It has been used as a sealing material.
  • the sealing material cannot cope with weight reduction and flexibility, and sealing materials using various polymer materials are being studied.
  • the problem to be solved by the present invention is to provide a sealing material composition for a display element having high gas barrier property and water vapor barrier property, and at the same time, a sealing agent for display element and substrate sealing using the composition It is providing the liquid crystal display element using the protective agent, the said sealing agent, and / or base-material sealing protective agent, an organic light emitting display element, and a quantum dot display element.
  • the present invention has been conducted by paying attention to using a polymerizable liquid crystal compound and a filler, and as a result, has come to provide the present invention.
  • this invention provides the sealing material composition for display elements containing at least 1 or more types of fillers and 1 type, or 2 or more types of polymerizable liquid crystal compounds. Moreover, the sealing agent using the composition of this invention, a base-material sealing protective agent, and the display element using the said sealing agent and / or base-material sealing protective agent are also provided.
  • a sealing protective layer having high gas barrier properties and water vapor barrier properties can be formed. is there.
  • the “liquid crystal” of the polymerizable liquid crystal compound is a compound of only one kind of the polymerizable liquid crystal compound to be used. It is intended to exhibit liquid crystallinity when it is intended to show or when mixed with other liquid crystal compounds to form a mixture.
  • the sealing material composition for display elements can be polymerized (formed into a film) by performing a polymerization treatment by irradiation with light such as ultraviolet rays, heating, or a combination thereof.
  • the sealing material composition for display elements of the present invention is characterized by containing at least one filler. By using a filler together with one or more polymerizable liquid crystal compounds, the sealing composition for a display element of the present invention can have high gas barrier properties and high water vapor barrier properties.
  • an organic filler or an inorganic filler can be used according to the shape to be used.
  • the shape of the inorganic filler is preferably a powdery filler.
  • the maximum particle size of the powdery filler used in the present invention is preferably 0.01 ⁇ m or more and 50 ⁇ m or less, more preferably 0.01 ⁇ m or more and 40 ⁇ m or less, further preferably 0.01 ⁇ m or more and 35 ⁇ m or less, and 0.01 ⁇ m or more and 30 ⁇ m or less. Is particularly preferred.
  • the average particle diameter is preferably 0.002 ⁇ m or more and 20 ⁇ m or less, more preferably 0.002 ⁇ m or more and 15 ⁇ m or less, further preferably 0.002 ⁇ m or more and 12 ⁇ m or less, and particularly preferably 0.002 ⁇ m or more and 10 ⁇ m or less.
  • the average particle diameter is less than 0.002 ⁇ m or exceeds 50 ⁇ m, it does not have a great influence on the improvement of the gas barrier performance and the water vapor barrier performance, so it is preferable to use a powdery filler in the above range.
  • examples of the powdery filler include lamellar plate-like or scale-like, spherical or indeterminate, rod-like needle-like or fiber-like. These may be used alone or in combination of two or more. Since the shape of the filler is excellent in gas barrier properties and high water vapor barrier properties, a layered inorganic filler, a spherical or amorphous filler, or a rod-like organic filler is preferably used.
  • the total content of the filler in the display element sealing material composition is 3 parts by mass to 40 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used in the display element sealing material composition. It is preferably 3 to 30 parts by mass, more preferably 3 to 25 parts by mass.
  • the plate-like or scale-like fillers forming the layer form include talc, graphite, plate-like calcium carbonate, plate-like alumina, and silicates such as bentonite group clay minerals, smectite group clay minerals and mica group clay minerals. At least one selected can be preferably used.
  • the clay mineral include synthetic smectite, hectorite, beidellite, saponite, montmorillonite, vermiculite, stevensite, mica, synthetic mica, sodium tetrasilicon mica, and the like.
  • the clay mineral may be a modified clay mineral modified with a silylating agent so as to have a water vapor barrier property.
  • a known silylating agent such as methyltrimethoxysilane can be used as the silylating agent, but the silylating agent used is preferably 30% by weight or less based on the total amount of clay and silylating agent.
  • the average thickness of the layered filler is preferably less than 0.5 ⁇ m, more preferably less than 0.2 ⁇ m, still more preferably less than 0.1 ⁇ m, and particularly preferably less than 0.05 ⁇ m.
  • the average particle diameter (particle width) of the layered filler is preferably 0.01 ⁇ m or more and 10 ⁇ m or less, more preferably 0.02 ⁇ m or more and 5 ⁇ m or less, and still more preferably, as observed by an electron microscope.
  • the aspect ratio of the layered filler is in the range of 100 to 2500, more preferably in the range of 200 to 2000, and still more preferably in the range of 250 to 1500, particularly when the particle diameter is microscopically observed.
  • the range of 300 to 1000 is preferable.
  • the layered filler is preferably used in an amount of 3 to 40 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements. More preferably, 3 parts by mass to 25 parts by mass is used.
  • Spherical or amorphous shapes include calcium carbonate, powdered silica, powdered metal powder, alumina, boehmite, hydrotalcite, magnesium hydroxide, magnesium oxide, zinc oxide, aluminum silicate, calcium silicate, aluminum hydroxide, carbon black , Titanium oxide, barium titanate and the like.
  • aluminum silicate, alumina, powder silica, and zinc oxide are preferably used from the viewpoints of transparency and gas barrier properties, and alumina and powder silica are more preferably used.
  • the average particle size of the fine powder filler is such that the primary particle size by electron microscope observation is preferably 0.5 ⁇ m or more and 30 ⁇ m or less, more preferably 0.5 ⁇ m or more and 20 ⁇ m or less, and further preferably 0.5 ⁇ m or more. It is 15 ⁇ m or less, and particularly preferably 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the powder filler is used in an amount of 5 to 35 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used in the sealing material composition for display elements. It is preferable to use 8 to 35 parts by mass, and it is particularly preferable to use 10 to 30 parts by mass.
  • the needle-like or fibrous fillers that form fine rods, glass fiber, carbon fiber (carbon nanofiller), boron fiber, zonolite, wollastonite, apatalite, calcium carbonate whisker, aluminum borate whisker as inorganic materials Zinc oxide whisker, potassium titanate whisker and the like, and examples of the organic material include aramid fiber and liquid crystal polyester fiber.
  • wollastonite and zinc oxide whiskers are preferably used from the viewpoint of impact strength, heat resistance, and gas barrier properties, and wollastonite is more preferably used.
  • the average particle diameter of the rod-shaped filler is preferably 1 ⁇ m or more and 30 ⁇ m or less, more preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 1 ⁇ m or more and 20 ⁇ m or less. Preferably they are 1 micrometer or more and 15 micrometers or less, Most preferably, they are 1 micrometer or more and 10 micrometers or less.
  • the average particle diameter by electron microscope observation is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 1 ⁇ m or more and 15 ⁇ m or less, further preferably 1 ⁇ m or more and 12 ⁇ m or less, and particularly preferably 1 ⁇ m or more and 10 ⁇ m or less. It is.
  • the rod-shaped filler is preferably used in an amount of 5 to 30 parts by mass, preferably 5 to 25 parts by mass, with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the display element sealing material composition. More preferably, 10 to 20 parts by mass is used.
  • the polymerizable liquid crystal compound used in the present invention is not particularly limited as long as it is a compound that exhibits liquid crystallinity alone or in a composition with another compound and has at least one polymerizable functional group. Conventional ones can be used.
  • a rod-like polymerizable liquid crystal compound having a polymerizable functional group such as a vinyl group, an acrylic group or a (meth) acryl group, or a maleimide as described in JP-A Nos. 2004-2373 and 2004-99446
  • a rod-like polymerizable liquid crystal compound having a group examples thereof include a rod-like polymerizable liquid crystal compound having a group.
  • a rod-like liquid crystal compound having a polymerizable group is preferable because it can easily produce a liquid crystal having a temperature range around room temperature.
  • the polymerizable liquid crystal compound is preferably a compound represented by the following general formula (II).
  • P 21 represents a polymerizable functional group
  • Sp 21 represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is a group having one or more halogen atoms, a CN group, or a polymerizable functional group). may be substituted, each of the one CH 2 group or nonadjacent two or more CH 2 groups existing in the alkylene group independently of one another by, -O -, - COO -, - OCO Or may be replaced by-or -OCO-O-).
  • X 21 represents —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S.
  • one —CH 2 — or two or more non-adjacent —CH 2 — 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—CH ⁇ CH—, —OCO—CH ⁇ CH—, —CH ⁇ CH—, —CF ⁇ CF— or —C ⁇ C— may be substituted, or R 21 may have the general formula (II-a)
  • P 22 represents a polymerizable functional group
  • Sp 22 represents the same as defined in Sp 21
  • X 22 represents that defined in X 21.
  • P 22 -Sp 22 and Sp 22 -X 22 do not include —O—O—, —O—NH—, —S—S— and —O—S— groups).
  • Q22 represents 0 or 1.
  • the mesogenic group represented by the above MG has the general formula (II-b)
  • B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2, 5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2, 6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4 Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-d
  • P 23 represents a polymerizable functional group
  • Sp 23 represents the same as defined in Sp 21 above
  • X 23 represents —O—, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, or
  • a single bond is represented
  • q23 represents 0 or 1
  • q24 represents 0 or 1.
  • Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH ⁇ CH—.
  • Sp 21 represents an alkylene group having 1 to 18 carbon atoms, and the hydrogen atom in the alkylene group may be substituted with a group having a polymerizable functional group.
  • examples of a group preferable as the group having a polymerizable functional group include a group represented by the general formula (II-c).
  • P 21 , P 22 and P 23 are each independently represented by the following formula (P-2-1): It preferably represents a substituent selected from a polymerizable group represented by the formula (P-2-20).
  • B1, B2 and B3 may each independently have the above-mentioned substituents, 1,4-phenylene group, 1,4-cyclohexylene group, 2,6 -Preferably represents a naphthylene group.
  • Sp 21 , Sp 22 and Sp 23 are each independently from the viewpoint of enhancing storage stability. preferably represents an 1-14 alkylene group, two or more CH 2 groups not one CH 2 group or adjacent existing in the alkylene group independently of one another each, -O -, - COO It may be replaced by-or -OCO-. Further, Sp 21 , Sp 22 and Sp 23 each independently preferably represent an alkylene group having 1 to 12 carbon atoms, and are not adjacent to one CH 2 group present in the alkylene group. Two or more CH 2 groups may be replaced by —O—.
  • X 21 , X 22, and X 23 are each independently —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO —CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 —, — It preferably represents OCO—CH 2 —, —CH 2 —COO—, —CH 2 —OCO—, —CH ⁇ CH—, —C ⁇ C— or a single bond, —O—, —COO—, —OCO
  • Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 O—, —CH ⁇ CH—, —C ⁇ C—, —CH 2 CH 2. It preferably represents COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, —C ⁇ N—, —N ⁇ C—, or a single bond.
  • r1 preferably represents 0 or 1.
  • r1 preferably represents 0 or 1.
  • the compound represented by the following general formula (II-1) is preferable as the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule.
  • R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent —CH 2 —, each independently —O—.
  • B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group,
  • the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
  • Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH
  • P 211 is the above-described formula (P-2-1), (P-2-2), (P-2-7), (P— 2-12) and (P-2-13) are preferable, and formulas (P-2-1), (P-2-2), and (P-2-7) are more preferable.
  • Sp 211 is preferably each independently an alkylene group having 1 to 14 carbon atoms from the viewpoint of enhancing storage stability, and is present in the alkylene group.
  • Two CH 2 groups or two or more non-adjacent CH 2 groups may be each independently replaced by —O—, —COO— or —OCO—.
  • Sp 211 are each independently more preferably an alkylene group having 1 to 12 carbon atoms, not one CH 2 group or adjacent existing in the alkylene group two or more CH 2 The group may be replaced by -O-.
  • X 211 each independently represents —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —O—CO.
  • R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent —CH 2 —, each independently —O —, —CO—, —COO—, —OCO—, —O—CO—O—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH
  • R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent —CH 2 —, each independently —O—, —CO—, —COO.
  • one or more hydrogen atoms of the alkyl group or alkenyl group may be substituted with a halogen atom or a cyano group, and when a plurality of substituents are substituted, they may be the same or different. Also good.
  • B11, B21 and B31 each independently may have the above-mentioned substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, and Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH ⁇ CH It is preferable to represent —, —C ⁇ C—, —C ⁇ N—, —N ⁇ C—, or a single bond, and r11 preferably represents 0 or 1.
  • Examples of the general formula (II-1) include compounds represented by the following general formulas (II-1-1) to (II-1-4), but are not limited to the following general formulas is not.
  • P 211 , Sp 211 , X 211 , and q 211 are the same as defined in the general formula (II-1).
  • B111, B112, B113, B21, and B31 are the same as the definitions of B11 to B31 in the general formula (II-1-b).
  • preferred groups also represent the same as defined for B11 to B31, and may be the same or different.
  • Z111, Z112, Z113, and Z21 represent the same definitions as Z11 to Z21 in the general formula (II-1-b).
  • R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent — CH 2 — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO.
  • the compounds represented by the general formulas (II-1-1) to (II-1-4) are represented by the following formulas (II-1-1-1) to (II-1-1-26).
  • the compounds represented are exemplified, but not limited thereto.
  • R c represents a hydrogen atom or a methyl group
  • m represents an integer of 0 to 18, n represents 0 or 1
  • R 211 represents the above general formulas (II-1-1) to (II- 1-4) is the same as defined above, except that R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 — is —O—, —CO—, —COO—, —OCO—, It preferably represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 1 to 6 carbon atoms, which may be substituted by
  • the cyclic group includes one or more F, Cl, CF 3 , OCF 3 , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 8 alkanoyl groups, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbon
  • the compounds represented by the general formulas (II-1-1-1) to (II-1-1-26) are more specifically represented by the following general formulas (II-1-2-1) to The compound represented by (II-1-2-37) can be exemplified, but is not limited thereto.
  • the total content of the polymerizable liquid crystal compound is preferably 0 to 90% by mass, and preferably 0 to 85% by mass, based on the total amount of the polymerizable liquid crystal compound used in the sealing material composition for display elements. More preferably, the content is particularly preferably 0 to 80% by mass.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and when emphasizing the hardness of the coating film, the upper limit Is preferably 80% by mass or less, and more preferably 70% by mass or less.
  • the compound represented by the following general formula (II-2) is preferable as the bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule.
  • P 221 , X 211 , q 221 , X 222 , q 222 , and P 222 are P 21 , X 21 , q 21 , X 22 , q 22 in the general formula (II) or the general formula (II-a), respectively.
  • Sp 221 and Sp 222 each independently represent an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is one or more halogen atoms, or CN It may be substituted by a group, two or more of CH 2 groups, independently of one another each of the present in the radical is not one CH 2 group or adjacent, -O -, - COO -, - OCO -Or -OCO-O- may be substituted).
  • MG 2 represents a mesogenic group, and the mesogenic group includes the general formula (II-2-b)
  • B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group,
  • the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
  • Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH
  • P 221 and P 222 are each independently from the above formulas (P-2-1), (P-2-2), (P— 2-7), (P-2-12), and (P-2-13) are preferable, and formulas (P-2-1) and (P-2-2) are more preferable.
  • Sp 221 and Sp 222 are preferably each independently an alkylene group having 1 to 14 carbon atoms from the viewpoint of enhancing storage stability.
  • One CH 2 group present or two or more non-adjacent CH 2 groups may each be independently replaced by —O—, —COO— or —OCO—.
  • each of Sp 221 and Sp 222 preferably independently represents an alkylene group having 1 to 12 carbon atoms, and one CH 2 group present in the alkylene group or two or more not adjacent to each other The CH 2 group may be replaced by —O—.
  • X 221 and X 222 each independently represent —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, — O—CO—O—, —CH ⁇ CH—COO—, —CH ⁇ CH—OCO—, —COO—CH ⁇ CH—, —OCO—CH ⁇ CH—, —COO—CH 2 CH 2 —, —OCO -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 - It preferably represents OCO—, —CH ⁇ CH—, —C ⁇ C— or a single bond, more preferably —O—, —COO—, —OCO— or a single bond (provided that P 221 —
  • B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, and Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH ⁇ CH It is preferable to represent —, —C ⁇ C—, —C ⁇ N—, —N ⁇ C—, or a single bond, and r11 preferably represents 0 or 1.
  • Examples of the general formula (II-2) include compounds represented by the following general formulas (II-2-1) to (II-2-4), but are not limited to the following general formulas is not.
  • P 221 , Sp 221 , X 221 , q 221 , X 222 , Sp 222 , q 222 , and P 222 are respectively the above general formulas.
  • B111, B112, B113, B21, and B31 are the same as the definitions of B11 to B31 in the general formula (II-2-b).
  • Z111, Z112, Z113, and Z21 represent the same definitions as Z11 to Z21 in the general formula (II-2-b).
  • Preferred groups also represent the same definitions as Z11 to Z21, and may be the same or different.
  • the compounds represented by the general formulas (II-2-1) to (II-2-4) include the following general formulas (II-2-1-1) to (II-2-1-25): ) Is exemplified, but not limited thereto.
  • R d and R e each independently represent a hydrogen atom or a methyl group
  • the cyclic group includes one or more F, Cl, CF 3 , OCF 3 , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 8 alkanoyl groups, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkenyloxy groups having 2 to 8 carbon atoms, carbon atoms It may have an alkenoyl group having 2 to 8 carbon atoms and an alkenoyloxy group having 2 to 8 carbon atoms.
  • M1, m2, m3, and m4 each independently represent an integer of 0 to 8, and n1, n2, n3, and n4 each independently represent 0 or 1.
  • the compounds represented by the general formulas (II-2-1-1) to (II-2-1-21) are more specifically represented by the following general formulas (II-2-2-1) to The compound represented by (II-2-2-35) can be exemplified, but is not limited thereto.
  • the polymerizable liquid crystal compound having two polymerizable functional groups can be used singly or in combination of two or more, preferably 1 to 5 types, more preferably 2 to 5 types.
  • the total content of the conductive liquid crystal compound is preferably 10 to 100% by mass, more preferably 15 to 85% by mass, based on the total amount of the polymerizable liquid crystal compound used for the sealing material composition for display elements. A content of 20 to 80% by mass is particularly preferable.
  • the lower limit is preferably 30% by mass or more, more preferably 50% by mass or more, and when importance is attached to the orientation of the film, the upper limit is 85% by mass. % Or less, and more preferably 80% by mass or less.
  • the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups it is preferable to use a compound having three polymerizable functional groups.
  • the compounds represented by the general formula (II) the following general formulas (II-3-1) to (II) are used as polyfunctional polymerizable liquid crystal compounds having three or four polymerizable functional groups in the molecule. Illustrative are compounds represented by II-3-2).
  • P 231 , X 231 , q231, X 232 , q232, P 232 , P 233 , X 233 , q234, q233, X 234 , Q236, q235, P 234 , X 235 , q238, q237, and P 235 are P 21 , X 21 in the general formula (II), general formula (II-a), and general formula (II-c), respectively.
  • Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 are each independently an alkylene having 1 to 18 carbon atoms.
  • a hydrogen atom in the alkylene group may be substituted by one or more halogen atoms or a CN group, one CH 2 group present in the group or two or more non-adjacent Each independently of the CH 2 group may be replaced by —O—, —COO—, —OCO— or —OCO—O—.
  • j3 represents 0 or 1
  • MG 3 represents a mesogenic group, and the mesogenic group includes the general formula (II-3-b)
  • B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group,
  • the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
  • Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH
  • Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 are each independently from the viewpoint of enhancing storage stability.
  • , preferably represents an alkylene group having 1 to 14 carbon atoms, and each of the two or more CH 2 groups not one CH 2 group or adjacent existing in the alkylene group independently of one another, -O It may be replaced by-, -COO- or -OCO-.
  • Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 each independently preferably represent an alkylene group having 1 to 12 carbon atoms, and one CH 2 present in the alkylene group. A group or two or more non-adjacent CH 2 groups may be replaced by —O—.
  • B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, and Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH ⁇ CH It is preferable to represent —, —C ⁇ C—, —C ⁇ N—, —N ⁇ C—, or a single bond, and r11 preferably represents 0 or 1.
  • Examples of the compounds represented by the above general formula (II-3-1) to general formula (II-3-2) include the following general formulas (II-3-3-1) to (II-3-3-1-10) ), But is not limited to the following general formula.
  • P 231 to P 235 , Sp 231 to Sp 235 , X 231 to X 235 , q231 to q238, and MG 3 are Each represents the same definition as in general formula (II-3-1) to general formula (II-3-2).
  • B111, B112, B113, B21, and B31 are respectively B11 of the general formula (II-3-b), It represents the same as the definition of B21 and B31, and preferred groups also represent the same as the definitions of B11 to B31, and may be the same or different.
  • Z111, Z112, Z113, and Z21 are the same as Z11 and Z21 in the general formula (II-3-b), respectively. It represents the same as the definition, and preferred groups also represent the same as the definitions of Z11 to Z21, and may be the same or different.
  • Examples of the compounds represented by the general formulas (II-3-3-1) to (II-3-3-10) include the following formulas (II-3-3-3-1) to (II-3): Although the compound represented by -3-3-3) is exemplified, the compound is not limited thereto.
  • R f , R g, and R h each independently represent a hydrogen atom or a methyl group
  • R i , R j, and R k are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 6
  • m4 to m9 each independently represents an integer of 0 to 18, and n4 to n9 each independently represents 0 or 1.
  • the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups can be used alone or in combination of two or more.
  • the total content of the polyfunctional polymerizable liquid crystal compound having 3 or more polymerizable functional groups in the molecule is 0 to 80% by mass of the total amount of the polymerizable liquid crystal compound used in the sealing material composition for display elements.
  • the content is preferably 0 to 60% by mass, more preferably 0 to 40% by mass.
  • the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more
  • the upper limit is preferably 50% by mass or less, more preferably 35% by mass or less, and particularly preferably 20% by mass or less.
  • the sealing material composition for display elements of the present invention it is preferable to use a mixture of a plurality of the polymerizable liquid crystal compounds.
  • the curability of the resulting film is improved. It is preferable to use at least one monofunctional polymerizable liquid crystal compound and at least one bifunctional polymerizable liquid crystal compound in combination.
  • the compound when it is desired to further improve curability when the sealing material composition for display elements of the present invention is used as a film, the compound has three or more ring structures as a bifunctional polymerizable liquid crystal compound.
  • a compound selected from (II-2-2) to (II-2-4) is preferably used as a mixture of polymerizable liquid crystal compounds.
  • the total amount of the monofunctional polymerizable liquid crystal compound and the bifunctional polymerizable liquid crystal compound is 70% by mass to 100% by mass of the total amount of the polymerizable liquid crystal compound used for the sealing material composition for display elements. It is particularly preferable that the content be 80% by mass to 100% by mass.
  • a compound containing a mesogenic group having no polymerizable group may be added to the sealing material composition for a display element of the present invention, and an ordinary liquid crystal device such as STN (Super Twisted Nematic) is used. Examples thereof include compounds used for liquid crystals, TN (twisted nematic) liquid crystals, TFT (thin film transistor) liquid crystals, and the like.
  • the compound containing a mesogenic group having no polymerizable functional group is preferably a compound represented by the following general formula (5).
  • the mesogenic group or mesogenic supporting group represented by MG3 has the general formula (5-b)
  • A1 d , A2 d and A3 d are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-d
  • -O -, - S may, independently each two or more CH 2 groups not one CH 2 group or adjacent present in this group to each other, in a manner that oxygen atoms are not directly bonded to each other, -O -, - S May be replaced by —, —NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C ⁇ C—. . ).
  • Ra and Rb each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a cyano group.
  • an alkyl group of ⁇ 6 or an alkoxy group of 1 to 6 carbon atoms all may be unsubstituted or substituted by one or more halogen atoms.
  • the total content of the compound having a mesogen group is preferably 0 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used for the sealing material composition for display elements. In this case, it is preferably 1 part by mass or more, preferably 2 parts by mass or more, preferably 5 parts by mass or more, and preferably 15 parts by mass or less, and 10 parts by mass or less. Preferably there is. (Other ingredients) (Chiral compound)
  • the sealing material composition for display elements in the present invention contains a polymerizable chiral compound that may exhibit liquid crystallinity other than the polymerizable compound represented by the general formula (II) or may be non-liquid crystalline. You can also
  • the polymerizable chiral compound used in the present invention preferably has one or more polymerizable functional groups.
  • examples of such compounds include JP-A-11-193287, JP-A-2001-158788, JP-T 2006-52669, JP-A-2007-269639, JP-A-2007-269640, 2009.
  • -84178 which contains chiral saccharides such as isosorbide, isomannite, glucoside, etc., and a rigid group such as 1,4-phenylene group and 1,4-cyclohexylene group, and a vinyl group
  • a polymerizable chiral compound having a polymerizable functional group such as an acryloyl group, a (meth) acryloyl group, or a maleimide group, a polymerizable chiral compound comprising a terpenoid derivative as described in JP-A-8-239666, NATURE VOL35, pages 467-469 (November 30, 1995) Issue), NATURE VOL392, pages 476-479 (issued on April 2, 1998), or the like, or a polymerizable chiral compound comprising a mesogenic group and a spacer having a chiral moiety, or JP-T-2004-504285.
  • a polymerizable chiral compound containing a binaphthyl group as described in JP-A-2007-248945 is preferable for the sealing material composition for display elements of the present invention.
  • the compounding amount of the polymerizable chiral compound needs to be appropriately adjusted depending on the helical induction force of the compound, but it is preferably 0 to 25% by mass, preferably 0 to 20% by mass in the polymerizable liquid crystal composition. More preferably, the content is particularly preferably 0 to 15% by mass.
  • Examples of the general formula of the polymerizable chiral compound include general formulas (3-1) to (3-4), but are not limited to the following general formula.
  • Sp 3a and Sp 3b each independently represent an alkylene group having 0 to 18 carbon atoms, and the alkylene group is a carbon atom having one or more halogen atoms, a CN group, or a polymerizable functional group.
  • alkyl group having 1 to 8 may be substituted by an alkyl group having 1 to 8, two or more of CH 2 groups, independently of one another each of the present in the radical is not one CH 2 group or adjacent, each other oxygen atom -O-, -S-, -NH-, -N (CH 3 )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- Or it may be replaced by -C ⁇ C- A1, A2, A3, A4 and A5 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, , 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2
  • R 3a and R 3b are represented by the general formula (3-a)
  • P 3a represents a polymerizable functional group, and Sp 3a represents the same meaning as Sp 1 ).
  • P 3a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).
  • the formula (P-1) or the formulas (P-2), (P-7), (P-12), and (P-13) are preferable from the viewpoint of increasing the polymerizability.
  • Formulas (P-1), (P-7), and (P-12) are more preferable.
  • polymerizable chiral compound examples include compounds represented by the following general formulas (3-5) to (3-26), but are not limited to the following compounds.
  • m, n, k, and l each independently represent an integer of 1 to 18, and R 1 to R 4 each independently represents a hydrogen atom, carbon An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, and a cyano group; When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, all of them may be unsubstituted or substituted by one or more halogen atoms. .
  • a polymerizable discotic liquid crystal compound exhibiting liquid crystallinity can also be used as the polymerizable liquid crystal compound.
  • the sealing material composition for display elements of this invention can also contain a non-liquid crystalline polymerizable discotic compound.
  • the polymerizable discotic compound used in the present invention preferably has one or more polymerizable functional groups.
  • examples of such compounds include polymerizable compounds described in, for example, JP-A-7-281028, JP-A-7-287120, JP-A-7-333431, and JP-A-8-27284. Is mentioned.
  • Examples of the polymerizable discotic liquid crystal compound exhibiting liquid crystallinity as the polymerizable liquid crystal compound include compounds represented by the following general formula (III).
  • each R 7 independently represents a substituent represented by the general formula (III-a).
  • R 9 and R 10 each independently represent a hydrogen atom, a halogen atom or a methyl group
  • R 8 represents an alkoxy group having 1 to 20 carbon atoms
  • the hydrogen atom in the alkoxy group is generally May be substituted by a substituent represented by the formula (III-b), the general formula (III-c), or the general formula (III-d), and at least R 8 present in the general formula (III)
  • One is substituted by a substituent represented by general formula (III-b), general formula (III-c), or general formula (III-d).
  • R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 and R 89 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms.
  • N1 represents 0 or 1
  • At least one of R 8 present in the general formula (III) is substituted with a substituent represented by the general formula (III-b), the general formula (III-c), or the general formula (III-d).
  • all R 8 present in the general formula (III) is independently represented by the general formula (III-b), the general formula (III-c), or the general formula (III-d). It is preferably substituted by the substituent represented.
  • the substituent represented by the general formula (III-a) is specifically preferably a substituent represented by the general formula (III-e).
  • n2 represents an integer of 1 to 18
  • Preferred examples of the compound represented by the general formula (III) include compounds represented by the following general formula (III-1) and general formula (III-2).
  • n an integer of 1 to 18
  • the polymerizable liquid crystal compound one or more polymerizable discotic liquid crystal compounds exhibiting liquid crystallinity can be used.
  • polymerizable liquid crystal compound only a polymerizable discotic liquid crystal compound can be used, or a polymerizable rod-like liquid crystal compound and a polymerizable discotic liquid crystal compound can be used in combination.
  • the total content of the polymerizable discotic liquid crystal compound exhibiting liquid crystallinity is the polymerizability used in the sealing material composition for display elements.
  • the total amount of the liquid crystal compound is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 80% by mass.
  • Examples of general formulas of other polymerizable discotic compounds include general formulas (4-1) to (4-3), but are not limited to the following general formulas.
  • Sp 4 represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with one or more halogen atoms, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group.
  • Z 4a represents —CO—, —CH 2 CH 2 —, —CH 2 O—, —CH ⁇ CH—, —CH ⁇ CHCOO—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, — COCH 2 CH 2 — represents an alkyl group which may have a halogen atom having 2 to 10 carbon atoms or a single bond
  • R 4 represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN.
  • One CH 2 group present or two or more non-adjacent CH 2 groups are each independently of each other in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, May be replaced by —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C ⁇ C—, Or R 4 represents the general formula (4-a)
  • P 4a represents a polymerizable functional group
  • Sp 3a represents the same meaning as Sp 1
  • P 4a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).
  • the formula (P-1) or the formulas (P-2), (P-7), (P-12), and (P-13) are preferable from the viewpoint of increasing the polymerizability.
  • Formulas (P-1), (P-7), and (P-12) are more preferable.
  • polymerizable discotic compound examples include compounds (4-4) to (4-6), but are not limited to the following compounds.
  • n represents an integer of 1 to 18.
  • a compound having a polymerizable group but not a liquid crystal compound can be added.
  • Such a compound can be used without particular limitation as long as it is generally recognized as a polymerizable monomer or polymerizable oligomer in this technical field.
  • it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less, with respect to 100 parts by mass of the total content of polymerizable compounds contained in the polymerizable composition. preferable.
  • organic solvent You may add an organic solvent to the sealing material composition for display elements in this invention.
  • the organic solvent in which a polymeric liquid crystal compound shows favorable solubility is preferable, and it is preferable that it is an organic solvent which can be dried at the temperature of 100 degrees C or less.
  • solvents examples include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexane, and the like.
  • Ketone solvents such as pentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate , Diethylene glycol monomethyl ether acetate, ⁇ -butyrolactone, chlorobenzene and the like.
  • amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone
  • propylene glycol monomethyl ether acetate Diethylene glycol monomethyl ether acetate, ⁇ -butyrolactone, chlorobenzene and the like.
  • amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone
  • propylene glycol monomethyl ether acetate Diethylene glycol monomethyl ether acetate, ⁇ -butyrolactone, chlorobenzene and the like.
  • the sealing material composition for display elements used in the present invention can be applied to the substrate as a solution using an organic solvent, and the ratio of the organic solvent used for the sealing material composition for display elements was applied.
  • the total amount of the organic solvent contained in the sealing material composition for display elements is preferably 0 to 90% by mass, and preferably 0 to 85% by mass. Is more preferable, and 0 to 80% by mass is particularly preferable.
  • the filler used in the present invention is dispersed in the organic solvent to obtain a dispersion, and then the dispersion A polymerizable liquid crystal compound or the like used in the present invention may be dissolved therein to form a composition.
  • the polymerizable liquid crystal compound used in the present invention is first dissolved to obtain a polymerizable liquid crystal composition.
  • a composition in which the filler used in the present invention is dispersed in the polymerizable liquid crystal composition may be used.
  • the dispersion in which the filler used in the present invention is dispersed and the polymerizable liquid crystal compound used in the present invention are dissolved.
  • Each of the prepared polymerizable liquid crystal compositions may be prepared and then mixed to form a sealing material composition for a display element.
  • the heating temperature at the time of heating and stirring may be appropriately adjusted in consideration of the solubility of the composition to be used in the organic solvent, but is preferably 15 ° C. to 110 ° C., more preferably 15 ° C. to 105 ° C. from the viewpoint of productivity. 15 to 100 ° C. is more preferable, and 20 to 90 ° C. is particularly preferable.
  • a dispersion stirrer having a stirring blade such as a wet bead mill, a disper, a propeller, or a turbine blade, a paint shaker, a planetary stirring device, a shaker, a shaker, or a rotary evaporator can be used as the dispersion stirrer.
  • a stirring blade such as a wet bead mill, a disper, a propeller, or a turbine blade, a paint shaker, a planetary stirring device, a shaker, a shaker, or a rotary evaporator
  • an ultrasonic irradiation apparatus can be used.
  • wet bead mills and dispersers are preferably used when preparing a dispersion in which a filler is dispersed in an organic solvent, and stirring blades are used when preparing a solution in which a polymerizable liquid crystal compound is dissolved in an organic solvent. It is preferable to use a disperser, a planetary stirrer and a shaker.
  • the number of rotations of stirring when adding the solvent is preferably adjusted appropriately depending on the stirring device used, but the number of rotations of stirring is preferably 10 rpm to 1000 rpm in order to obtain a uniform sealing material composition solution for display elements. 50 rpm to 800 rpm is more preferable, and 100 rpm to 600 rpm is particularly preferable.
  • the sealing material composition for display elements of the present invention may contain the chiral compound and the following components as other components, but the chiral compound and the components described below are organic solvents, packing
  • the material and / or the polymerizable liquid crystal compound can be appropriately used when dispersed or dissolved in the composition.
  • Polymerization inhibitor It is preferable to add a polymerization inhibitor to the sealing material composition for display elements in the present invention.
  • the polymerization inhibitor include phenol compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like.
  • phenolic compounds include p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol) 2.2′-methylenebis (4-ethyl-6-tert-butylphenol), 4.4′-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4′- Dialkoxy-2,2′-bi-1-naphthol, and the like.
  • quinone compounds include hydroquinone, methylhydroquinone (MEHQ), tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1, Examples include 4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, and diphenoquinone.
  • MEHQ methylhydroquinone
  • p-benzoquinone methyl-p-benzoquinone
  • 2,5-diphenylbenzoquinone 2-hydroxy-1
  • Examples include 4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone
  • amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N.I. N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I. N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl- ⁇ -naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine and the like.
  • thioether compounds include phenothiazine and distearyl thiodipropionate.
  • nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, ⁇ -nitroso- ⁇ -naphthol, and the like, N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl- 4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitros
  • the addition amount of the polymerization inhibitor is preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used in the sealing material composition for display elements, and 0.05 to More preferably, it is 0.5 parts by mass.
  • Antioxidant In order to improve the stability of the sealing material composition for display elements in the present invention, it is preferable to add an antioxidant or the like. Examples of such compounds include hydroquinone derivatives, nitrosamine polymerization inhibitors, hindered phenol antioxidants, and more specifically, tert-butyl hydroquinone, methyl hydroquinone, manufactured by Wako Pure Chemical Industries, Ltd.
  • IRGANOX1010 “IRGANOX1035”, “IRGANOX1076”, “IRGANOX1098”, “IRGANOX1135”, “IRGANOX1330”, “IRGANOX1425”, “IRGANOX1520”, “IRGANOX1726”, BASF Corporation “IRGANOX245”, “IRGANOX259”, “IRGANOX3114”, “IRGANOX3790”, “IRGANOX5057”, “IRGANOX565” And so on.
  • the addition amount of the antioxidant is preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements, and 0.05 to More preferably, it is 1.0 part by mass.
  • the sealing material composition for display elements in this invention contains a photoinitiator. It is preferable to contain at least one photopolymerization initiator.
  • the amount is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements of the photopolymerization initiator. These can be used alone or in combination of two or more, and a sensitizer or the like may be added.
  • Thermal polymerization initiator A thermal polymerization initiator may be used in combination with the photopolymerization initiator in the sealing material composition for display elements in the present invention. Specifically, “V-40” and “VF-096” manufactured by Wako Pure Chemical Industries, Ltd., “Perhexyl D” and “Perhexyl I” of Nippon Oil & Fats Co., Ltd. (currently Nippon Oil Co., Ltd.) Etc.
  • the amount of the thermal polymerization initiator used is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements. Particularly preferred. These can be used alone or in combination of two or more.
  • the sealing material composition for display elements in the present invention further contains at least one surfactant in a range that does not impair the effects of the present invention in order to reduce film thickness unevenness in the case of an optical anisotropic body. May be.
  • Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like, and fluorine-containing surfactants are particularly preferable.
  • the addition amount of the surfactant is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements, and 0.05 to 0 More preferably, it is 5 parts by mass.
  • the tilt angle at the air interface can be effectively reduced.
  • the sealing material composition for display elements in the present invention is represented by the following general formula (7), which has the effect of effectively reducing the tilt angle of the air interface when it is used as a film without impairing the effects of the present invention. And a compound having a repeating unit having a weight average molecular weight of 100 or more.
  • each of R 11 , R 12 , R 13 and R 14 independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group It may be substituted with a halogen atom.
  • Examples of suitable compounds represented by the general formula (7) include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin.
  • the addition amount of the compound represented by the general formula (7) is 0.01 to 1 part by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements. Preferably, the amount is 0.05 to 0.5 parts by mass.
  • additives such as polymerizable compounds having no liquid crystallinity, thixotropic agents, dispersants, chain transfer agents and the like are not impaired in the properties of the sealing material composition for display elements of the present invention. Can be added.
  • the content is preferably 0.01 to 1 part by mass, and 0.05 to 0.5 part by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used in the sealing material composition for display elements. It is more preferable that (Method for producing sealing material composition for display element)
  • the sealing material composition for display elements of the present invention can be produced by mixing at least one or more fillers and two or more polymerizable liquid crystal compounds.
  • a sealing material composition for a display element in which a polymerizable liquid crystal compound is brought into a liquid crystal state and a filler is dispersed can be obtained by stirring or ultrasonic irradiation.
  • a stirring method a planetary stirring apparatus, a shaker, a laboratory mixer, a stirring propeller, a shaker, a rotary evaporator, or the like can be used.
  • the temperature during the production may rise, but the heating from the outside is arbitrary, and the heating is performed even when heated. It is not necessary.
  • the temperature during production is preferably 15 ° C. or higher and 70 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, and particularly preferably 25 ° C. or higher and 45 ° C. or lower.
  • the composition consisting of 2 or more types of polymeric liquid crystal compounds to be used maintains liquid crystallinity at room temperature.
  • the filler used in the present invention is first dispersed in the organic solvent to obtain a dispersion, and then the present invention is applied.
  • a polymerizable liquid crystal compound to be used may be dissolved to form a composition.
  • the polymerizable liquid crystal compound used in the present invention is first dissolved to obtain a polymerizable liquid crystal composition.
  • a composition in which the filler used in the present invention is dispersed may be used.
  • the dispersion in which the filler used in the present invention is dispersed and the polymerizable liquid crystal compound used in the present invention are dissolved.
  • the prepared polymerizable liquid crystal composition may be prepared and mixed to form a sealing material composition for a display element.
  • heating from the outside during production is optional, and it may be heated or not heated.
  • the temperature during production is preferably 15 ° C. or higher and 70 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, and particularly preferably 25 ° C. or higher and 45 ° C. or lower.
  • the sealing material composition for a display element of the present invention can also be produced by adding and stirring a filler to a liquid state product obtained by heating and melting one or more polymerizable liquid crystal compounds. In this case, heating is required to melt the polymerizable compound, but the heating temperature is preferably set to a temperature of ⁇ 10 ° C. from the temperature at which all the polymerizable compounds used melt.
  • the sealing material composition for display elements of the present invention is used as a base material sealing protective agent or a sealing agent for display elements.
  • Examples of the display element include a liquid crystal display element using a liquid crystal material, an organic light emitting display element using an organic light emitting diode, a quantum dot display element using a quantum dot, etc., and sealing a substrate and a substrate of each display element It can be suitably used as a protective agent or a sealing agent for the frame portion of each display element.
  • the display element of the present invention is a laminate in which a base material layer, a base material sealing protective layer using the display element sealing material composition of the present invention, and other layers such as an inorganic layer are laminated as necessary. It is preferable that (Inorganic layer) In the present invention, an inorganic layer may be laminated on the substrate in order to develop higher gas barrier properties and water vapor barrier properties.
  • the inorganic layer is an oxide of at least one metal selected from the group consisting of Al, Si, Zn, Sn, Ti, Cr, Ni, and In, a nitride of the metal, or an oxynitride of the metal. Preferably there is.
  • the inorganic layer is more preferably formed of an oxide or a double oxide of Al, Si, Zn, Sn, Ti, Cr, Ni, and In.
  • the inorganic layer may be provided only on one side of the substrate, or may be provided on both sides of the substrate.
  • the content of Si in the double oxide is not particularly limited, but is preferably 20 parts by mass to 80 parts by mass, and more preferably 30 parts by mass to 70 parts by mass.
  • Si content is within the above range, a barrier film having higher transparency and excellent gas barrier performance can be provided.
  • the weight ratio of Zn to the total amount of Zn and Sn (Zn / Zn + Sn) in the double oxide is preferably 0.3 to 0.99, more preferably 0.5 to 0.9. preferable. When it exists in the said range, gas barrier property can be improved further.
  • the film thickness of the inorganic layer is not particularly limited, but is preferably 30 nm to 3000 nm, and more preferably 50 nm to 1000 nm. When the film thickness is in the above range, the gas barrier performance can be further enhanced.
  • the refractive index of the inorganic layer is not particularly limited, but is preferably 1.9 or less, and more preferably 1.8 or less. Since the refractive index of a plastic film such as polyethylene naphthalate or polyethylene terephthalate used as the substrate is about 1.6 to 1.75, the refractive index of the inorganic layer can be reduced to 1.9 or less. The reflection of light at the interface between the inorganic layer and the inorganic layer can be further suppressed. That is, the transparency of the barrier layer is further enhanced. (Base material)
  • the sealing material composition for display elements of the present invention is used as a base material sealing protective agent for display elements, but the base material used for the display elements is usually used for liquid crystal devices, displays, optical components and optical films.
  • a base material that has heat resistance that can withstand heating as needed during drying after application of the sealing material composition for display elements of the present invention.
  • a base material include organic materials such as a glass base material, a metal base material, a ceramic base material, and a plastic base material, but the sealing material composition for a display element of the present invention having excellent gas barrier properties and water vapor barrier properties.
  • the product is particularly effective in improving gas barrier properties and water vapor barrier properties when the following organic material base is used.
  • the substrate is an organic material
  • examples thereof include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates (acrylic resins), polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, and polystyrene.
  • plastic base materials such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, and base materials such as polyacrylate, polyolefin, and cellulose derivative are more preferable, and COP (cycloolefin polymer) is used as the polyolefin.
  • TAC triacetyl cellulose
  • PMMA polymethyl methacrylate
  • these substrates may be subjected to surface treatment.
  • the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like.
  • an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value.
  • the material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like.
  • a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
  • Substrate orientation treatment In addition, the substrate is usually subjected to an orientation treatment so that the display element sealing material composition is oriented when the display element sealing material composition of the present invention is applied and dried, or the orientation is applied.
  • a film may be provided. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used.
  • Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone.
  • the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds.
  • the compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment.
  • the substrate and the alignment-treated film using an alignment film may be collectively referred to as a substrate.
  • the sealing material composition for display elements of the present invention is used as a sealant for display elements. Specifically, it is used as a layer for sealing the side surface of the barrier layer covering the layer containing a light-emitting organic compound.
  • sealing material composition for display element As a method for applying the sealing material composition for display elements of the present invention to a substrate, a substrate or a material to be sealed, an applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating Known and commonly used methods such as a method, a flexo coating method, an ink jet method, a die coating method, a cap coating method, a dip coating method, a slit coating method, and a discharge method using a dispenser can be performed.
  • the dispenser method and the like can be used without using an organic solvent. However, when an organic solvent is used, the organic solvent is required for volatilization after the display element sealing material composition is applied to the substrate. Dry accordingly.
  • the liquid crystal compound in the sealing material composition for display elements of the present invention is horizontal with respect to the substrate after volatilizing the organic solvent.
  • the alignment, vertical alignment, hybrid alignment, or cholesteric alignment is performed by irradiation with light such as ultraviolet rays or heating.
  • irradiation with ultraviolet light specifically, irradiation with ultraviolet light of 390 nm or less is preferable, and irradiation with light having a wavelength of 250 to 370 nm is most preferable.
  • the sealing material composition for a display element causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more.
  • This light is preferably diffused light and unpolarized light.
  • Examples of the method for polymerizing the sealing material composition for a display device of the present invention include a method of irradiating active energy rays and a thermal polymerization method. However, it does not require heating and is active because the reaction proceeds at room temperature. A method of irradiating energy rays is preferable, and among them, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.
  • the temperature at the time of irradiation is set to 40 ° C. or less as much as possible in order to avoid the induction of thermal polymerization of the sealing material composition for display elements, so that the sealing material composition for display elements of the present invention can maintain the liquid crystal phase. It is preferable to do.
  • the liquid crystal composition usually has a liquid crystal phase within a range from the C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as the CN transition temperature) to the NI transition temperature in the temperature rising process. Indicates.
  • the temperature lowering process since the thermodynamically non-equilibrium state is obtained, there is a case where the liquid crystal state is not solidified even at a temperature below the CN transition temperature.
  • the liquid crystal composition in a supercooled state is also included in the state in which the liquid crystal phase is retained.
  • irradiation with ultraviolet light of 390 nm or less is preferable, and irradiation with light having a wavelength of 250 to 370 nm is most preferable.
  • the sealing material composition for a display element causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light. Ultraviolet irradiation intensity in the range of 0.05kW / m 2 ⁇ 10kW / m 2 is preferred.
  • the range of 0.2 kW / m 2 to 2 kW / m 2 is preferable.
  • the ultraviolet intensity is less than 0.05 kW / m 2 , it takes a lot of time to complete the polymerization.
  • the strength exceeds 2 kW / m 2 , liquid crystal molecules in the sealing material composition for display elements tend to be photodecomposed, and a large amount of polymerization heat is generated, resulting in an increase in temperature during the polymerization.
  • the order parameter of the liquid crystal changes, and there is a possibility that the retardation of the film after polymerization is distorted.
  • the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized.
  • An optical anisotropic body having a plurality of regions having orientation directions can also be obtained.
  • the orientation is regulated by applying an electric field, a magnetic field, or temperature to the display element sealing material composition in an unpolymerized state in advance.
  • a film having a plurality of regions having different orientation directions can also be obtained by polymerizing by irradiating light from above the mask while maintaining.
  • the sealing material composition for display elements of the present invention can be suitably used as a sealing agent for liquid crystal display elements and organic light emitting display elements. Specifically, it can be suitably used as a sealing agent for display elements such as liquid crystal displays, organic EL displays, inorganic EL displays, quantum dot displays, and quantum rod displays.
  • the coating amount of the sealing material composition for display elements is not limited, but it is usually preferable that the layer thickness of the sealing agent after drying is 50 ⁇ m to 200 ⁇ m on the sealing material. 50 ⁇ m to 150 ⁇ m is more preferable, and 50 ⁇ m to 120 ⁇ m is particularly preferable.
  • the sealing material composition for a display element of the present invention can be suitably used as a substrate sealing protective agent used for a display element. Specifically, it can be used for display elements such as an organic EL display, an inorganic EL display, a quantum dot display, and a quantum rod display, and can be suitably used as a base material sealing protective layer when used on a base material. .
  • the layer thickness of the base material sealing protective agent after drying is usually 40 ⁇ m to 80 ⁇ m on the base material. It is preferably 40 ⁇ m to 70 ⁇ m, more preferably 40 ⁇ m to 60 ⁇ m.
  • Polymeric liquid crystal compositions (U-2) to (U-15) were obtained under the same conditions as in the preparation. (Adjustment of polymerizable liquid crystal composition (U-16)) 45 parts of the compound represented by formula (B-1), 45 parts of the compound represented by formula (B-2), 10 parts of the compound represented by formula (C-1), p-methoxyphenol (MEHQ) 0 .1 part was heated and stirred at 100 ° C.
  • Irgacure 907 (Irg.907: manufactured by BASF Japan Ltd.), Irgacure TPO (TPO: BASF) 3 parts of Japan Co., Ltd.) and 0.2 part of MegaFuck F-554 (F-554: manufactured by DIC Corporation) were added and further stirred to obtain a solution (U-16).
  • Tables 1 to 3 show specific compositions of the polymerizable liquid crystal compositions (U-1) to (U-17) of the present invention.
  • phase transition temperatures of the polymerizable liquid crystal compositions (U-2) to (U-13) are the same as those of (U-1), and the phase transition temperatures of (U-14) to (U-15) are After raising the temperature to 190 ° C., the measurement was performed under the same conditions as (U-1).
  • phase transition temperature of the polymerizable liquid crystal compositions (U-16) and (U-17) is the same as (U-1), which is obtained by thinly spreading the polymerizable liquid crystal composition on a glass substrate with a spatula. It was observed and measured after drying and heating up under conditions.
  • phase transition temperatures of the polymerizable liquid crystal compositions (U-1) to (U-17) are shown in Table 4 below.
  • P (water vapor transmission rate) ⁇ P (laminate) ⁇ P (PET base material) ⁇ / ⁇ P (PET base material) ⁇ P (laminate) ⁇ : Formula (1) (In formula (1), P represents the water vapor transmission rate of each layer.) (Flexibility evaluation) Using a mandrel type bending tester having a curvature radius of 6 mm, the bending property of the sealing material laminate (1) was evaluated (JIS SK5600-5-1), and no defects such as cracks were generated. The flexibility was evaluated as follows according to the occurrence of cracks.
  • sealing material laminate (16) in which a sealing material layer was laminated on PET.
  • Preparation of sealing material laminate (17) A sealing material laminate (17) was obtained under the same conditions as in the production of the sealing material laminate (16) except that the sealing material composition (16) was changed to the sealing material composition (17).
  • Comparative Example 1 By adding 82.5 g of toluene to 75 g of the polymerizable liquid crystal composition (U-4) and stirring at room temperature, a comparative sealing material composition (C1) was obtained.
  • a sealing material composition for comparison using a wire bar on a PET film having a thickness of 12 microns rubbed with a nylon cloth (water vapor transmission rate at 40 ° C. and 90% RH of 50 g / m 2 ⁇ day (100 ⁇ m conversion)).
  • (C1) was applied, and after solvent drying at 80 ° C., UV irradiation was performed at 500 mJ / cm 2 using a conveyor-type high-pressure mercury lamp, and a comparative laminate in which a sealing material layer was laminated on PET ( C1) was obtained.
  • the water vapor transmission rate was measured by a 40 ° C. 90% RH cup method (JIS Z0208-1976).
  • the water vapor permeability of the sealing material layer calculated from the above formula (1) was 104 g / m 2 ⁇ day (100 ⁇ m conversion).
  • the bending property of the comparative laminate was evaluated using a mandrel type bending tester having a curvature radius of 6 mm (JIS SK5600-5-1), and no defects such as cracks were generated.
  • Example 18 (Lamination of inorganic film)
  • the film forming chamber was evacuated by a vacuum pump and the pressure was reduced to 5.0 ⁇ 10 ⁇ 4 Pa. Thereafter, sputtering was performed under the conditions shown in the following film formation condition A to form a SiZnSnO film having a thickness of 150 nm as an inorganic film on the laminate (1) to obtain a vapor deposition laminate (18).
  • Example 19 Flexibility evaluation of the obtained vapor-deposited laminate (18) was performed in the same manner as in Example 1. (Examples 19 to 22) Except for changing the sealing material laminate (1) to the sealing material laminate (2), (8), (10) and (14), respectively, under the same conditions as the production of the vapor deposition laminate (1), Vapor deposited laminates (19) to (22) were obtained.
  • Example 23 Al is attached to the second cathode, and sputtering is performed under the conditions shown in the following film formation condition B to form an Al 2 O 3 film having a thickness of 150 nm as an inorganic film on the sealing material stack (1). 23) was obtained.
  • the water vapor transmission rate measurement and the flexibility evaluation of the obtained vapor-deposited laminate (23) were carried out in the same manner as in Example 18.
  • Comparative Example 2 A comparative vapor deposition laminate (C2) was obtained in the same manner as in Example 18 except that the sealing material layer (1) was changed to a PET film having a thickness of 12 microns.
  • sealing material composition (18) 100 g of dispersion B was added to 90 g of the polymerizable liquid crystal composition (U-18), stirred at room temperature, and then degassed with a solvent in a planetary mixer to thereby uniformly disperse the filler b (18) Got.
  • a sealing material composition (18) is applied on a PET substrate film having a thickness of 50 ⁇ m rubbed with a nylon cloth using an applicator, and UV irradiation is performed at 500 mJ / cm 2 using a conveyor type high-pressure mercury lamp. Then, a cured product of the sealing material composition (18) was obtained.
  • the cured product was peeled off from the PET substrate to obtain a sealing sheet (18) having a thickness of 50 ⁇ m.
  • the water vapor transmission rate was measured by the 40 ° C. 90% RH cup method (JIS Z0208-1976), and it was 15.2 g / m 2 ⁇ day (100 ⁇ m conversion).
  • the sealing material layer using the sealing material composition of the present invention containing a filler in the polymerizable liquid crystal composition has excellent barrier properties and imparts flexibility to the inorganic vapor deposition layer. It became clear that it was excellent also as a vapor deposition anchor layer which can be performed.

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Abstract

Provided is a sealing material composition for a display element, said sealing material composition having a strong gas barrier property and water vapor barrier property, and also provided are a sealing agent for a display element and a substrate sealing and protection agent in which the composition is used, and a liquid crystal display element, an organic light emitting display element, and a quantum dot display element in which the sealing agent and/or the substrate seal and protection agent are used. The present invention provides a sealing material composition for a display element, said sealing material composition comprising at least one type of filler, and one or more polymerizable liquid crystal compound. In addition, also provided are a sealing agent and a substrate sealing and protection agent in which this composition is used, and a display element in which the sealing agent and/or the substrate sealing and protection agent are used.

Description

表示素子用封止材料組成物、及び、それを用いた表示素子Sealing material composition for display element and display element using the same
　本願発明は、液晶表示素子、有機発光表示素子等のシール剤として用いる、充填材及び重合性液晶化合物を含有する表示素子用封止材料組成物、及び該組成物を用いたシール剤、基材封止保護剤、液晶表示素子、有機発光表示素子に関する。 The present invention relates to a sealing material composition for a display element containing a filler and a polymerizable liquid crystal compound, which is used as a sealing agent for liquid crystal display elements, organic light emitting display elements, and the like, and a sealing agent and a base material using the composition The present invention relates to a sealing protective agent, a liquid crystal display element, and an organic light emitting display element.
　液晶表示素子や有機発光表示素子などの表示素子は、素子の長寿命化が重要な開発課題となっている。これらの表示素子に使用される液晶材料、有機発光ダイオード、量子ドットといった有機発光物質は、水分や酸素の影響を受けやすく、長期間安定した動作性を確保するために、ガラスシートや金属シートが封止材料として使用されてきた。しかし、近年の表示素子の多様化により、軽量化やフレキシブル化には、当該封止材料では対応できず、種々のポリマー材料を用いた封止材料の検討が行われている。 In a display element such as a liquid crystal display element or an organic light emitting display element, it is an important development subject to extend the life of the element. Organic light-emitting substances such as liquid crystal materials, organic light-emitting diodes, and quantum dots used in these display elements are easily affected by moisture and oxygen, and glass sheets and metal sheets are used to ensure stable operation over a long period of time. It has been used as a sealing material. However, due to the diversification of display elements in recent years, the sealing material cannot cope with weight reduction and flexibility, and sealing materials using various polymer materials are being studied.
　ポリマー材料を使用した封止材料は、ガラスシートや金属シートに比べ、ガスバリア性や水蒸気バリア性が劣るため表示素子に侵入した酸素や水分により液晶材料や有機発光物質が劣化するという問題が生じていた。そこで、ポリマー材料として液晶ポリマーを用いた基材層上に、ガスバリア及び／又は水蒸気バリアを目的としてバリア層を設けた積層フィルムの開発が進められている（特許文献１～２）。しかしながら、当該積層フィルムを作製するには、液晶ポリマーをフィルム化するために当該ポリマーを２００℃以上に加熱溶融しフィルム状に押出成形する必要があり、高温加熱による液晶ポリマーの分解生成物等が、液晶材料、有機発光ダイオード、量子ドットといった有機発光物質に対し性能低下を及ぼす原因となっていた。 Sealing materials that use polymer materials have poor gas barrier properties and water vapor barrier properties compared to glass sheets and metal sheets, so there has been a problem that liquid crystal materials and organic light-emitting substances deteriorate due to oxygen and moisture that have entered the display element. It was. Therefore, development of a laminated film in which a barrier layer is provided on a base material layer using a liquid crystal polymer as a polymer material for the purpose of a gas barrier and / or a water vapor barrier is being promoted (Patent Documents 1 and 2). However, in order to produce the laminated film, it is necessary to heat and melt the polymer to 200 ° C. or higher and to extrude it into a film in order to form a liquid crystal polymer. In other words, the organic light-emitting substances such as liquid crystal materials, organic light-emitting diodes, and quantum dots cause performance degradation.
特開２０１２－０８１７５０号公報JP 2012-081750 A 特開２００９－０３２４６４号公報JP 2009-032464 A
　本発明が解決しようとする課題は、高いガスバリア性及び水蒸気バリア性を有する表示素子用封止材料組成物を提供し、併せて、当該組成物を用いた表示素子用シール剤、基材封止保護剤、当該シール剤及び／又は基材封止保護剤を用いた液晶表示素子、有機発光表示素子、量子ドット表示素子を提供することである。 The problem to be solved by the present invention is to provide a sealing material composition for a display element having high gas barrier property and water vapor barrier property, and at the same time, a sealing agent for display element and substrate sealing using the composition It is providing the liquid crystal display element using the protective agent, the said sealing agent, and / or base-material sealing protective agent, an organic light emitting display element, and a quantum dot display element.
　本発明は、上記課題を解決するために、重合性液晶化合物及び充填材を用いることに着目して鋭意研究を重ねた結果、本発明を提供するに至った。 In order to solve the above-mentioned problems, the present invention has been conducted by paying attention to using a polymerizable liquid crystal compound and a filler, and as a result, has come to provide the present invention.
　即ち、本発明は、少なくとも１種以上の充填材、及び、１種又は２種以上の重合性液晶化合物を含有する表示素子用封止材料組成物を提供する。また、本発明の組成物を用いたシール剤、基材封止保護剤、及び当該シール剤及び／又は基材封止保護剤を用いた表示素子も提供する。 That is, this invention provides the sealing material composition for display elements containing at least 1 or more types of fillers and 1 type, or 2 or more types of polymerizable liquid crystal compounds. Moreover, the sealing agent using the composition of this invention, a base-material sealing protective agent, and the display element using the said sealing agent and / or base-material sealing protective agent are also provided.
　本発明の表示素子用封止材料組成物を用いることで、高いガスバリア性及び水蒸気バリア性を有する封止保護層を形成できることから、表示素子のシール剤、基材封止保護剤用途に有用である。 By using the sealing material composition for display elements of the present invention, a sealing protective layer having high gas barrier properties and water vapor barrier properties can be formed. is there.
　以下に本発明による表示素子用封止材料組成物の最良の形態について説明するが、本発明において、重合性液晶化合物の「液晶」とは、用いる重合性液晶化合物１種のみの化合物で液晶性を示すことを意図する場合や、その他の液晶化合物と混合し混合物とした場合に液晶性を示すことを意図する。なお、表示素子用封止材料組成物は紫外線等の光照射、加熱又はそれらの併用によって重合処理を行うことでポリマー化（フィルム化）することができる。
（充填材）
　本発明の表示素子用封止材料組成物には、少なくとも１種以上の充填材を含有することを特徴とする。１種又は２種以上の重合性液晶化合物と共に、充填材を併用することにより本発明の表示素子用封止材料組成物は、高いガスバリア性及び高い水蒸気バリア性を有することが可能となる。 Hereinafter, the best mode of the sealing material composition for display elements according to the present invention will be described. In the present invention, the “liquid crystal” of the polymerizable liquid crystal compound is a compound of only one kind of the polymerizable liquid crystal compound to be used. It is intended to exhibit liquid crystallinity when it is intended to show or when mixed with other liquid crystal compounds to form a mixture. In addition, the sealing material composition for display elements can be polymerized (formed into a film) by performing a polymerization treatment by irradiation with light such as ultraviolet rays, heating, or a combination thereof.
(Filler)
The sealing material composition for display elements of the present invention is characterized by containing at least one filler. By using a filler together with one or more polymerizable liquid crystal compounds, the sealing composition for a display element of the present invention can have high gas barrier properties and high water vapor barrier properties.
　用いる充填材は、使用する形状に合わせ、有機充填材又は無機充填材の何れも使用することが可能である。無機充填材の形状は、粉末状の充填材であることが好ましい。本発明に用いる粉末状の充填材の最大粒子径は、０．０１μｍ以上５０μｍ以下が好ましく、０．０１μｍ以上４０μｍ以下がより好ましく、０．０１μｍ以上３５μｍ以下がさらに好ましく、０．０１μｍ以上３０μｍ以下が特に好ましい。更に平均粒子径は、０．００２μｍ以上２０μｍ以下が好ましく、０．００２μｍ以上１５μｍ以下がより好ましく、０．００２μｍ以上１２μｍ以下がさらに好ましく、０．００２μｍ以上１０μｍ以下が特に好ましい。平均粒子径が０．００２μｍ未満であると又は５０μｍを超えるとガスバリア性能及び水蒸気バリア性能の向上にあまり大きな影響を与えないため上記範囲の粉末状の充填材を用いることが好ましい。 As the filler to be used, either an organic filler or an inorganic filler can be used according to the shape to be used. The shape of the inorganic filler is preferably a powdery filler. The maximum particle size of the powdery filler used in the present invention is preferably 0.01 μm or more and 50 μm or less, more preferably 0.01 μm or more and 40 μm or less, further preferably 0.01 μm or more and 35 μm or less, and 0.01 μm or more and 30 μm or less. Is particularly preferred. Furthermore, the average particle diameter is preferably 0.002 μm or more and 20 μm or less, more preferably 0.002 μm or more and 15 μm or less, further preferably 0.002 μm or more and 12 μm or less, and particularly preferably 0.002 μm or more and 10 μm or less. When the average particle diameter is less than 0.002 μm or exceeds 50 μm, it does not have a great influence on the improvement of the gas barrier performance and the water vapor barrier performance, so it is preferable to use a powdery filler in the above range.
　また、前記粉末状の充填材としては、層状である板状或いは鱗片状のもの、球状或いは無定形状のもの、棒状である針状或いは繊維状等が挙げられる。これらは単独で用いてもよく、２種類以上を併用して用いても良い。充填材の形状は、ガスバリア性及び高い水蒸気バリア性に優れることから、層状の無機充填材や、球状或いは無定形状の充填材や、棒状の有機充填材が好ましく用いられる。表示素子用封止材料組成物中の充填材の合計含有量は、表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して３質量部～４０質量部用いることが好ましく、３質量部～３０質量部用いることがより好ましく、３質量部～２５質量部用いることが特に好ましい。 Further, examples of the powdery filler include lamellar plate-like or scale-like, spherical or indeterminate, rod-like needle-like or fiber-like. These may be used alone or in combination of two or more. Since the shape of the filler is excellent in gas barrier properties and high water vapor barrier properties, a layered inorganic filler, a spherical or amorphous filler, or a rod-like organic filler is preferably used. The total content of the filler in the display element sealing material composition is 3 parts by mass to 40 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used in the display element sealing material composition. It is preferably 3 to 30 parts by mass, more preferably 3 to 25 parts by mass.
　層状を形成する板状或いは鱗片状充填材としては、タルク、黒鉛、板状炭酸カルシウム、板状アルミナ等のほか、ベントナイト族粘土鉱物、スメクタイト族粘土鉱物及び雲母族粘土鉱物等のケイ酸塩から選ばれる少なくとも１種を好ましく使用できる。粘土鉱物の具体例としては、合成スメクタイト、ヘクトライト、バイデライト、サポナイト、モンモリロナイト、バーミキュライト、スチブンサイト、マイカ、合成マイカ、ナトリウム四ケイ素雲母等が挙げられる。また、前記粘土鉱物は、より水蒸気バリア性を持たせるためシリル化剤により変性した変性粘土鉱物を用いても良い。前記シリル化剤としてはメチルトリメトキシシラン等の公知のシリル化剤を用いることができるが用いるシリル化剤は、粘土とシリル化剤の合計量に対し３０重量％以下であることが好ましい。層状充填材の平均厚は、好ましくは０．５μｍ未満であり、より好ましくは０．２μｍ未満であり、さらに好ましくは０．１μｍ未満であり、特に好ましくは０．０５μｍ未満である。また、層状充填材の平均粒子径（粒子幅）は、電子顕微鏡観察による一次粒子径が、好ましくは０．０１μｍ以上１０μｍ以下であり、より好ましくは０．０２μｍ以上５μｍ以下であり、さらに好ましくは０．０２μｍ以上２μｍ以下であり、特に好ましくは０．１μｍ以上１μｍ以下である。なお、前記粒子径は、顕微鏡観察により層状充填材のアスペクト比は、１００～２５００の範囲であり、より好ましくは２００～２０００の範囲であり、さらに好ましくは２５０～１５００の範囲でであり、特に好ましくは３００～１０００の範囲である。層状充填材は表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して３質量部～４０質量部用いることが好ましく、３質量部～３０質量部用いることがより好ましく、３質量部～２５質量部用いることが特に好ましい。 The plate-like or scale-like fillers forming the layer form include talc, graphite, plate-like calcium carbonate, plate-like alumina, and silicates such as bentonite group clay minerals, smectite group clay minerals and mica group clay minerals. At least one selected can be preferably used. Specific examples of the clay mineral include synthetic smectite, hectorite, beidellite, saponite, montmorillonite, vermiculite, stevensite, mica, synthetic mica, sodium tetrasilicon mica, and the like. In addition, the clay mineral may be a modified clay mineral modified with a silylating agent so as to have a water vapor barrier property. A known silylating agent such as methyltrimethoxysilane can be used as the silylating agent, but the silylating agent used is preferably 30% by weight or less based on the total amount of clay and silylating agent. The average thickness of the layered filler is preferably less than 0.5 μm, more preferably less than 0.2 μm, still more preferably less than 0.1 μm, and particularly preferably less than 0.05 μm. In addition, the average particle diameter (particle width) of the layered filler is preferably 0.01 μm or more and 10 μm or less, more preferably 0.02 μm or more and 5 μm or less, and still more preferably, as observed by an electron microscope. It is 0.02 μm or more and 2 μm or less, and particularly preferably 0.1 μm or more and 1 μm or less. Note that the aspect ratio of the layered filler is in the range of 100 to 2500, more preferably in the range of 200 to 2000, and still more preferably in the range of 250 to 1500, particularly when the particle diameter is microscopically observed. The range of 300 to 1000 is preferable. The layered filler is preferably used in an amount of 3 to 40 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements. More preferably, 3 parts by mass to 25 parts by mass is used.
　球状或いは無定形状としては、炭酸カルシウム、粉末シリカ、粉末金属粉、アルミナ、ベーマイト、ハイドロタルサイト、水酸化マグネシウム、酸化マグネシウム、酸化亜鉛、ケイ酸アルミニウム、ケイ酸カルシウム、水酸化アルミニウム、カーボンブラック、酸化チタン、チタン酸バリウム等が挙げられる。中でも、透明性、ガスバリア性の観点からケイ酸アルミニウム、アルミナ、粉末シリカ、酸化亜鉛を用いることが好ましく、アルミナ、粉末シリカを用いることがより好ましい。微粉末状充填材の平均粒子径は、電子顕微鏡観察による一次粒子径が、好ましくは０．５μｍ以上３０μｍ以下であり、より好ましくは０．５μｍ以上２０μｍ以下であり、さらに好ましくは０．５μｍ以上１５μｍ以下であり、特に好ましくは０．５μｍ以上１０μｍ以下である。充填材として粉末状充填材を主に用いる場合、粉末状充填材は表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して５質量部～３５質量部用いることが好ましく、８質量部～３５質量部用いることがより好ましく、１０質量部～３０質量部用いることが特に好ましい。 Spherical or amorphous shapes include calcium carbonate, powdered silica, powdered metal powder, alumina, boehmite, hydrotalcite, magnesium hydroxide, magnesium oxide, zinc oxide, aluminum silicate, calcium silicate, aluminum hydroxide, carbon black , Titanium oxide, barium titanate and the like. Among these, aluminum silicate, alumina, powder silica, and zinc oxide are preferably used from the viewpoints of transparency and gas barrier properties, and alumina and powder silica are more preferably used. The average particle size of the fine powder filler is such that the primary particle size by electron microscope observation is preferably 0.5 μm or more and 30 μm or less, more preferably 0.5 μm or more and 20 μm or less, and further preferably 0.5 μm or more. It is 15 μm or less, and particularly preferably 0.5 μm or more and 10 μm or less. When a powder filler is mainly used as the filler, the powder filler is used in an amount of 5 to 35 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used in the sealing material composition for display elements. It is preferable to use 8 to 35 parts by mass, and it is particularly preferable to use 10 to 30 parts by mass.
　微細棒状を形成する針状或いは繊維状充填材のうち、無機材料としてガラス繊維、炭素繊維（カーボンナノフィラー）、ホウ素繊維、ゾノトライト、ワラストナイト、アパタルジャイト、炭酸カルシウムウィスカー、ホウ酸アルミニウムウィスカー、酸化亜鉛ウィスカー、チタン酸カリウムウィスカー等が挙げられ、有機材料としてアラミド繊維、液晶ポリエステル繊維等が挙げられる。中でも、耐衝撃強度、耐熱性およびガスバリア性の観点からワラストナイト、酸化亜鉛ウィスカーを用いることが好ましく、ワラストナイトを用いることがより好ましい。充填材として棒状充填材を主に用いる場合、棒状充填材の平均粒子径は、電子顕微鏡観察による平均粒子径が、好ましくは１μｍ以上３０μｍ以下であり、より好ましくは１μｍ以上２０μｍ以下であり、さらに好ましくは１μｍ以上１５μｍ以下であり、特に好ましくは１μｍ以上１０μｍ以下である。また、直径は、電子顕微鏡観察による平均粒子径が、好ましくは１μｍ以上２０μｍ以下であり、より好ましくは１μｍ以上１５μｍ以下であり、さらに好ましくは１μｍ以上１２μｍ以下であり、特に好ましくは１μｍ以上１０μｍ以下である。棒状充填材は表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して５質量部～３０質量部用いることが好ましく、５質量部～２５質量部用いることがより好ましく、１０質量部～２０質量部用いることが特に好ましい。
（重合性液晶化合物）
　本発明において用いられる、重合性液晶化合物としては、単独または他の化合物との組成物において液晶性を示し、少なくとも１つ以上の重合性官能基を有する化合物であれば、特に限定はなく、公知慣用のものを用いることができる。 Among the needle-like or fibrous fillers that form fine rods, glass fiber, carbon fiber (carbon nanofiller), boron fiber, zonolite, wollastonite, apatalite, calcium carbonate whisker, aluminum borate whisker as inorganic materials Zinc oxide whisker, potassium titanate whisker and the like, and examples of the organic material include aramid fiber and liquid crystal polyester fiber. Among these, wollastonite and zinc oxide whiskers are preferably used from the viewpoint of impact strength, heat resistance, and gas barrier properties, and wollastonite is more preferably used. When a rod-shaped filler is mainly used as the filler, the average particle diameter of the rod-shaped filler is preferably 1 μm or more and 30 μm or less, more preferably 1 μm or more and 20 μm or less, and more preferably 1 μm or more and 20 μm or less. Preferably they are 1 micrometer or more and 15 micrometers or less, Most preferably, they are 1 micrometer or more and 10 micrometers or less. The average particle diameter by electron microscope observation is preferably 1 μm or more and 20 μm or less, more preferably 1 μm or more and 15 μm or less, further preferably 1 μm or more and 12 μm or less, and particularly preferably 1 μm or more and 10 μm or less. It is. The rod-shaped filler is preferably used in an amount of 5 to 30 parts by mass, preferably 5 to 25 parts by mass, with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the display element sealing material composition. More preferably, 10 to 20 parts by mass is used.
(Polymerizable liquid crystal compound)
The polymerizable liquid crystal compound used in the present invention is not particularly limited as long as it is a compound that exhibits liquid crystallinity alone or in a composition with another compound and has at least one polymerizable functional group. Conventional ones can be used.
　例えば、Ｈａｎｄｂｏｏｋ　ｏｆ　Ｌｉｑｕｉｄ　Ｃｒｙｓｔａｌｓ（Ｄ．Ｄｅｍｕｓ，Ｊ．Ｗ．Ｇｏｏｄｂｙ，Ｇ．Ｗ．Ｇｒａｙ，Ｈ．Ｗ．Ｓｐｉｅｓｓ，Ｖ．Ｖｉｌｌ編集、Ｗｉｌｅｙ－ＶＣＨ社発行，１９９８年）、季刊化学総説Ｎｏ．２２、液晶の化学（日本化学会編，１９９４年）、あるいは、特開平７－２９４７３５号公報、特開平８－３１１１号公報、特開平８－２９６１８号公報、特開平１１－８００９０号公報、特開平１１－１１６５３８号公報、特開平１１－１４８０７９号公報、等に記載されているような、１，４－フェニレン基１，４－シクロヘキレン基等の構造が複数繋がったメソゲンと呼ばれる剛直な部位と、ビニル基、アクリル基、（メタ）アクリル基といった重合性官能基を有する棒状重合性液晶化合物、あるいは特開２００４－２３７３号公報、特開２００４－９９４４６号公報に記載されているようなマレイミド基を有する棒状重合性液晶化合物が挙げられる。中でも、重合性基を有する棒状液晶化合物が、液晶温度範囲として室温前後の低温を含むものを作りやすく好ましい。 For example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, HW Spices, V. Vill, edited by Wiley-VCH, 1998), Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (edited by the Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, A rigid site called a mesogen in which a plurality of structures such as 1,4-phenylene group and 1,4-cyclohexylene group are connected as described in Kaihei 11-116538, JP-A-11-148079, etc. And a rod-like polymerizable liquid crystal compound having a polymerizable functional group such as a vinyl group, an acrylic group or a (meth) acryl group, or a maleimide as described in JP-A Nos. 2004-2373 and 2004-99446 Examples thereof include a rod-like polymerizable liquid crystal compound having a group. Among these, a rod-like liquid crystal compound having a polymerizable group is preferable because it can easily produce a liquid crystal having a temperature range around room temperature.
　重合性液晶化合物は、具体的には以下の一般式（ＩＩ）で表される化合物が好ましい。 Specifically, the polymerizable liquid crystal compound is preferably a compound represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記一般式（ＩＩ）中、Ｐ２１は重合性官能基を表し、
上記一般式（ＩＩ）中、Ｓｐ２１は炭素原子数１～１８のアルキレン基を表し（該アルキレン基中の水素原子は、１つ以上のハロゲン原子、ＣＮ基、又は重合性官能基を有する基により置換されていても良く、このアルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）、
上記一般式（ＩＩ）中、Ｘ２１は－Ｏ－、－Ｓ－、－ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＳＣＨ２－、－ＣＨ２Ｓ－、－ＣＦ２Ｏ－、－ＯＣＦ２－、－ＣＦ２Ｓ－、－ＳＣＦ２－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＯＯ－ＣＨ２ＣＨ２－、－ＯＣＯ－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２－ＣＯＯ－、－ＣＨ２ＣＨ２－ＯＣＯ－、－ＣＯＯ－ＣＨ２－、－ＯＣＯ－ＣＨ２－、－ＣＨ２－ＣＯＯ－、－ＣＨ２－ＯＣＯ－、－ＣＨ＝ＣＨ－、－Ｎ＝Ｎ－、－ＣＨ＝Ｎ－Ｎ＝ＣＨ－、－ＣＦ＝ＣＦ－、－Ｃ≡Ｃ－又は単結合を表し（ただし、Ｐ２１－Ｓｐ２１、及びＳｐ２１－Ｘ２１は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－基を含まない。）、
上記一般式（ＩＩ）中、ｑ２１は０又は１を表し、
上記一般式（ＩＩ）中、ＭＧはメソゲン基を表し、
上記一般式（ＩＩ）中、Ｒ２１は、水素原子、ハロゲン原子、シアノ基、又は炭素原子数１から１２の直鎖又は分岐アルキル基を表し、該アルキル基は直鎖状であっても分岐していてもよく、該アルキル基は１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－が各々独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－又は－Ｃ≡Ｃ－によって置換されても良く、あるいはＲ２１は、一般式（ＩＩ－ａ） In the general formula (II), P 21 represents a polymerizable functional group,
In the general formula (II), Sp 21 represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is a group having one or more halogen atoms, a CN group, or a polymerizable functional group). may be substituted, each of the one CH 2 group or nonadjacent two or more CH 2 groups existing in the alkylene group independently of one another by, -O -, - COO -, - OCO Or may be replaced by-or -OCO-O-).
In the general formula (II), X 21 represents —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S. —CO—, —O—CO—O—, —CO—NH—, —NH—CO—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S —, —SCF 2 —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 - OCO—, —CH═CH—, —N═N—, —CH═NN—CH—, —CF═CF—, —C≡C— or a single bond Represents, (however, P 21 -Sp 21, and Sp 21 -X 21 are, -O-O -, - O -NH - -, do not contain S-S- and -O-S- group.)
In the general formula (II), q21 represents 0 or 1,
In the general formula (II), MG represents a mesogenic group,
In the general formula (II), R 21 represents a hydrogen atom, a halogen atom, a cyano group, or a linear or branched alkyl group having 1 to 12 carbon atoms, and the alkyl group is branched even if it is linear. In the alkyl group, one —CH 2 — or two or more non-adjacent —CH 2 — 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—CH═CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted, or R 21 may have the general formula (II-a)
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（上記一般式（ＩＩ－ａ）中、Ｐ２２は重合性官能基を表し、Ｓｐ２２は、Ｓｐ２１で定義されたものと同一のものを表し、Ｘ２２は、Ｘ２１で定義されたものと同一のものを表し（ただし、Ｐ２２－Ｓｐ２２、及びＳｐ２２－Ｘ２２は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－基を含まない。）、ｑ２２は０又は１を表す。）を表し、
上記ＭＧで表されるメソゲン基は、一般式（ＩＩ－ｂ） (In the general formula (II-a), P 22 represents a polymerizable functional group, Sp 22 represents the same as defined in Sp 21 , and X 22 represents that defined in X 21. (Wherein P 22 -Sp 22 and Sp 22 -X 22 do not include —O—O—, —O—NH—, —S—S— and —O—S— groups). .), Q22 represents 0 or 1.)
The mesogenic group represented by the above MG has the general formula (II-b)
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（上記一般式（ＩＩ－ｂ）中、Ｂ１、Ｂ２及びＢ３はそれぞれ独立的に、１，４－フェニレン基、１，４－シクロヘキシレン基、１，４－シクロヘキセニル基、テトラヒドロピラン－２，５－ジイル基、１，３－ジオキサン－２，５－ジイル基、テトラヒドロチオピラン－２，５－ジイル基、１，４－ビシクロ（２，２，２）オクチレン基、デカヒドロナフタレン－２，６－ジイル基、ピリジン－２，５－ジイル基、ピリミジン－２，５－ジイル基、ピラジン－２，５－ジイル基、チオフェン－２，５－ジイル基－、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、２，６－ナフチレン基、フェナントレン－２，７－ジイル基、９，１０－ジヒドロフェナントレン－２，７－ジイル基、１，２，３，４，４ａ，９，１０ａ－オクタヒドロフェナントレン－２，７－ジイル基、１，４－ナフチレン基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジチオフェン－２，６－ジイル基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジセレノフェン－２，６－ジイル基、［１］ベンゾチエノ［３，２－ｂ］チオフェン－２，７－ジイル基、［１］ベンゾセレノフェノ［３，２－ｂ］セレノフェン－２，７－ジイル基、又はフルオレン－２，７－ジイル基を表し、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基（当該アルキル基中の水素原子は、１つ以上のフェニル基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、炭素原子数２～８のアルケノイル基、炭素原子数２～８のアルケノイルオキシ基、及び／又は一般式（ＩＩ－ｃ） (In the above general formula (II-b), B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2, 5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2, 6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4 Tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-o Tahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene -2,7-diyl group or fluorene-2,7-diyl group, and one or more F, Cl, CF 3 , OCF 3 , CN groups, alkyl groups having 1 to 8 carbon atoms as substituents ( hydrogen atoms in the alkyl group may be substituted with one or more phenyl groups, in each of two or more CH 2 groups not one CH 2 group or adjacent present in this group interconversion Independently, —O—, —COO—, —OCO— or —O O—O— may be substituted.), An alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms An alkoxycarbonyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, an alkenoyl group having 2 to 8 carbon atoms, an alkenoyloxy group having 2 to 8 carbon atoms, and / Or general formula (II-c)
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（上記式（ＩＩ－ｃ）中、Ｐ２３は重合性官能基を表し、
Ｓｐ２３は、上記Ｓｐ２１で定義されたものと同一のものを表し、
Ｘ２３は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、又は単結合を表し、ｑ２３は０又は１を表し、ｑ２４は０又は１を表す。（ただし、Ｐ２３－Ｓｐ２３、及びＳｐ２３－Ｘ２３は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－基を含まない。））を有していても良く、
上記一般式（ＩＩ－ｂ）中、Ｚ１及びＺ２はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－Ｃ（ＣＦ３）２－、ハロゲン原子を有してもよい炭素原子数２～１０のアルキル基又は単結合を表すが、Ｚ１、Ｚ２が単結合を表す場合、上記Ｂ１、Ｂ２、Ｂ３のうち、隣接して存在する２つの環構造がそれぞれ有する置換基が結合して環状基を形成しても良く、ｒ１は０、１、２又は３を表し、Ｂ１、及びＺ１が複数存在する場合は、それぞれ、同一であっても、異なっていても良い。）で表される。 (In the above formula (II-c), P 23 represents a polymerizable functional group,
Sp 23 represents the same as defined in Sp 21 above,
X 23 represents —O—, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, or A single bond is represented, q23 represents 0 or 1, and q24 represents 0 or 1. (However, P 23 -Sp 23 and Sp 23 -X 23 do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.) You may,
In the general formula (II-b), Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH—. , —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, — C═N—, —N═C—, —CONH—, —NHCO—, —C (CF 3 ) 2 —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom or a single bond However, when Z1 and Z2 represent a single bond, among the above B1, B2 and B3, the substituents which two adjacent ring structures each have may be combined to form a cyclic group, and r1 is Represents 0, 1, 2 or 3, and when there are a plurality of B1 and Z1, It may be one or different. ).
　前述のとおり、上記一般式（ＩＩ）中、Ｓｐ２１は炭素原子数１～１８のアルキレン基を表し、該アルキレン基中の水素原子は、重合性官能基を有する基により置換されていても良いが、該重合性官能基を有する基として好ましい基としては、上記一般式（ＩＩ－ｃ）で表される基が挙げられる。 As described above, in the general formula (II), Sp 21 represents an alkylene group having 1 to 18 carbon atoms, and the hydrogen atom in the alkylene group may be substituted with a group having a polymerizable functional group. However, examples of a group preferable as the group having a polymerizable functional group include a group represented by the general formula (II-c).
　上記一般式（ＩＩ）、一般式（ＩＩ－ａ）、一般式（ＩＩ－ｃ）中、Ｐ２１、Ｐ２２及びＰ２３は、それぞれ独立して、下記の式（Ｐ－２－１）から式（Ｐ－２－２０）で表される重合性基から選ばれる置換基を表すのが好ましい。 In the above general formula (II), general formula (II-a), and general formula (II-c), P 21 , P 22 and P 23 are each independently represented by the following formula (P-2-1): It preferably represents a substituent selected from a polymerizable group represented by the formula (P-2-20).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　これらの重合性官能基のうち、重合性を高める観点から、式（Ｐ－２－１）、（Ｐ－２－２）、（Ｐ－２－７）、（Ｐ－２－１２）、（Ｐ－２－１３）が好ましく、式（Ｐ－２－１）、（Ｐ－２－２）、（Ｐ－２－７）がより好ましい。 Among these polymerizable functional groups, from the viewpoint of increasing the polymerizability, the formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), ( P-2-13) is preferred, and formulas (P-2-1), (P-2-2), and (P-2-7) are more preferred.
　上記一般式（ＩＩ－ｂ）中、Ｂ１、Ｂ２及びＢ３はそれぞれ独立して、上述した置換基を有しても良い、１，４－フェニレン基、１，４－シクロヘキシレン基、２，６－ナフチレン基を表すことが好ましい。 In the above general formula (II-b), B1, B2 and B3 may each independently have the above-mentioned substituents, 1,4-phenylene group, 1,4-cyclohexylene group, 2,6 -Preferably represents a naphthylene group.
　上記一般式（ＩＩ）、一般式（ＩＩ－ａ）、一般式（ＩＩ－ｃ）中、Ｓｐ２１、Ｓｐ２２及びＳｐ２３は、保存安定性を高める観点から、それぞれ独立して、炭素原子数１～１４のアルキレン基を表すことが好ましく、当該アルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－又は－ＯＣＯ－により置き換えられていても良い。また、Ｓｐ２１、Ｓｐ２２及びＳｐ２３は、それぞれ独立して、炭素原子数１～１２のアルキレン基を表すことがより好ましく、当該アルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基は－Ｏ－により置き換えられていても良い。 In the general formula (II), the general formula (II-a), and the general formula (II-c), Sp 21 , Sp 22 and Sp 23 are each independently from the viewpoint of enhancing storage stability. preferably represents an 1-14 alkylene group, two or more CH 2 groups not one CH 2 group or adjacent existing in the alkylene group independently of one another each, -O -, - COO It may be replaced by-or -OCO-. Further, Sp 21 , Sp 22 and Sp 23 each independently preferably represent an alkylene group having 1 to 12 carbon atoms, and are not adjacent to one CH 2 group present in the alkylene group. Two or more CH 2 groups may be replaced by —O—.
　上記一般式（ＩＩ）、一般式（ＩＩ－ａ）、一般式（ＩＩ－ｃ）中、Ｘ２１、Ｘ２２及びＸ２３は、それぞれ独立して、－Ｏ－、－ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＯＯ－ＣＨ２ＣＨ２－、－ＯＣＯ－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２－ＣＯＯ－、－ＣＨ２ＣＨ２－ＯＣＯ－、－ＣＯＯ－ＣＨ２－、－ＯＣＯ－ＣＨ２－、－ＣＨ２－ＣＯＯ－、－ＣＨ２－ＯＣＯ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－又は単結合を表すことが好ましく、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、又は単結合を表すことがより好ましい（ただし、Ｐ２１－Ｓｐ２１、Ｓｐ２１－Ｘ２１、Ｐ２２－Ｓｐ２２、Ｓｐ２２－Ｘ２２、Ｐ２３－Ｓｐ２３、及びＳｐ２３－Ｘ２３は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－基を含まない。）。 In the above general formula (II), general formula (II-a), and general formula (II-c), X 21 , X 22, and X 23 are each independently —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO —CH═CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, —CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 —, — It preferably represents OCO—CH 2 —, —CH 2 —COO—, —CH 2 —OCO—, —CH═CH—, —C≡C— or a single bond, —O—, —COO—, —OCO -, or is more preferably a single bond (provided that, P 21 -Sp 21, Sp 21 -X 1, P 22 -Sp 22, Sp 22 -X 22, P 23 -Sp 23, and Sp 23 -X 23 are, -O-O -, - O -NH -, - S-S- and -O-S -Does not contain groups).
　上記一般式（ＩＩ－ｂ）中、Ｚ１及びＺ２はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、又は単結合を表すことが好ましい。 In the general formula (II-b), Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 O—, —CH═CH—, —C≡C—, —CH 2 CH 2. It preferably represents COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, —C═N—, —N═C—, or a single bond.
　上記一般式（ＩＩ－ｂ）中、ｒ１は０又は１を表すことが好ましい。
（単官能重合性液晶化合物）
前記一般式（ＩＩ）で表される化合物のうち、分子内に１個の重合性官能基を有する単官能重合性液晶化合物として、下記一般式（ＩＩ－１）で表される化合物が好ましい。 In the general formula (II-b), r1 preferably represents 0 or 1.
(Monofunctional polymerizable liquid crystal compound)
Among the compounds represented by the general formula (II), the compound represented by the following general formula (II-1) is preferable as the monofunctional polymerizable liquid crystal compound having one polymerizable functional group in the molecule.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　一般式（ＩＩ－１）中、Ｐ２１１、Ｘ２１１、及びｑ２１１は、それぞれ、上記一般式（ＩＩ）中のＰ２１、Ｘ２１、及びｑ２１として定義したものと同じものを表し、
一般式（ＩＩ－１）中、Ｒ２１１は、水素原子、ハロゲン原子、シアノ基、１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－が各々独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＮＨ－、－Ｎ（ＣＨ３）－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－又は－Ｃ≡Ｃ－によって置換されても良い、炭素原子数１から１２の直鎖又は分岐アルキル基、炭素原子数１から１２の直鎖又は分岐アルケニル基を表し、該アルキル基、アルケニル基の有する１個又は２個以上の水素原子は、ハロゲン原子、シアノ基によって置換されても良く、複数置換されている場合それぞれ同一であっても、異なっていても良く、
一般式（ＩＩ－１）中、Ｓｐ２１１は炭素原子数１～１８のアルキレン基を表し（該アルキレン基中の水素原子は、１つ以上のハロゲン原子、又はＣＮ基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）を表し、
一般式（ＩＩ－１）中、ＭＧ１はメソゲン基を表し、当該メソゲン基としては、一般式（ＩＩ－１－ｂ） In the general formula (II-1), P 211 , X 211 , and q211 each represent the same as defined as P 21 , X 21 , and q21 in the general formula (II),
In General Formula (II-1), R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent —CH 2 —, each independently —O—. , —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—, —NH—CO—, — NH—, —N (CH 3 ) —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, — Represents a linear or branched alkyl group having 1 to 12 carbon atoms and a linear or branched alkenyl group having 1 to 12 carbon atoms, which may be substituted by CF═CF— or —C≡C—, and the alkyl group , One or more hydrogen atoms of the alkenyl group are substituted with a halogen atom or a cyano group If multiple substitutions are made, they may be the same or different,
In the general formula (II-1), Sp 211 represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group may be substituted with one or more halogen atoms or a CN group) In this group, one CH 2 group or two or more non-adjacent CH 2 groups are each independently represented by —O—, —COO—, —OCO— or —OCO—O—. May be replaced)
In the general formula (II-1), MG 1 represents a mesogenic group, and the mesogenic group includes the general formula (II-1-b)
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
（上記一般式（ＩＩ－１－ｂ）中、Ｂ１１、Ｂ２１及びＢ３１はそれぞれ独立的に、１，４－フェニレン基、１，４－シクロヘキシレン基、１，４－シクロヘキセニル基、テトラヒドロピラン－２，５－ジイル基、１，３－ジオキサン－２，５－ジイル基、テトラヒドロチオピラン－２，５－ジイル基、１，４－ビシクロ（２，２，２）オクチレン基、デカヒドロナフタレン－２，６－ジイル基、ピリジン－２，５－ジイル基、ピリミジン－２，５－ジイル基、ピラジン－２，５－ジイル基、チオフェン－２，５－ジイル基－、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、２，６－ナフチレン基、フェナントレン－２，７－ジイル基、９，１０－ジヒドロフェナントレン－２，７－ジイル基、１，２，３，４，４ａ，９，１０ａ－オクタヒドロフェナントレン－２，７－ジイル基、１，４－ナフチレン基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジチオフェン－２，６－ジイル基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジセレノフェン－２，６－ジイル基、［１］ベンゾチエノ［３，２－ｂ］チオフェン－２，７－ジイル基、［１］ベンゾセレノフェノ［３，２－ｂ］セレノフェン－２，７－ジイル基、又はフルオレン－２，７－ジイル基を表し、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基（当該アルキル基中の水素原子は、１つ以上のフェニル基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、及び／又は、炭素原子数２～８のアルケノイル基を有していても良く、
上記一般式（ＩＩ－１－ｂ）中、Ｚ１１及びＺ２１はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－Ｃ（ＣＦ３）２－、ハロゲン原子を有してもよい炭素原子数２～１０のアルキル基又は単結合を表し、ｒ１１は０、１、２又は３を表し、Ｂ１１、及びＺ１１が複数存在する場合は、それぞれ、同一であっても、異なっていても良い。）で表されるが、Ｚ１１、Ｚ２１が単結合を表す場合、上記Ｂ１１、Ｂ２１、Ｂ３１のうち、隣接して存在する２つの環構造がそれぞれ有する置換基が結合して環状基を形成しても良く、
　上記一般式（ＩＩ－１）中、Ｐ２１１は重合性を高める観点から、上述の式（Ｐ－２－１）、（Ｐ－２－２）、（Ｐ－２－７）、（Ｐ－２－１２）、（Ｐ－２－１３）が好ましく、式（Ｐ－２－１）、（Ｐ－２－２）、（Ｐ－２－７）がより好ましい。 (In the general formula (II-1-b), B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4, 4a, 9, 0a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2- b: 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b ] Represents a selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and has at least one F, Cl, CF 3 , OCF 3 , CN group or an alkyl having 1 to 8 carbon atoms as a substituent. group (the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
In the general formula (II-1-b), Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═ CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 — , —C═N—, —N═C—, —CONH—, —NHCO—, —C (CF 3 ) 2 —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom, or a single bond , R11 represents 0, 1, 2, or 3, and when there are a plurality of B11 and Z11, they may be the same or different. In the case where Z11 and Z21 represent a single bond, the substituents of the two adjacent ring structures among B11, B21 and B31 are combined to form a cyclic group. Well,
In the general formula (II-1), P 211 is the above-described formula (P-2-1), (P-2-2), (P-2-7), (P— 2-12) and (P-2-13) are preferable, and formulas (P-2-1), (P-2-2), and (P-2-7) are more preferable.
　上記一般式（ＩＩ－１）中、Ｓｐ２１１は、保存安定性を高める観点から、それぞれ独立して、炭素原子数１～１４のアルキレン基を表すことが好ましく、当該アルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－又は－ＯＣＯ－により置き換えられていても良い。また、Ｓｐ２１１は、それぞれ独立して、炭素原子数１～１２のアルキレン基を表すことがより好ましく、当該アルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基は－Ｏ－により置き換えられていても良い。 In the general formula (II-1), Sp 211 is preferably each independently an alkylene group having 1 to 14 carbon atoms from the viewpoint of enhancing storage stability, and is present in the alkylene group. Two CH 2 groups or two or more non-adjacent CH 2 groups may be each independently replaced by —O—, —COO— or —OCO—. Also, Sp 211 are each independently more preferably an alkylene group having 1 to 12 carbon atoms, not one CH 2 group or adjacent existing in the alkylene group two or more CH 2 The group may be replaced by -O-.
　上記一般式（ＩＩ－１）中、Ｘ２１１は、それぞれ独立して、－Ｏ－、－ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＯＯ－ＣＨ２ＣＨ２－、－ＯＣＯ－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２－ＣＯＯ－、－ＣＨ２ＣＨ２－ＯＣＯ－、－ＣＯＯ－ＣＨ２－、－ＯＣＯ－ＣＨ２－、－ＣＨ２－ＣＯＯ－、－ＣＨ２－ＯＣＯ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－又は単結合を表すことが好ましく、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、又は単結合を表すことがより好ましい（ただし、Ｐ２１１－Ｓｐ２１１、及びＳｐ２１１－Ｘ２１１は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－基を含まない。）。 In the general formula (II-1), X 211 each independently represents —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —O—CO. —O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO-, It preferably represents —CH═CH—, —C≡C— or a single bond, and more preferably represents —O—, —COO—, —OCO—, or a single bond (provided that P 211 -Sp 211 , and Sp 211 -X 211 may, -O-O -, - O -NH -, - S-S And it does not contain -O-S- group.).
　上記一般式（ＩＩ－１）中、Ｒ２１１は、水素原子、ハロゲン原子、シアノ基、１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－が各々独立して－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、又は－Ｃ≡Ｃ－によって置換されても良い、炭素原子数１から１２の直鎖又は分岐アルキル基、炭素原子数１から１２の直鎖又は分岐アルケニル基を表すことが好ましく、該アルキル基、アルケニル基の有する１個又は２個以上の水素原子は、ハロゲン原子、シアノ基によって置換されても良く、複数置換されている場合それぞれ同一であっても、異なっていても良い。また、Ｒ２１１は、水素原子、ハロゲン原子、シアノ基、１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－が各々独立して－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、又は－Ｃ≡Ｃ－によって置換されても良い、炭素原子数１から１２の直鎖又は分岐アルキル基、炭素原子数１から８の直鎖又は分岐アルケニル基を表すことがより好ましく、該アルキル基、アルケニル基の有する１個又は２個以上の水素原子は、ハロゲン原子、シアノ基によって置換されても良く、複数置換されている場合それぞれ同一であっても、異なっていても良い。 In the general formula (II-1), R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent —CH 2 —, each independently —O —, —CO—, —COO—, —OCO—, —O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH A linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched alkenyl group having 1 to 12 carbon atoms, which may be substituted by ═CH—, —CH═CH—, or —C≡C— It is preferable that one or two or more hydrogen atoms of the alkyl group or alkenyl group may be substituted with a halogen atom or a cyano group. It may be different. R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent —CH 2 —, each independently —O—, —CO—, —COO. Represents a linear or branched alkyl group having 1 to 12 carbon atoms and a linear or branched alkenyl group having 1 to 8 carbon atoms, which may be substituted by —, —OCO—, or —C≡C—. More preferably, one or more hydrogen atoms of the alkyl group or alkenyl group may be substituted with a halogen atom or a cyano group, and when a plurality of substituents are substituted, they may be the same or different. Also good.
　上記一般式（ＩＩ－１－ｂ）中、Ｂ１１、Ｂ２１及びＢ３１はそれぞれ独立的に、上述した置換基を有しても良い、１，４－フェニレン基、１，４－シクロヘキシレン基、２，６－ナフチレン基を表すことが好ましく、Ｚ１１及びＺ２１はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、又は単結合を表すことが好ましく、ｒ１１は０又は１を表すことが好ましい。 In the above general formula (II-1-b), B11, B21 and B31 each independently may have the above-mentioned substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, and Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH It is preferable to represent —, —C≡C—, —C═N—, —N═C—, or a single bond, and r11 preferably represents 0 or 1.
　一般式（ＩＩ－１）の例として、下記一般式（ＩＩ－１－１）～（ＩＩ－１－４）で表される化合物を挙げることができるが、下記の一般式に限定されるわけではない。 Examples of the general formula (II-1) include compounds represented by the following general formulas (II-1-1) to (II-1-4), but are not limited to the following general formulas is not.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記一般式（ＩＩ－１－１）～（ＩＩ－１－４）中、Ｐ２１１、Ｓｐ２１１、Ｘ２１１、及び、ｑ２１１は、それぞれ、上記一般式（ＩＩ－１）の定義と同じものを表し、
上記一般式（ＩＩ－１－１）～（ＩＩ－１－４）中、Ｂ１１１、Ｂ１１２、Ｂ１１３、Ｂ２１、Ｂ３１は、上記一般式（ＩＩ－１－ｂ）のＢ１１～Ｂ３１の定義と同じものを表し、好ましい基もＢ１１～Ｂ３１の定義と同じものを表し、それぞれ、同一であっても、異なっていても良く、
上記一般式（ＩＩ－１－１）～（ＩＩ－１－４）中、Ｚ１１１、Ｚ１１２、Ｚ１１３、Ｚ２１は、上記一般式（ＩＩ－１－ｂ）のＺ１１～Ｚ２１の定義と同じものを表し、好ましい基もＺ１１～Ｚ２１の定義と同じものを表し、それぞれ、同一であっても、異なっていても良く、
上記一般式（ＩＩ－１－１）～（ＩＩ－１－４）中、Ｒ２１１は、水素原子、ハロゲン原子、シアノ基、１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－が各々独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＮＨ－、－Ｎ（ＣＨ３）－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－又は－Ｃ≡Ｃ－によって置換されても良い、炭素原子数１から１２の直鎖又は分岐アルキル基、炭素原子数１から１２の直鎖又は分岐アルケニル基を表し、該アルキル基、アルケニル基の有する１個又は２個以上の水素原子は、ハロゲン原子、シアノ基によって置換されても良く、複数置換されている場合それぞれ同一であっても、異なっていても良い。 In the general formulas (II-1-1) to (II-1-4), P 211 , Sp 211 , X 211 , and q 211 are the same as defined in the general formula (II-1). Represent,
In the above general formulas (II-1-1) to (II-1-4), B111, B112, B113, B21, and B31 are the same as the definitions of B11 to B31 in the general formula (II-1-b). And preferred groups also represent the same as defined for B11 to B31, and may be the same or different,
In the general formulas (II-1-1) to (II-1-4), Z111, Z112, Z113, and Z21 represent the same definitions as Z11 to Z21 in the general formula (II-1-b). The preferred groups also represent the same definitions as Z11 to Z21, and may be the same or different,
In the general formulas (II-1-1) to (II-1-4), R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 —, or two or more non-adjacent — CH 2 — is independently —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO. —NH—, —NH—CO—, —NH—, —N (CH 3 ) —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH A straight-chain or branched alkyl group having 1 to 12 carbon atoms, which may be substituted by ═CH—, —CH═CH—, —CF═CF— or —C≡C—; Represents a chain or branched alkenyl group, and one or more hydrogen atoms of the alkyl group or alkenyl group are a halogen atom, It may be substituted with a cyano group, and when multiple substitutions are made, they may be the same or different.
　上記一般式（ＩＩ－１－１）～（ＩＩ－１－４）のうち、重合後の配向性の観点から、一般式（ＩＩ－１－１）～一般式（ＩＩ－１－２）で表される化合物が好ましい。 Of the above general formulas (II-1-1) to (II-1-4), from the viewpoint of orientation after polymerization, the general formulas (II-1-1) to (II-1-2) The compounds represented are preferred.
　上記一般式（ＩＩ－１－１）～（ＩＩ－１－４）で表される化合物としては、以下の式（ＩＩ－１－１－１）～式（ＩＩ－１－１－２６）で表される化合物を例示されるが、これらに限定される訳ではない。 The compounds represented by the general formulas (II-1-1) to (II-1-4) are represented by the following formulas (II-1-1-1) to (II-1-1-26). The compounds represented are exemplified, but not limited thereto.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式中、Ｒｃは水素原子又はメチル基を表し、ｍは０～１８の整数を表し、ｎは０又は１を表し、Ｒ２１１は、上記一般式（ＩＩ－１－１）～（ＩＩ－１－４）の定義と同じものを表すが、Ｒ２１１は、水素原子、ハロゲン原子、シアノ基、１個の－ＣＨ２－が－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、によって置換されても良い、炭素原子数１から６の直鎖アルキル基又は炭素原子数１から６の直鎖アルケニル基を表すことが好ましく、
上記環状基は、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、炭素原子数２～８のアルケノイル基、炭素原子数２～８のアルケノイルオキシ基を有していても良い。 In the formula, R c represents a hydrogen atom or a methyl group, m represents an integer of 0 to 18, n represents 0 or 1, and R 211 represents the above general formulas (II-1-1) to (II- 1-4) is the same as defined above, except that R 211 represents a hydrogen atom, a halogen atom, a cyano group, one —CH 2 — is —O—, —CO—, —COO—, —OCO—, It preferably represents a linear alkyl group having 1 to 6 carbon atoms or a linear alkenyl group having 1 to 6 carbon atoms, which may be substituted by
The cyclic group includes one or more F, Cl, CF 3 , OCF 3 , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 8 alkanoyl groups, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkenyloxy groups having 2 to 8 carbon atoms, carbon atoms It may have an alkenoyl group having 2 to 8 carbon atoms and an alkenoyloxy group having 2 to 8 carbon atoms.
　上記一般式（ＩＩ－１－１－１）～一般式（ＩＩ－１－１－２６）で表される化合物はさらに具体的に以下の一般式（ＩＩ－１－２－１）～一般式（ＩＩ－１－２－３７）で表される化合物を例示できるが、これらに限定される訳ではない。 The compounds represented by the general formulas (II-1-1-1) to (II-1-1-26) are more specifically represented by the following general formulas (II-1-2-1) to The compound represented by (II-1-2-37) can be exemplified, but is not limited thereto.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　上記一般式（ＩＩ－１）、上記一般式（ＩＩ－１－１）～上記一般式（ＩＩ－１－４）、上記一般式（ＩＩ－１－１－１）～一般式（ＩＩ－１－１－２６）、又は、一般式（ＩＩ－１－２－１）～一般式（ＩＩ－１－２－３７）で表される、分子内に１個の重合性官能基を有する単官能重合性液晶化合物の合計含有量は、表示素子用封止材料組成物に用いる重合性液晶化合物の合計量のうち、０～９０質量％含有することが好ましく、０～８５質量％含有することがより好ましく、０～８０質量％含有することが特に好ましい。光学異方体の配向性を重視する場合には下限値を５質量％以上にすることが好ましく、１０質量％以上にすることがより好ましく、塗膜の硬さを重視する場合には上限値を８０質量％以下とすることが好ましく、７０質量％以下とすることがより好ましい。
（２官能重合性液晶化合物）
前記一般式（ＩＩ）で表される化合物のうち、分子内に２個の重合性官能基を有する２官能重合性液晶化合物として、下記一般式（ＩＩ－２）で表される化合物が好ましい。 General Formula (II-1), General Formula (II-1-1) to General Formula (II-1-4), General Formula (II-1-1-1) to General Formula (II-1) -1-26), or a monofunctional compound having one polymerizable functional group in the molecule represented by general formula (II-1-2-1) to general formula (II-1-2-37) The total content of the polymerizable liquid crystal compound is preferably 0 to 90% by mass, and preferably 0 to 85% by mass, based on the total amount of the polymerizable liquid crystal compound used in the sealing material composition for display elements. More preferably, the content is particularly preferably 0 to 80% by mass. When placing importance on the orientation of the optical anisotropic body, the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and when emphasizing the hardness of the coating film, the upper limit Is preferably 80% by mass or less, and more preferably 70% by mass or less.
(Bifunctional polymerizable liquid crystal compound)
Of the compounds represented by the general formula (II), the compound represented by the following general formula (II-2) is preferable as the bifunctional polymerizable liquid crystal compound having two polymerizable functional groups in the molecule.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
式中、Ｐ２２１、Ｘ２１１、ｑ２２１、Ｘ２２２、ｑ２２２、Ｐ２２２は、それぞれ、上記一般式（ＩＩ）又は一般式（ＩＩ－ａ）中のＰ２１、Ｘ２１、ｑ２１、Ｘ２２、ｑ２２、Ｐ２２の定義と同じものを表し、
一般式（ＩＩ－２）中、Ｓｐ２２１及びＳｐ２２２はそれぞれ独立して、炭素原子数１～１８のアルキレン基を表し（該アルキレン基中の水素原子は、１つ以上のハロゲン原子、又はＣＮ基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）を表し、
一般式（ＩＩ－２）中、ＭＧ２はメソゲン基を表し、当該メソゲン基としては、一般式（ＩＩ－２－ｂ） In the formula, P 221 , X 211 , q 221 , X 222 , q 222 , and P 222 are P 21 , X 21 , q 21 , X 22 , q 22 in the general formula (II) or the general formula (II-a), respectively. represent the same as the definition of P 22,
In the general formula (II-2), Sp 221 and Sp 222 each independently represent an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group is one or more halogen atoms, or CN It may be substituted by a group, two or more of CH 2 groups, independently of one another each of the present in the radical is not one CH 2 group or adjacent, -O -, - COO -, - OCO -Or -OCO-O- may be substituted).
In the general formula (II-2), MG 2 represents a mesogenic group, and the mesogenic group includes the general formula (II-2-b)
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
（上記一般式（ＩＩ－２－ｂ）中、Ｂ１１、Ｂ２１及びＢ３１はそれぞれ独立的に、１，４－フェニレン基、１，４－シクロヘキシレン基、１，４－シクロヘキセニル基、テトラヒドロピラン－２，５－ジイル基、１，３－ジオキサン－２，５－ジイル基、テトラヒドロチオピラン－２，５－ジイル基、１，４－ビシクロ（２，２，２）オクチレン基、デカヒドロナフタレン－２，６－ジイル基、ピリジン－２，５－ジイル基、ピリミジン－２，５－ジイル基、ピラジン－２，５－ジイル基、チオフェン－２，５－ジイル基－、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、２，６－ナフチレン基、フェナントレン－２，７－ジイル基、９，１０－ジヒドロフェナントレン－２，７－ジイル基、１，２，３，４，４ａ，９，１０ａ－オクタヒドロフェナントレン－２，７－ジイル基、１，４－ナフチレン基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジチオフェン－２，６－ジイル基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジセレノフェン－２，６－ジイル基、［１］ベンゾチエノ［３，２－ｂ］チオフェン－２，７－ジイル基、［１］ベンゾセレノフェノ［３，２－ｂ］セレノフェン－２，７－ジイル基、又はフルオレン－２，７－ジイル基を表し、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基（当該アルキル基中の水素原子は、１つ以上のフェニル基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、及び／又は、炭素原子数２～８のアルケノイル基を有していても良く、
上記一般式（ＩＩ－２－ｂ）中、Ｚ１１及びＺ２１はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－Ｃ（ＣＦ３）２－、ハロゲン原子を有してもよい炭素原子数２～１０のアルキル基又は単結合を表し、ｒ１１は０、１、２又は３を表し、Ｂ１１、及びＺ１１が複数存在する場合は、それぞれ、同一であっても、異なっていても良いが、Ｚ１１、Ｚ２１が単結合を表す場合、上記Ｂ１１、Ｂ２１、Ｂ３１のうち、隣接して存在する２つの環構造がそれぞれ有する置換基が結合して環状基を形成しても良い。）が好ましい。 (In the general formula (II-2-b), B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4, 4a, 9, 0a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2- b: 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b ] Represents a selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and has at least one F, Cl, CF 3 , OCF 3 , CN group or an alkyl having 1 to 8 carbon atoms as a substituent. group (the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
In the general formula (II-2-b), Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═ CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 — , —C═N—, —N═C—, —CONH—, —NHCO—, —C (CF 3 ) 2 —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom, or a single bond R11 represents 0, 1, 2 or 3, and when there are a plurality of B11 and Z11, they may be the same or different, but Z11 and Z21 each represent a single bond B11, B21 and B31, two adjacent ring structures Substituents each having a structure may combine to form a cyclic group. ) Is preferred.
　上記一般式（ＩＩ－２）中、Ｐ２２１及びＰ２２２は重合性を高める観点から、それぞれ独立して、上述の式（Ｐ－２－１）、（Ｐ－２－２）、（Ｐ－２－７）、（Ｐ－２－１２）、（Ｐ－２－１３）が好ましく、式（Ｐ－２－１）、（Ｐ－２－２）がより好ましい。 In the general formula (II-2), P 221 and P 222 are each independently from the above formulas (P-2-1), (P-2-2), (P— 2-7), (P-2-12), and (P-2-13) are preferable, and formulas (P-2-1) and (P-2-2) are more preferable.
　上記一般式（ＩＩ－２）中、Ｓｐ２２１及びＳｐ２２２は、保存安定性を高める観点から、それぞれ独立して、炭素原子数１～１４のアルキレン基を表すことが好ましく、当該アルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－又は－ＯＣＯ－により置き換えられていても良い。また、Ｓｐ２２１及びＳｐ２２２は、それぞれ独立して、炭素原子数１～１２のアルキレン基を表すことがより好ましく、当該アルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基は－Ｏ－により置き換えられていても良い。 In the general formula (II-2), Sp 221 and Sp 222 are preferably each independently an alkylene group having 1 to 14 carbon atoms from the viewpoint of enhancing storage stability. One CH 2 group present or two or more non-adjacent CH 2 groups may each be independently replaced by —O—, —COO— or —OCO—. Further, each of Sp 221 and Sp 222 preferably independently represents an alkylene group having 1 to 12 carbon atoms, and one CH 2 group present in the alkylene group or two or more not adjacent to each other The CH 2 group may be replaced by —O—.
　上記一般式（ＩＩ－２）中、Ｘ２２１及びＸ２２２は、それぞれ独立して、－Ｏ－、－ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＯＯ－ＣＨ２ＣＨ２－、－ＯＣＯ－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２－ＣＯＯ－、－ＣＨ２ＣＨ２－ＯＣＯ－、－ＣＯＯ－ＣＨ２－、－ＯＣＯ－ＣＨ２－、－ＣＨ２－ＣＯＯ－、－ＣＨ２－ＯＣＯ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－又は単結合を表すことが好ましく、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、又は単結合を表すことがより好ましい（ただし、Ｐ２２１－Ｓｐ２２１、Ｓｐ２２１－Ｘ２２１、Ｐ２２２－Ｓｐ２２２、及びＳｐ２２２－Ｘ２２２は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－基を含まない。）。 In the general formula (II-2), X 221 and X 222 each independently represent —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, — O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO -CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 - It preferably represents OCO—, —CH═CH—, —C≡C— or a single bond, more preferably —O—, —COO—, —OCO— or a single bond (provided that P 221 — Sp 221, Sp 221 -X 221, P 222 -Sp 222,及Sp 222 -X 222 may, -O-O -, - O -NH -, - does not contain S-S- and -O-S- group)..
　上記一般式（ＩＩ－２－ｂ）中、Ｂ１１、Ｂ２１及びＢ３１はそれぞれ独立的に、上述した置換基を有しても良い、１，４－フェニレン基、１，４－シクロヘキシレン基、２，６－ナフチレン基を表すことが好ましく、Ｚ１１及びＺ２１はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、又は単結合を表すことが好ましく、ｒ１１は０又は１を表すことが好ましい。
一般式（ＩＩ－２）の例として、下記一般式（ＩＩ－２－１）～（ＩＩ－２－４）で表される化合物を挙げることができるが、下記の一般式に限定されるわけではない。 In the above general formula (II-2-b), B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, and Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH It is preferable to represent —, —C≡C—, —C═N—, —N═C—, or a single bond, and r11 preferably represents 0 or 1.
Examples of the general formula (II-2) include compounds represented by the following general formulas (II-2-1) to (II-2-4), but are not limited to the following general formulas is not.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　上記一般式（ＩＩ－２－１）～（ＩＩ－２－４）中、Ｐ２２１、Ｓｐ２２１、Ｘ２２１、ｑ２２１、Ｘ２２２、Ｓｐ２２２、ｑ２２２、及び、Ｐ２２２は、それぞれ、上記一般式（ＩＩ－２）の定義と同じものを表し、好ましい基も一般式（ＩＩ－２）の定義と同じものを表し、
上記一般式（ＩＩ－２－１）～（ＩＩ－２－４）中、Ｂ１１１、Ｂ１１２、Ｂ１１３、Ｂ２１、Ｂ３１は、上記一般式（ＩＩ－２－ｂ）のＢ１１～Ｂ３１の定義と同じものを表し、好ましい基もＢ１１～Ｂ３１の定義と同じものを表し、それぞれ、同一であっても、異なっていても良く、
上記一般式（ＩＩ－２－１）～（ＩＩ－２－４）中、Ｚ１１１、Ｚ１１２、Ｚ１１３、Ｚ２１は、上記一般式（ＩＩ－２－ｂ）のＺ１１～Ｚ２１の定義と同じものを表し、好ましい基もＺ１１～Ｚ２１の定義と同じものを表し、それぞれ、同一であっても、異なっていても良い。 In the general formulas (II-2-1) to (II-2-4), P 221 , Sp 221 , X 221 , q 221 , X 222 , Sp 222 , q 222 , and P 222 are respectively the above general formulas. Represents the same definition as in (II-2), and a preferred group represents the same definition as in formula (II-2);
In the above general formulas (II-2-1) to (II-2-4), B111, B112, B113, B21, and B31 are the same as the definitions of B11 to B31 in the general formula (II-2-b). And preferred groups also represent the same as defined for B11 to B31, and may be the same or different,
In the general formulas (II-2-1) to (II-2-4), Z111, Z112, Z113, and Z21 represent the same definitions as Z11 to Z21 in the general formula (II-2-b). Preferred groups also represent the same definitions as Z11 to Z21, and may be the same or different.
　上記一般式（ＩＩ－２－１）～（ＩＩ－２－４）で表される化合物のうち、一般式（ＩＩ－２－２）～（ＩＩ－２－４）で表される、化合物中に３つ以上の環構造を有する化合物を用いると、得られるフィルムの配向性が良好で、かつ硬化性も良好であるため好ましく、化合物中に３つの環構造を有する一般式（ＩＩ－２－２）で表される化合物を用いることが特に好ましい。 Of the compounds represented by the general formulas (II-2-1) to (II-2-4), among the compounds represented by the general formulas (II-2-2) to (II-2-4) It is preferable to use a compound having three or more ring structures for the reason that the resulting film has good orientation and good curability, and the compound represented by the general formula (II-2- It is particularly preferable to use the compound represented by 2).
　上記一般式（ＩＩ－２－１）～（ＩＩ－２－４）で表される化合物としては、以下の一般式（ＩＩ－２－１－１）～一般式（ＩＩ－２－１－２５）で表される化合物を例示されるが、これらに限定される訳ではない。 The compounds represented by the general formulas (II-2-1) to (II-2-4) include the following general formulas (II-2-1-1) to (II-2-1-25): ) Is exemplified, but not limited thereto.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　式中、Ｒｄ及びＲｅは、それぞれ独立して水素原子又はメチル基を表し、
上記環状基は、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、炭素原子数２～８のアルケノイル基、炭素原子数２～８のアルケノイルオキシ基を有していても良い。 In the formula, R d and R e each independently represent a hydrogen atom or a methyl group,
The cyclic group includes one or more F, Cl, CF 3 , OCF 3 , CN groups, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and 1 to 8 alkanoyl groups, alkanoyloxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkenyloxy groups having 2 to 8 carbon atoms, carbon atoms It may have an alkenoyl group having 2 to 8 carbon atoms and an alkenoyloxy group having 2 to 8 carbon atoms.
　ｍ１、ｍ２、ｍ３、ｍ４はそれぞれ独立して０～８の整数を表し、ｎ１、ｎ２、ｎ３、ｎ４はそれぞれ独立して０又は１を表す。 M1, m2, m3, and m4 each independently represent an integer of 0 to 8, and n1, n2, n3, and n4 each independently represent 0 or 1.
　上記一般式（ＩＩ－２－１－１）～一般式（ＩＩ－２－１－２１）で表される化合物はさらに具体的に以下の一般式（ＩＩ－２－２－１）～一般式（ＩＩ－２－２－３５）で表される化合物を例示できるが、これらに限定される訳ではない。 The compounds represented by the general formulas (II-2-1-1) to (II-2-1-21) are more specifically represented by the following general formulas (II-2-2-1) to The compound represented by (II-2-2-35) can be exemplified, but is not limited thereto.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　２つの重合性官能基を有する重合性液晶化合物は、１種又は２種以上用いることができるが、１種～５種が好ましく、２種～５種がより好ましい。 The polymerizable liquid crystal compound having two polymerizable functional groups can be used singly or in combination of two or more, preferably 1 to 5 types, more preferably 2 to 5 types.
　上記一般式（ＩＩ－２）、上記一般式（ＩＩ－２－１）～上記一般式（ＩＩ－２－４）、上記一般式（ＩＩ－２－１－１）～一般式（ＩＩ－２－１－２１）、又は、一般式（ＩＩ－２－２－１）～一般式（ＩＩ－２－２－３５）で表される、分子内に２つの重合性官能基を有する２官能重合性液晶化合物の合計含有量は、表示素子用封止材料組成物に用いる重合性液晶化合物の合計量のうち、１０～１００質量％含有することが好ましく、１５～８５質量％含有することがより好ましく２０～８０質量％含有することが特に好ましい。塗膜の硬さを重視する場合には下限値を３０質量％以上にすることが好ましく、５０質量％以上にすることがより好ましく、フィルムの配向性を重視する場合には上限値を８５質量％以下とすることが好ましく、８０質量％以下とすることがより好ましい。
（多官能重合性液晶化合物）
　３つ以上の重合性官能基を有する多官能重合性液晶化合物としては、３つの重合性官能基を有する化合物を用いることが好ましい。前記一般式（ＩＩ）で表される化合物のうち、分子内に３つ又は４つの重合性官能基を有する多官能重合性液晶化合物として、下記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）で表される化合物を例示できる。 General Formula (II-2), General Formula (II-2-1) to General Formula (II-2-4), General Formula (II-2-1-1) to General Formula (II-2) -1-21), or bifunctional polymerization having two polymerizable functional groups in the molecule represented by general formula (II-2-2-1) to general formula (II-2-2-35) The total content of the conductive liquid crystal compound is preferably 10 to 100% by mass, more preferably 15 to 85% by mass, based on the total amount of the polymerizable liquid crystal compound used for the sealing material composition for display elements. A content of 20 to 80% by mass is particularly preferable. When importance is attached to the hardness of the coating film, the lower limit is preferably 30% by mass or more, more preferably 50% by mass or more, and when importance is attached to the orientation of the film, the upper limit is 85% by mass. % Or less, and more preferably 80% by mass or less.
(Polyfunctional polymerizable liquid crystal compound)
As the polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups, it is preferable to use a compound having three polymerizable functional groups. Of the compounds represented by the general formula (II), the following general formulas (II-3-1) to (II) are used as polyfunctional polymerizable liquid crystal compounds having three or four polymerizable functional groups in the molecule. Illustrative are compounds represented by II-3-2).
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　上記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）中、Ｐ２３１、Ｘ２３１、ｑ２３１、Ｘ２３２、ｑ２３２、Ｐ２３２、Ｐ２３３、Ｘ２３３、ｑ２３４、ｑ２３３、Ｘ２３４、ｑ２３６、ｑ２３５、Ｐ２３４、Ｘ２３５、ｑ２３８、ｑ２３７、Ｐ２３５は、それぞれ、上記一般式（ＩＩ）、一般式（ＩＩ－ａ）、一般式（ＩＩ－ｃ）中のＰ２１、Ｘ２１、ｑ２１、Ｘ２２、ｑ２２、Ｐ２２、Ｐ２３、Ｘ２３、ｑ２４、ｑ２３、Ｘ２３、ｑ２４、ｑ２３、Ｐ２３、Ｘ２３、ｑ２４、ｑ２３、Ｐ２３の定義と同じものを表し、
上記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）中、Ｓｐ２３１、Ｓｐ２３２、Ｓｐ２３３、Ｓｐ２３４及びＳｐ２３５はそれぞれ独立して、炭素原子数１～１８のアルキレン基を表し（該アルキレン基中の水素原子は、１つ以上のハロゲン原子、又はＣＮ基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）を表し、
上記一般式（ＩＩ－３－２）中、ｊ３は０又は１を表し、
上記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）中、ＭＧ３はメソゲン基を表し、当該メソゲン基としては、一般式（ＩＩ－３－ｂ） In the general formula (II-3-1) to the general formula (II-3-2), P 231 , X 231 , q231, X 232 , q232, P 232 , P 233 , X 233 , q234, q233, X 234 , Q236, q235, P 234 , X 235 , q238, q237, and P 235 are P 21 , X 21 in the general formula (II), general formula (II-a), and general formula (II-c), respectively. represent the same as the definition of q21, X 22, q22, P 22, P 23, X 23, q24, q23, X 23, q24, q23, P 23, X 23, q24, q23, P 23,
In the general formulas (II-3-1) to (II-3-2), Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 are each independently an alkylene having 1 to 18 carbon atoms. A hydrogen atom in the alkylene group may be substituted by one or more halogen atoms or a CN group, one CH 2 group present in the group or two or more non-adjacent Each independently of the CH 2 group may be replaced by —O—, —COO—, —OCO— or —OCO—O—.
In the general formula (II-3-2), j3 represents 0 or 1,
In the above general formulas (II-3-1) to (II-3-2), MG 3 represents a mesogenic group, and the mesogenic group includes the general formula (II-3-b)
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
（上記一般式（ＩＩ－３－ｂ）中、Ｂ１１、Ｂ２１及びＢ３１はそれぞれ独立的に、１，４－フェニレン基、１，４－シクロヘキシレン基、１，４－シクロヘキセニル基、テトラヒドロピラン－２，５－ジイル基、１，３－ジオキサン－２，５－ジイル基、テトラヒドロチオピラン－２，５－ジイル基、１，４－ビシクロ（２，２，２）オクチレン基、デカヒドロナフタレン－２，６－ジイル基、ピリジン－２，５－ジイル基、ピリミジン－２，５－ジイル基、ピラジン－２，５－ジイル基、チオフェン－２，５－ジイル基－、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、２，６－ナフチレン基、フェナントレン－２，７－ジイル基、９，１０－ジヒドロフェナントレン－２，７－ジイル基、１，２，３，４，４ａ，９，１０ａ－オクタヒドロフェナントレン－２，７－ジイル基、１，４－ナフチレン基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジチオフェン－２，６－ジイル基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジセレノフェン－２，６－ジイル基、［１］ベンゾチエノ［３，２－ｂ］チオフェン－２，７－ジイル基、［１］ベンゾセレノフェノ［３，２－ｂ］セレノフェン－２，７－ジイル基、又はフルオレン－２，７－ジイル基を表し、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基（当該アルキル基中の水素原子は、１つ以上のフェニル基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、及び／又は炭素原子数２～８のアルケノイル基を有していても良く、
上記一般式（ＩＩ－３－ｂ）中、Ｚ１１及びＺ２１はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－Ｃ（ＣＦ３）２－、ハロゲン原子を有してもよい炭素原子数２～１０のアルキル基又は単結合を表し、ｒ１１は０、１、２又は３を表し、Ｂ１１、及びＺ１１が複数存在する場合は、それぞれ、同一であっても、異なっていても良い。）で表されるが、Ｚ１１、Ｚ２１が単結合を表す場合、上記Ｂ１１、Ｂ２１、Ｂ３１のうち、隣接して存在する２つの環構造がそれぞれ有する置換基が結合して環状基を形成しても良く、
　上記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）中、Ｐ２３１、Ｐ２３２、Ｐ２３３、Ｐ２３４、及びＰ２３５は重合性を高める観点から、それぞれ独立して、上述の式（Ｐ－２－１）、（Ｐ－２－２）、（Ｐ－２－７）、（Ｐ－２－１２）、（Ｐ－２－１３）が好ましく、式（Ｐ－２－１）、（Ｐ－２－２）がより好ましい。 (In the general formula (II-3-b), B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran- 2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene- 2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3 4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4, 4a, 9, 0a-octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2- b: 4,5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b ] Represents a selenophene-2,7-diyl group or a fluorene-2,7-diyl group, and has at least one F, Cl, CF 3 , OCF 3 , CN group or an alkyl having 1 to 8 carbon atoms as a substituent. group (the hydrogen atom in the alkyl group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent present in this group Independently of each other, —O—, —COO—, —OCO Or may be replaced by —OCO—O—), an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or the number of carbon atoms May have an alkoxycarbonyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
In the general formula (II-3-b), Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═ CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 — , —C═N—, —N═C—, —CONH—, —NHCO—, —C (CF 3 ) 2 —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom, or a single bond , R11 represents 0, 1, 2, or 3, and when there are a plurality of B11 and Z11, they may be the same or different. In the case where Z11 and Z21 represent a single bond, the substituents of the two adjacent ring structures among B11, B21 and B31 are combined to form a cyclic group. Well,
In the general formulas (II-3-1) to (II-3-2), P 231 , P 232 , P 233 , P 234 , and P 235 are each independently from the viewpoint of improving the polymerizability, The above formulas (P-2-1), (P-2-2), (P-2-7), (P-2-12), and (P-2-13) are preferable, and the formula (P-2 -1) and (P-2-2) are more preferable.
　上記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）中、Ｓｐ２３１、Ｓｐ２３２、Ｓｐ２３３、Ｓｐ２３４及びＳｐ２３５は、保存安定性を高める観点から、それぞれ独立して、炭素原子数１～１４のアルキレン基を表すことが好ましく、当該アルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－又は－ＯＣＯ－により置き換えられていても良い。また、Ｓｐ２３１、Ｓｐ２３２、Ｓｐ２３３、Ｓｐ２３４及びＳｐ２３５は、それぞれ独立して、炭素原子数１～１２のアルキレン基を表すことがより好ましく、当該アルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基は－Ｏ－により置き換えられていても良い。 In the above general formulas (II-3-1) to (II-3-2), Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 are each independently from the viewpoint of enhancing storage stability. , preferably represents an alkylene group having 1 to 14 carbon atoms, and each of the two or more CH 2 groups not one CH 2 group or adjacent existing in the alkylene group independently of one another, -O It may be replaced by-, -COO- or -OCO-. Further, Sp 231 , Sp 232 , Sp 233 , Sp 234 and Sp 235 each independently preferably represent an alkylene group having 1 to 12 carbon atoms, and one CH 2 present in the alkylene group. A group or two or more non-adjacent CH 2 groups may be replaced by —O—.
　上記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）中、Ｘ２３１、Ｘ２３２、Ｘ２３３、Ｘ２３４及びＸ２３５は、それぞれ独立して、－Ｏ－、－ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＯＯ－ＣＨ２ＣＨ２－、－ＯＣＯ－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２－ＣＯＯ－、－ＣＨ２ＣＨ２－ＯＣＯ－、－ＣＯＯ－ＣＨ２－、－ＯＣＯ－ＣＨ２－、－ＣＨ２－ＣＯＯ－、－ＣＨ２－ＯＣＯ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－又は単結合を表すことが好ましく、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、又は単結合を表すことがより好ましい（ただし、Ｐ２３１－Ｓｐ２３１、Ｓｐ２３１－Ｘ２３１、Ｐ２３２－Ｓｐ２３２、Ｓｐ２３２－Ｘ２３２、Ｐ２３３－Ｓｐ２３３、Ｓｐ２３３－Ｘ２３３、Ｐ２３４－Ｓｐ２３４、Ｓｐ２３４－Ｘ２３４、Ｐ２３５－Ｓｐ２３５、及びＳｐ２３５－Ｘ２３５は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－基を含まない。）。　上記一般式（ＩＩ－３－ｂ）中、Ｂ１１、Ｂ２１及びＢ３１はそれぞれ独立的に、上述した置換基を有しても良い、１，４－フェニレン基、１，４－シクロヘキシレン基、２，６－ナフチレン基を表すことが好ましく、Ｚ１１及びＺ２１はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、又は単結合を表すことが好ましく、ｒ１１は０又は１を表すことが好ましい。 In the general formulas (II-3-1) to (II-3-2), X 231 , X 232 , X 233 , X 234 and X 235 are each independently —O—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO -, - CH = CH -, - C≡C- or preferably a single bond, -O -, - COO -, - OCO-, or more preferably a single bond (provided that, P 231 -S 231, Sp 231 -X 231, P 232 -Sp 232, Sp 232 -X 232, P 233 -Sp 233, Sp 233 -X 233, P 234 -Sp 234, Sp 234 -X 234, P 235 -Sp 235, And Sp 235 —X 235 does not include —O—O—, —O—NH—, —S—S—, and —O—S— groups. In the above general formula (II-3-b), B11, B21 and B31 each independently may have the above-described substituents such as 1,4-phenylene group, 1,4-cyclohexylene group, 2 , 6-naphthylene group, and Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH It is preferable to represent —, —C≡C—, —C═N—, —N═C—, or a single bond, and r11 preferably represents 0 or 1.
　上記一般式（ＩＩ－３－１）中、ＭＧ３において、－（Ｘ２３３）ｑ２３４－（Ｓｐ２３３）ｑ２３３－Ｐ２３３基で表される重合性基を有する基は、ＭＧ３中の存在するＢ１１、Ｂ２１及び/又はＢ３１の置換基として置換される。 In the general formula (II-3-1), in MG 3, - (X 233) q234 - group having represented by polymerizable groups (Sp 233) q233 -P 233 groups are present in the MG 3 Substitution as a substituent of B11, B21 and / or B31.
　上記一般式（ＩＩ－３－２）中、Ｓｐ基において、－（Ｘ２３４）ｑ２３６－（Ｓｐ２３４）ｑ２３５－Ｐ２３４基、及び、存在する－（Ｘ２３４）ｑ２３６－（Ｓｐ２３４）ｑ２３５－Ｐ２３４基で表される重合性基を有する基は、Ｓｐ基中に存在するアルキレン基中の水素原子に置換される。 In the general formula (II-3-2), in the Sp group,-(X 234 ) q236- (Sp 234 ) q235 -P 234 group and the existing-(X 234 ) q236- (Sp 234 ) q235- The group having a polymerizable group represented by the P 234 group is substituted with a hydrogen atom in the alkylene group present in the Sp group.
　上記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）で表される化合物の例として、下記一般式（ＩＩ－３－３－１）～（ＩＩ－３－３－１０）で表される化合物を挙げることができるが、下記の一般式に限定されるわけではない。 Examples of the compounds represented by the above general formula (II-3-1) to general formula (II-3-2) include the following general formulas (II-3-3-1) to (II-3-3-1-10) ), But is not limited to the following general formula.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　上記一般式（ＩＩ－３－３－１）～（ＩＩ－３－３－１０）において、Ｐ２３１～Ｐ２３５、Ｓｐ２３１～Ｓｐ２３５、Ｘ２３１～Ｘ２３５、ｑ２３１～ｑ２３８、ＭＧ３は、それぞれ、上記一般式（ＩＩ－３－１）～一般式（ＩＩ－３－２）の定義と同じものを表す。 In the above general formulas (II-3-3-1) to (II-3-3-10), P 231 to P 235 , Sp 231 to Sp 235 , X 231 to X 235 , q231 to q238, and MG 3 are Each represents the same definition as in general formula (II-3-1) to general formula (II-3-2).
　上記一般式（ＩＩ－３－３－１）～（ＩＩ－３－３－１０）において、Ｂ１１１とＢ１１２とＢ１１３、Ｂ２１、Ｂ３１は、それぞれ、上記一般式（ＩＩ－３－ｂ）のＢ１１、Ｂ２１、Ｂ３１の定義と同じものを表し、好ましい基もＢ１１～Ｂ３１の定義と同じものを表し、それぞれ、同一であっても、異なっていても良い。 In the above general formulas (II-3-3-1) to (II-3-3-10), B111, B112, B113, B21, and B31 are respectively B11 of the general formula (II-3-b), It represents the same as the definition of B21 and B31, and preferred groups also represent the same as the definitions of B11 to B31, and may be the same or different.
　上記一般式（ＩＩ－３－３－１）～（ＩＩ－３－３－１０）において、Ｚ１１１とＺ１１２とＺ１１３、Ｚ２１は、それぞれ、上記一般式（ＩＩ－３－ｂ）のＺ１１、Ｚ２１の定義と同じものを表し、好ましい基もＺ１１～Ｚ２１の定義と同じものを表し、それぞれ、同一であっても、異なっていても良い。 In the general formulas (II-3-3-1) to (II-3-3-10), Z111, Z112, Z113, and Z21 are the same as Z11 and Z21 in the general formula (II-3-b), respectively. It represents the same as the definition, and preferred groups also represent the same as the definitions of Z11 to Z21, and may be the same or different.
　上記一般式（ＩＩ－３－３－１）～（ＩＩ－３－３－１０）で表される化合物としては、以下の式（ＩＩ－３－３－３－１）～式（ＩＩ－３－３－３－６）で表される化合物を例示されるが、これらに限定される訳ではない。 Examples of the compounds represented by the general formulas (II-3-3-1) to (II-3-3-10) include the following formulas (II-3-3-3-1) to (II-3): Although the compound represented by -3-3-3) is exemplified, the compound is not limited thereto.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　式中、Ｒｆ、Ｒｇ及びＲｈは、それぞれ独立して水素原子又はメチル基を表し、Ｒｉ、Ｒｊ及びＲｋはそれぞれ独立して水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、シアノ基を表し、これらの基が炭素数１～６のアルキル基、あるいは炭素数１～６のアルコキシ基の場合、全部が未置換であるか、あるいは１つまたは２つ以上のハロゲン原子により置換されていてもよく、上記環状基は、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、炭素原子数２～８のアルケノイル基、炭素原子数２～８のアルケノイルオキシ基を有していても良い。
ｍ４～ｍ９はそれぞれ独立して０～１８の整数を表し、ｎ４～ｎ９はそれぞれ独立して０又は１を表す。 In the formula, R f , R g, and R h each independently represent a hydrogen atom or a methyl group, and R i , R j, and R k are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 6 Represents an alkyl group, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, and when these groups are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, they are all unsubstituted, Alternatively, it may be substituted with one or two or more halogen atoms, and the cyclic group has one or more F, Cl, CF 3 , OCF 3 , CN groups, 1 to 8 carbon atoms as a substituent. An alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and 2 to 2 carbon atoms 8 alkenyl groups, carbon atoms Alkenyloxy group having 2-8, alkenoyl group having 2 to 8 carbon atoms, which may have a alkenoyloxy group having a carbon number of 2-8.
m4 to m9 each independently represents an integer of 0 to 18, and n4 to n9 each independently represents 0 or 1.
　３個以上の重合性官能基を有する多官能重合性液晶化合物は、１種又は２種以上用いることができる。 The polyfunctional polymerizable liquid crystal compound having three or more polymerizable functional groups can be used alone or in combination of two or more.
　分子内に３個以上の重合性官能基を有する多官能重合性液晶化合物の合計含有量は、表示素子用封止材料組成物に用いる重合性液晶化合物の合計量のうち、０～８０質量％含有することが好ましく、０～６０質量％含有することがより好ましく、０～４０質量％含有することが特に好ましい。得られるフィルムの剛直性を重視する場合には、下限値を１０質量％以上にすることが好ましく、２０質量％以上にすることがより好ましく、３０質量％以上にすることが特に好ましく、一方、得られるフィルムの低硬化収縮性を重視する場合には上限値を５０質量％以下とすることが好ましく、３５質量％以下とすることがより好ましく、２０質量％以下とすることが特に好ましい。
（重合性液晶化合物の複数種併用）
　本発明の表示素子用封止材料組成物には、上記重合性液晶化合物を複数種混合して用いることが好ましい。上記少なくとも１種以上の単官能重合性液晶化合物と、少なくとも１種以上の２官能重合性液晶化合物及び／又は多官能重合性液晶化合物を併用して用いると得られるフィルムの硬化性が向上するため好ましく、少なくとも１種以上の単官能重合性液晶化合物と、少なくとも１種以上の２官能重合性液晶化合物を併用することがより好ましい。中でも、本発明の表示素子用封止材料組成物を用いてフィルムとした時に、より硬化性を向上させたい場合、２官能重合性液晶化合物として、化合物中に３つ以上の環構造を有する上記（ＩＩ－２－２）～（ＩＩ－２－４）から選択される化合物を用いて重合性液晶化合物の混合物とすることが好ましい。 The total content of the polyfunctional polymerizable liquid crystal compound having 3 or more polymerizable functional groups in the molecule is 0 to 80% by mass of the total amount of the polymerizable liquid crystal compound used in the sealing material composition for display elements. The content is preferably 0 to 60% by mass, more preferably 0 to 40% by mass. When importance is attached to the rigidity of the obtained film, the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more, When emphasizing the low curing shrinkage of the resulting film, the upper limit is preferably 50% by mass or less, more preferably 35% by mass or less, and particularly preferably 20% by mass or less.
(Combination of multiple types of polymerizable liquid crystal compounds)
In the sealing material composition for display elements of the present invention, it is preferable to use a mixture of a plurality of the polymerizable liquid crystal compounds. When at least one monofunctional polymerizable liquid crystal compound and at least one bifunctional polymerizable liquid crystal compound and / or polyfunctional polymerizable liquid crystal compound are used in combination, the curability of the resulting film is improved. It is preferable to use at least one monofunctional polymerizable liquid crystal compound and at least one bifunctional polymerizable liquid crystal compound in combination. Among these, when it is desired to further improve curability when the sealing material composition for display elements of the present invention is used as a film, the compound has three or more ring structures as a bifunctional polymerizable liquid crystal compound. A compound selected from (II-2-2) to (II-2-4) is preferably used as a mixture of polymerizable liquid crystal compounds.
　上記単官能重合性液晶化合物と２官能重合性液晶化合物との合計量は、表示素子用封止材料組成物に用いる重合性液晶化合物の合計量のうち、７０質量％～１００質量％とすることが好ましく、８０質量％～１００質量％とすることが特に好ましい。
（その他の液晶化合物）
　また、本発明の表示素子用封止材料組成物には、重合性基を有さないメソゲン基を含有する化合物を添加しても良く、通常の液晶デバイス、例えばＳＴＮ（スーパー・ツイステッド・ネマチック）液晶や、ＴＮ（ツイステッド・ネマチック）液晶、ＴＦＴ（薄膜トランジスター）液晶等に使用される化合物が挙げられる。 The total amount of the monofunctional polymerizable liquid crystal compound and the bifunctional polymerizable liquid crystal compound is 70% by mass to 100% by mass of the total amount of the polymerizable liquid crystal compound used for the sealing material composition for display elements. It is particularly preferable that the content be 80% by mass to 100% by mass.
(Other liquid crystal compounds)
In addition, a compound containing a mesogenic group having no polymerizable group may be added to the sealing material composition for a display element of the present invention, and an ordinary liquid crystal device such as STN (Super Twisted Nematic) is used. Examples thereof include compounds used for liquid crystals, TN (twisted nematic) liquid crystals, TFT (thin film transistor) liquid crystals, and the like.
　重合性官能基を有さないメソゲン基を含有する化合物は、具体的には以下の一般式（５）で表される化合物が好ましい。 Specifically, the compound containing a mesogenic group having no polymerizable functional group is preferably a compound represented by the following general formula (5).
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　ＭＧ３で表されるメソゲン基又はメソゲン性支持基は、一般式（５－ｂ） The mesogenic group or mesogenic supporting group represented by MG3 has the general formula (5-b)
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
（式中、Ａ１ｄ、Ａ２ｄ及びＡ３ｄはそれぞれ独立的に、１，４－フェニレン基、１，４－シクロヘキシレン基、１，４－シクロヘキセニル基、テトラヒドロピラン－２，５－ジイル基、１，３－ジオキサン－２，５－ジイル基、テトラヒドロチオピラン－２，５－ジイル基、１，４－ビシクロ（２，２，２）オクチレン基、デカヒドロナフタレン－２，６－ジイル基、ピリジン－２，５－ジイル基、ピリミジン－２，５－ジイル基、ピラジン－２，５－ジイル基、チオフェン－２，５－ジイル基－、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、２，６－ナフチレン基、フェナントレン－２，７－ジイル基、９，１０－ジヒドロフェナントレン－２，７－ジイル基、１，２，３，４，４ａ，９，１０ａ－オクタヒドロフェナントレン－２，７－ジイル基、１，４－ナフチレン基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジチオフェン－２，６－ジイル基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジセレノフェン－２，６－ジイル基、［１］ベンゾチエノ［３，２－ｂ］チオフェン－２，７－ジイル基、［１］ベンゾセレノフェノ［３，２－ｂ］セレノフェン－２，７－ジイル基、又はフルオレン－２，７－ジイル基を表し、置換基として１個以上のＦ、Ｃｌ、ＣＦ３、ＯＣＦ３、ＣＮ基、炭素原子数１～８のアルキル基、アルコキシ基、アルカノイル基、アルカノイルオキシ基、炭素原子数２～８のアルケニル基、アルケニルオキシ基、アルケノイル基、アルケノイルオキシ基を有していても良く、
Ｚ０ｄ、Ｚ１ｄ、Ｚ２ｄ及びＺ３ｄはそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ２　ＣＨ２－、－ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ２ＣＨ２ＣＯＯ－、－ＣＨ２ＣＨ２ＯＣＯ－、－ＣＯＯＣＨ２ＣＨ２－、－ＯＣＯＣＨ２ＣＨ２－、－ＣＯＮＨ－、－ＮＨＣＯ－、炭素数２～１０のハロゲン原子を有してもよいアルキレン基又は単結合を表し、
ｎｅは０、１又は２を表し、
Ｒ５１及びＲ５２はそれぞれ独立して水素原子、ハロゲン原子、シアノ基又は炭素原子数１～１８のアルキル基を表すが、該アルキル基は１つ以上のハロゲン原子又はＣＮにより置換されていても良く、この基中に存在する１つのＣＨ２基又は隣接していない２つ以上のＣＨ２基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、－Ｏ－、－Ｓ－、－ＮＨ－、－Ｎ（ＣＨ３）－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＯ－、－ＳＣＯ－、－ＣＯＳ－又は－Ｃ≡Ｃ－により置き換えられていても良い。）で表される化合物が挙げられる。 Wherein A1 d , A2 d and A3 d are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a- Octahydrof Enanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group, or fluorene-2,7-diyl group, and one or more F, Cl, CF 3 , OCF 3 , CN groups, alkyl groups having 1 to 8 carbon atoms, alkoxy groups as substituents , An alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group, an alkenoyloxy group,
Z0 d , Z1 d , Z2 d and Z3 d are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH—, — C≡C -, - CH = CHCOO - , - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - OCOCH 2 CH 2 -, - CONH- , -NHCO-, an alkylene group which may have a halogen atom having 2 to 10 carbon atoms or a single bond,
n e represents 0, 1 or 2,
R 51 and R 52 each independently represent a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN. may, independently each two or more CH 2 groups not one CH 2 group or adjacent present in this group to each other, in a manner that oxygen atoms are not directly bonded to each other, -O -, - S May be replaced by —, —NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—. . ).
　具体的には、以下に示されるが、これらに限定される訳ではない。 Specific examples are shown below, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　Ｒａ及びＲｂはそれぞれ独立して水素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、炭素数１～６のアルケニル基、シアノ基を表し、これらの基が炭素数１～６のアルキル基、あるいは炭素数１～６のアルコキシ基の場合、全部が未置換であるか、あるいは１つまたは２つ以上のハロゲン原子により置換されていてもよい。 Ra and Rb each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or a cyano group. In the case of an alkyl group of ˜6 or an alkoxy group of 1 to 6 carbon atoms, all may be unsubstituted or substituted by one or more halogen atoms.
　メソゲン基を有する化合物の総含有量は、表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して０質量部以上２０質量部以下であることが好ましく、用いる場合は、１質量部以上であることが好ましく、２質量部以上であることが好ましく、５質量部以上であることが好ましく、また、１５質量部以下であることが好ましく、１０質量部以下であることが好ましい。
（その他の成分）
（キラル化合物）
　本発明における表示素子用封止材料組成物には、上記一般式（ＩＩ）に示す重合性化合物以外の液晶性を示してもよく、非液晶性であってもよい、重合性キラル化合物を含有することもできる。 The total content of the compound having a mesogen group is preferably 0 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used for the sealing material composition for display elements. In this case, it is preferably 1 part by mass or more, preferably 2 parts by mass or more, preferably 5 parts by mass or more, and preferably 15 parts by mass or less, and 10 parts by mass or less. Preferably there is.
(Other ingredients)
(Chiral compound)
The sealing material composition for display elements in the present invention contains a polymerizable chiral compound that may exhibit liquid crystallinity other than the polymerizable compound represented by the general formula (II) or may be non-liquid crystalline. You can also
　本発明に使用する重合性キラル化合物としては、重合性官能基を１つ以上有することが好ましい。このような化合物としては、例えば、特開平１１－１９３２８７号公報、特開２００１－１５８７８８号公報、特表２００６－５２６６９号公報、特開２００７－２６９６３９号公報、特開２００７－２６９６４０号公報、２００９－８４１７８号公報等に記載されているような、イソソルビド、イソマンニット、グルコシド等のキラルな糖類を含み、かつ、１，４－フェニレン基１，４－シクロヘキレン基等の剛直な部位と、ビニル基、アクリロイル基、（メタ）アクリロイル基、また、マレイミド基といった重合性官能基を有する重合性キラル化合物、特開平８－２３９６６６号公報に記載されているような、テルペノイド誘導体からなる重合性キラル化合物、ＮＡＴＵＲＥ　ＶＯＬ３５　４６７～４６９ページ（１９９５年１１月３０日発行）、ＮＡＴＵＲＥ　ＶＯＬ３９２　４７６～４７９ページ（１９９８年４月２日発行）等に記載されているような、メソゲン基とキラル部位を有するスペーサーからなる重合性キラル化合物、あるいは特表２００４－５０４２８５号公報、特開２００７－２４８９４５号公報に記載されているような、ビナフチル基を含む重合性キラル化合物が挙げられる。中でも、らせんねじれ力（ＨＴＰ）の大きなキラル化合物が、本発明の表示素子用封止材料組成物に好ましい。 The polymerizable chiral compound used in the present invention preferably has one or more polymerizable functional groups. Examples of such compounds include JP-A-11-193287, JP-A-2001-158788, JP-T 2006-52669, JP-A-2007-269639, JP-A-2007-269640, 2009. -84178, which contains chiral saccharides such as isosorbide, isomannite, glucoside, etc., and a rigid group such as 1,4-phenylene group and 1,4-cyclohexylene group, and a vinyl group A polymerizable chiral compound having a polymerizable functional group such as an acryloyl group, a (meth) acryloyl group, or a maleimide group, a polymerizable chiral compound comprising a terpenoid derivative as described in JP-A-8-239666, NATURE VOL35, pages 467-469 (November 30, 1995) Issue), NATURE VOL392, pages 476-479 (issued on April 2, 1998), or the like, or a polymerizable chiral compound comprising a mesogenic group and a spacer having a chiral moiety, or JP-T-2004-504285. And a polymerizable chiral compound containing a binaphthyl group as described in JP-A-2007-248945. Among these, a chiral compound having a large helical twisting power (HTP) is preferable for the sealing material composition for display elements of the present invention.
　重合性キラル化合物の配合量は、化合物の螺旋誘起力によって適宜調整することが必要であるが、重合性液晶組成物の内、０～２５質量％含有することが好ましく、０～２０質量％含有することがより好ましく、０～１５質量％含有することが特に好ましい。 The compounding amount of the polymerizable chiral compound needs to be appropriately adjusted depending on the helical induction force of the compound, but it is preferably 0 to 25% by mass, preferably 0 to 20% by mass in the polymerizable liquid crystal composition. More preferably, the content is particularly preferably 0 to 15% by mass.
　重合性キラル化合物の一般式の一例として、一般式（３－１）～（３－４）を挙げることができるが、下記の一般式に限定されるわけではない。 Examples of the general formula of the polymerizable chiral compound include general formulas (3-1) to (3-4), but are not limited to the following general formula.
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　式中、Ｓｐ３ａ、及び、Ｓｐ３ｂはそれぞれ独立して炭素原子数０～１８のアルキレン基を表し、該アルキレン基は１つ以上のハロゲン原子、ＣＮ基、又は重合性官能基を有する炭素原子数１～８のアルキル基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、－Ｏ－、－Ｓ－、－ＮＨ－、－Ｎ（ＣＨ３）－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＯ－、－ＳＣＯ－、－ＣＯＳ－又は－Ｃ≡Ｃ－により置き換えられていても良く、
　Ａ１、Ａ２、Ａ３、Ａ４、及びＡ５はそれぞれ独立して、１，４－フェニレン基、１，４－シクロヘキシレン基、１，４－シクロヘキセニル基、テトラヒドロピラン－２，５－ジイル基、１，３－ジオキサン－２，５－ジイル基、テトラヒドロチオピラン－２，５－ジイル基、１，４－ビシクロ（２，２，２）オクチレン基、デカヒドロナフタレン－２，６－ジイル基、ピリジン－２，５－ジイル基、ピリミジン－２，５－ジイル基、ピラジン－２，５－ジイル基、チオフェン－２，５－ジイル基－、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、２，６－ナフチレン基、フェナントレン－２，７－ジイル基、９，１０－ジヒドロフェナントレン－２，７－ジイル基、１，２，３，４，４ａ，９，１０ａ－オクタヒドロフェナントレン－２，７－ジイル基、１，４－ナフチレン基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジチオフェン－２，６－ジイル基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジセレノフェン－２，６－ジイル基、［１］ベンゾチエノ［３，２－ｂ］チオフェン－２，７－ジイル基、［１］ベンゾセレノフェノ［３，２－ｂ］セレノフェン－２，７－ジイル基、又はフルオレン－２，７－ジイル基を表し、n、ｌ及びｋはそれぞれ独立して、０又は１を表し、０≦ｎ＋ｌ＋ｋ≦３となり、
　Ｚ０、Ｚ１、Ｚ２、Ｚ３、Ｚ４、Ｚ５、及び、Ｚ６はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、－ＣＯＮＨ－、－ＮＨＣＯ－、炭素数２～１０のハロゲン原子を有してもよいアルキル基又は単結合を表し、
ｎ５、及び、ｍ５はそれぞれ独立して０又は１を表し、
Ｒ３ａ及びＲ３ｂは、水素原子、ハロゲン原子、シアノ基又は炭素原子数１～１８のアルキル基を表すが、該アルキル基は１つ以上のハロゲン原子又はＣＮにより置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、－Ｏ－、－Ｓ－、－ＮＨ－、－Ｎ（ＣＨ３）－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＯ－、－ＳＣＯ－、－ＣＯＳ－又は－Ｃ≡Ｃ－により置き換えられていても良く、
あるいはＲ３ａ及びＲ３ｂは一般式（３－ａ） In the formula, Sp 3a and Sp 3b each independently represent an alkylene group having 0 to 18 carbon atoms, and the alkylene group is a carbon atom having one or more halogen atoms, a CN group, or a polymerizable functional group. may be substituted by an alkyl group having 1 to 8, two or more of CH 2 groups, independently of one another each of the present in the radical is not one CH 2 group or adjacent, each other oxygen atom -O-, -S-, -NH-, -N (CH 3 )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- Or it may be replaced by -C≡C-
A1, A2, A3, A4 and A5 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, , 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine -2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6 -Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydro Fe Trento-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group or fluorene-2,7-diyl group, n, l and k each independently represent 0 or 1, and 0 ≦ n + 1 + k ≦ 3,
Z0, Z1, Z2, Z3, Z4, Z5, and Z6 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═ CH—, —C≡C—, —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 — , -CONH-, -NHCO-, an alkyl group which may have a halogen atom having 2 to 10 carbon atoms or a single bond;
n5 and m5 each independently represent 0 or 1,
R 3a and R 3b represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN. two or more CH 2 groups not one CH 2 group or adjacent present in the radical are each, independently of one another, in the form of oxygen atoms are not directly bonded to each other, -O -, - S -, - May be replaced by NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—,
Alternatively, R 3a and R 3b are represented by the general formula (3-a)
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
（式中、Ｐ３ａは重合性官能基を表し、Ｓｐ３ａはＳｐ１と同じ意味を表す。）
　Ｐ３ａは、下記の式（Ｐ－１）から式（Ｐ－２０）で表される重合性基から選ばれる置換基を表すのが好ましい。 (In the formula, P 3a represents a polymerizable functional group, and Sp 3a represents the same meaning as Sp 1 ).
P 3a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　これらの重合性官能基のうち、重合性を高める観点から、式（Ｐ－１）又は式（Ｐ－２）、（Ｐ－７）、（Ｐ－１２）、（Ｐ－１３）が好ましく、式（Ｐ－１）、（Ｐ－７）、（Ｐ－１２）がより好ましい。 Of these polymerizable functional groups, the formula (P-1) or the formulas (P-2), (P-7), (P-12), and (P-13) are preferable from the viewpoint of increasing the polymerizability. Formulas (P-1), (P-7), and (P-12) are more preferable.
　重合性キラル化合物の具体的例としては、下記一般式（３－５）～（３－２６）で表される化合物を挙げることができるが、下記の化合物に限定されるものではない。 Specific examples of the polymerizable chiral compound include compounds represented by the following general formulas (3-5) to (3-26), but are not limited to the following compounds.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
　上記一般式（３－５）～（３－２６）中、ｍ、ｎ、ｋ、ｌはそれぞれ独立して１～１８の整数を表し、Ｒ１～Ｒ４はそれぞれ独立して水素原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、カルボキシ基、シアノ基を示す。これらの基が炭素数１～６のアルキル基、あるいは炭素数１～６のアルコキシ基の場合、全部が未置換であるか、あるいは１つまたは２つ以上のハロゲン原子により置換されていてもよい。
（重合性ディスコチック化合物）
　本発明の表示素子用封止材料組成物において、重合性液晶化合物として液晶性を示す重合性ディスコチック液晶化合物を用いることもできる。また、本発明の表示素子用封止材料組成物には、非液晶性の重合性ディスコチック化合物を含有することもできる。 In the above general formulas (3-5) to (3-26), m, n, k, and l each independently represent an integer of 1 to 18, and R 1 to R 4 each independently represents a hydrogen atom, carbon An alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group, and a cyano group; When these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, all of them may be unsubstituted or substituted by one or more halogen atoms. .
(Polymerizable discotic compound)
In the sealing material composition for a display element of the present invention, a polymerizable discotic liquid crystal compound exhibiting liquid crystallinity can also be used as the polymerizable liquid crystal compound. Moreover, the sealing material composition for display elements of this invention can also contain a non-liquid crystalline polymerizable discotic compound.
　本発明に使用する重合性ディスコチック化合物としては、重合性官能基を１つ以上有することが好ましい。このような化合物としては、例えば、特開平７－２８１０２８号公報、特開平７－２８７１２０号公報、特開平７－３３３４３１号公報、特開平８－２７２８４号公報に記載されているような重合性化合物が挙げられる。 The polymerizable discotic compound used in the present invention preferably has one or more polymerizable functional groups. Examples of such compounds include polymerizable compounds described in, for example, JP-A-7-281028, JP-A-7-287120, JP-A-7-333431, and JP-A-8-27284. Is mentioned.
　前記重合性液晶化合物である液晶性を示す重合性ディスコチック液晶化合物としては、以下の一般式（ＩＩＩ）で表される化合物が挙げられる。 Examples of the polymerizable discotic liquid crystal compound exhibiting liquid crystallinity as the polymerizable liquid crystal compound include compounds represented by the following general formula (III).
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
（式中、Ｒ７はそれぞれ独立して一般式（ＩＩＩ－ａ）で表される置換基を表す。 (In the formula, each R 7 independently represents a substituent represented by the general formula (III-a).
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
（式中、Ｒ９およびＲ１０はそれぞれ独立的に水素原子、ハロゲン原子又はメチル基を表し、Ｒ８は炭素原子数１～２０のアルコキシ基を表すが、該アルコキシ基中の水素原子は一般式（ＩＩＩ－ｂ）、一般式（ＩＩＩ－ｃ）、又は一般式（ＩＩＩ－ｄ）で表される置換基によって置換されていても良く、一般式（ＩＩＩ）中に存在するＲ８の少なくとも１つは、一般式（ＩＩＩ－ｂ）、一般式（ＩＩＩ－ｃ）、又は一般式（ＩＩＩ－ｄ）で表される置換基によって置換されている。） (Wherein R 9 and R 10 each independently represent a hydrogen atom, a halogen atom or a methyl group, and R 8 represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group is generally May be substituted by a substituent represented by the formula (III-b), the general formula (III-c), or the general formula (III-d), and at least R 8 present in the general formula (III) One is substituted by a substituent represented by general formula (III-b), general formula (III-c), or general formula (III-d).)
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
（式中、Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４、Ｒ８５、Ｒ８６、Ｒ８７、Ｒ８８及びＲ８９はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１～５のアルキル基を表し、ｎ１は０又は１を表す。））
　前記一般式（ＩＩＩ）中に存在するＲ８の少なくとも１つは、一般式（ＩＩＩ－ｂ）、一般式（ＩＩＩ－ｃ）、又は一般式（ＩＩＩ－ｄ）で表される置換基によって置換されているが、前記一般式（ＩＩＩ）中に存在するすべてのＲ８は、それぞれ独立して一般式（ＩＩＩ－ｂ）、一般式（ＩＩＩ－ｃ）、又は一般式（ＩＩＩ－ｄ）で表される置換基によって置換されていることが好ましい。 (Wherein R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 and R 89 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. N1 represents 0 or 1))
At least one of R 8 present in the general formula (III) is substituted with a substituent represented by the general formula (III-b), the general formula (III-c), or the general formula (III-d). However, all R 8 present in the general formula (III) is independently represented by the general formula (III-b), the general formula (III-c), or the general formula (III-d). It is preferably substituted by the substituent represented.
　また、前記一般式（ＩＩＩ－ａ）で表される置換基は、具体的には一般式(ＩＩＩ－e)で表される置換基が好ましい。 The substituent represented by the general formula (III-a) is specifically preferably a substituent represented by the general formula (III-e).
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
（式中n２は１～１８の整数を表す。）
　前記一般式（ＩＩＩ）で表される化合物として、下記一般式（ＩＩＩ－１）、一般式（ＩＩＩ－２）で表される化合物を好適な化合物として挙げられる。 (Wherein n2 represents an integer of 1 to 18)
Preferred examples of the compound represented by the general formula (III) include compounds represented by the following general formula (III-1) and general formula (III-2).
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
（一般式（ＩＩＩ－１）、一般式（ＩＩＩ－２）中、ｎは１～１８の整数を表す。）
　重合性液晶化合物として液晶性を示す重合性ディスコチック液晶化合物は、１種又は２種以上用いることができる。 (In general formula (III-1) and general formula (III-2), n represents an integer of 1 to 18)
As the polymerizable liquid crystal compound, one or more polymerizable discotic liquid crystal compounds exhibiting liquid crystallinity can be used.
　重合性液晶化合物として重合性ディスコチック液晶化合物のみを用いることもできるし、重合性棒状液晶化合物と重合性ディスコチック液晶化合物を併用することもできる。 As the polymerizable liquid crystal compound, only a polymerizable discotic liquid crystal compound can be used, or a polymerizable rod-like liquid crystal compound and a polymerizable discotic liquid crystal compound can be used in combination.
　重合性液晶化合物として重合性棒状液晶化合物と重合性ディスコチック液晶化合物を併用する場合、液晶性を示す重合性ディスコチック液晶化合物の合計含有量は、表示素子用封止材料組成物に用いる重合性液晶化合物の合計量のうち、５～９５質量％含有することが好ましく、１０～９０質量％含有することがより好ましく、２０～８０質量％含有することが特に好ましい。 When a polymerizable rod-like liquid crystal compound and a polymerizable discotic liquid crystal compound are used in combination as the polymerizable liquid crystal compound, the total content of the polymerizable discotic liquid crystal compound exhibiting liquid crystallinity is the polymerizability used in the sealing material composition for display elements. The total amount of the liquid crystal compound is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and particularly preferably 20 to 80% by mass.
　その他の重合性ディスコチック化合物の一般式の一例として、一般式（４－１）～（４－３）を挙げることができるが、下記の一般式に限定されるわけではない。 Examples of general formulas of other polymerizable discotic compounds include general formulas (4-1) to (4-3), but are not limited to the following general formulas.
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
　式中、Ｓｐ４は炭素原子数０～１８のアルキレン基を表し、該アルキレン基は１つ以上のハロゲン原子、ＣＮ基、又は重合性官能基を有する炭素原子数１～８のアルキル基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、－Ｏ－、－Ｓ－、－ＮＨ－、－Ｎ（ＣＨ３）－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＯ－、－ＳＣＯ－、－ＣＯＳ－又は－Ｃ≡Ｃ－により置き換えられていても良く、
　Ｚ４ａは、－ＣＯ－、－ＣＨ2 ＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨＣＯＯ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＣＨ2ＣＨ2－、炭素数２～１０のハロゲン原子を有してもよいアルキル基又は単結合を表し、
　Ｒ４は、水素原子、ハロゲン原子、シアノ基又は炭素原子数１～１８のアルキル基を表すが、該アルキル基は１つ以上のハロゲン原子又はＣＮにより置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、－Ｏ－、－Ｓ－、－ＮＨ－、－Ｎ（ＣＨ３）－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＯ－、－ＳＣＯ－、－ＣＯＳ－又は－Ｃ≡Ｃ－により置き換えられていても良く、
あるいはＲ４は一般式（４－ａ） In the formula, Sp 4 represents an alkylene group having 0 to 18 carbon atoms, and the alkylene group is substituted with one or more halogen atoms, CN group, or an alkyl group having 1 to 8 carbon atoms having a polymerizable functional group. may be, independently each two or more CH 2 groups not one CH 2 group or adjacent present in this group to each other, in a manner that oxygen atoms are not directly bonded to each other, -O Replaced by —, —S—, —NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—. You may,
Z 4a represents —CO—, —CH 2 CH 2 —, —CH 2 O—, —CH═CH—, —CH═CHCOO—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, — COCH 2 CH 2 — represents an alkyl group which may have a halogen atom having 2 to 10 carbon atoms or a single bond,
R 4 represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having 1 to 18 carbon atoms, and the alkyl group may be substituted with one or more halogen atoms or CN. One CH 2 group present or two or more non-adjacent CH 2 groups are each independently of each other in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, May be replaced by —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS— or —C≡C—,
Or R 4 represents the general formula (4-a)
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
（式中、Ｐ４ａは重合性官能基を表し、Ｓｐ３ａはＳｐ１と同じ意味を表す。）
　Ｐ４ａは、下記の式（Ｐ－１）から式（Ｐ－２０）で表される重合性基から選ばれる置換基を表すのが好ましい。 (In the formula, P 4a represents a polymerizable functional group, and Sp 3a represents the same meaning as Sp 1 ).
P 4a preferably represents a substituent selected from the polymerizable groups represented by the following formulas (P-1) to (P-20).
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
　これらの重合性官能基のうち、重合性を高める観点から、式（Ｐ－１）又は式（Ｐ－２）、（Ｐ－７）、（Ｐ－１２）、（Ｐ－１３）が好ましく、式（Ｐ－１）、（Ｐ－７）、（Ｐ－１２）がより好ましい。 Of these polymerizable functional groups, the formula (P-1) or the formulas (P-2), (P-7), (P-12), and (P-13) are preferable from the viewpoint of increasing the polymerizability. Formulas (P-1), (P-7), and (P-12) are more preferable.
　重合性ディスコチック化合物の具体的例としては、化合物（４－４）～（４－６）の化合物を挙げることができるが、下記の化合物に限定されるものではない。 Specific examples of the polymerizable discotic compound include compounds (4-4) to (4-6), but are not limited to the following compounds.
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
　一般式（４－４）～一般式（４－６）中、ｎは１～１８の整数を表す。
（重合性基を有する非液晶性化合物）　
　本発明の重合性組成物は、重合性基を有するが液晶化合物ではない化合物を添加することもできる。このような化合物としては、通常、この技術分野で重合性モノマーあるいは重合性オリゴマーとして認識されるものであれば特に制限なく使用することができる。添加する場合は、重合性組成物中に含有する重合性化合物の合計含有量１００質量部に対し、３０質量部以下であることが好ましく、２０質量部以下が更に好ましく、１５質量部以下が特に好ましい。 In the general formulas (4-4) to (4-6), n represents an integer of 1 to 18.
(Non-liquid crystalline compound having a polymerizable group)
In the polymerizable composition of the present invention, a compound having a polymerizable group but not a liquid crystal compound can be added. Such a compound can be used without particular limitation as long as it is generally recognized as a polymerizable monomer or polymerizable oligomer in this technical field. When added, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less, with respect to 100 parts by mass of the total content of polymerizable compounds contained in the polymerizable composition. preferable.
　具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、２－ヒドロキシエチルアクリレート、プロピル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンタニルオキシルエチル（メタ）アクリレート、イソボルニルオキシルエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジメチルアダマンチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、２－フェノキシジエチレングリコール（メタ）アクリレート、２－ヒドロキシ－３－フェノキシエチル（メタ）アクリレート、（２－メチル－２－エチル－１，３－ジオキソラン－４－イル）メチル（メタ）アクリレート、（３－エチルオキセタン－３－イル）メチル（メタ）アクリレート、ｏ－フェニルフェノールエトキシ（メタ）アクリレート、ジメチルアミノ（メタ）アクリレート、ジエチルアミノ（メタ）アクリレート、２，２，３，３，３－ペンタフルオロプロピル（メタ）アクリレート、２，２，３，４，４，４－ヘキサフルオロブチル（メタ）アクリレート、２，２，３，３，４，４，４－ヘプタフルオロブチル（メタ）アクリレート、２－（パーフルオロブチル）エチル（メタ）アクリレート、２－（パーフルオロヘキシル）エチル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、１Ｈ，１Ｈ，７Ｈ－ドデカフルオロヘプチル（メタ）アクリレート、１Ｈ－１－（トリフルオロメチル）トリフルオロエチル（メタ）アクリレート、１Ｈ，１Ｈ，３Ｈ－ヘキサフルオロブチル（メタ）アクリレート、１，２，２，２－テトラフルオロ－１－（トリフルオロメチル）エチル（メタ）アクリレート、１Ｈ，１Ｈ－ペンタデカフルオロオクチル（メタ）アクリレート、１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロオクチル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルフタル酸、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸、グリシジル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルりん酸、アクリロイルモルホリン、ジメチルアクリルアミド、ジメチルアミノプロピルアクリルアミド、イロプロピルアクリルアミド、ジエチルアクリルアミド、ヒドロキシエチルアクリルアミド、２－アクリロイロキシエチル－コハク酸、Ｎ－アクリロイルオキシエチルヘキサヒドロフタルイミド等のモノ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ネオペンチルジオールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、９，９－ビス[４－（２－アクリロイルオキシエトキシ）フェニル]フルオレン、グリセリンジ（メタ）アクリレート、２－ヒドロキシ－３－アクロイルオキシプロピルメタクリレート、１，６－ヘキサンジオールジグリシジルエーテルのアクリル酸付加物、１，４－ブタンジオールジグリシジルエーテルのアクリル酸付加物、等のジアクリレート、トリメチロールプロパントリ（メタ）アクリレート、エトキシ化イソシアヌル酸トリアクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ε－カプロラクトン変性トリス－（２－アクリロイルオキシエチル）イソシアヌレート、等のトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、等のテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、オリゴマー型の（メタ）アクリレート、各種ウレタンアクリレート、各種マクロモノマー、エチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、ビスフェノールＡジグリシジルエーテル、等のエポキシ化合物、マレイミド等が挙げられる。これらは単独で使用することもできるし、２種類以上混合して使用することもできる。
（有機溶剤）
　本発明における表示素子用封止材料組成物には有機溶剤を添加してもよい。用いる有機溶剤としては特に限定はないが、重合性液晶化合物が良好な溶解性を示す有機溶剤が好ましく、１００℃以下の温度で乾燥できる有機溶剤であることが好ましい。そのような溶剤としては、例えば、トルエン、キシレン、クメン、メシチレン等の芳香族系炭化水素、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン等のケトン系溶剤、テトラヒドロフラン、１，２－ジメトキシエタン、アニソール等のエーテル系溶剤、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、等のアミド系溶剤、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、γ－ブチロラクトン及びクロロベンゼン等が挙げられる。これらは、単独で使用することもできるし、２種類以上混合して使用することもできるが、ケトン系溶剤、エーテル系溶剤、エステル系溶剤及び芳香族炭化水素系溶剤のうちのいずれか１種類以上を用いることが溶液安定性の点から好ましい。 Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl acrylate, propyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl Damantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, 2-phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, o-phenylphenol ethoxy (meth) acrylate, dimethylamino (meth) acrylate, diethylamino (Meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,3 4,4,4-heptafluorobutyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl ( (Meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H , 1H, 3H-Hexafluorobutyl (meth) acrylate, 1,2,2,2-the Trafluoro-1- (trifluoromethyl) ethyl (meth) acrylate, 1H, 1H-pentadecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 2- (meta ) Acrylyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphoric acid, acryloylmorpholine, dimethylacrylamide, dimethylaminopropylacrylamide, isopropyl Mono (meth) acrylates such as acrylamide, diethyl acrylamide, hydroxyethyl acrylamide, 2-acryloyloxyethyl-succinic acid, N-acryloyloxyethyl hexahydrophthalimide 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyldiol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 1,6-hexanedioe Diacrylate, trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri (meta), such as acrylic acid adduct of rudiglycidyl ether, acrylic acid adduct of 1,4-butanediol diglycidyl ether, etc. ) Acrylate, ε-caprolactone modified tris- (2-acryloyloxyethyl) isocyanurate, etc., tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, etc. Acrylate, dipentaerythritol hexa (meth) acrylate, oligomeric (meth) acrylate, various urethane acrylates, various macromonomers, ethylene glycol diglycidyl ester Terpene, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, bisphenol A diglycidyl ether, and the like, and maleimide It is done. These can be used alone or in combination of two or more.
(Organic solvent)
You may add an organic solvent to the sealing material composition for display elements in this invention. Although there is no limitation in particular as an organic solvent to be used, the organic solvent in which a polymeric liquid crystal compound shows favorable solubility is preferable, and it is preferable that it is an organic solvent which can be dried at the temperature of 100 degrees C or less. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexane, and the like. Ketone solvents such as pentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate , Diethylene glycol monomethyl ether acetate, γ-butyrolactone, chlorobenzene and the like. These can be used alone or in combination of two or more, but any one of ketone solvents, ether solvents, ester solvents and aromatic hydrocarbon solvents It is preferable to use the above from the viewpoint of solution stability.
　本発明に用いられる表示素子用封止材料組成物は有機溶剤を用いて溶液として基材に対して塗布することができ、表示素子用封止材料組成物に用いる有機溶剤の比率は、塗布した状態を著しく損なわない限りは特に制限はないが、表示素子用封止材料組成物中に含有する有機溶剤の合計量が０～９０質量％であることが好ましく、０～８５質量％であることが更に好ましく、０～８０質量％であることが特に好ましい。　本発明に用いられる表示素子用封止材料組成物を作製する際に有機溶剤を用いる場合、先に、本発明に用いる充填材を有機溶剤中に分散させ分散液とした上で、当該分散液中に本発明に用いる重合性液晶化合物等を溶解させて組成物としても良い。また、本発明に用いられる表示素子用封止材料組成物を作製する際に有機溶剤を用いる場合、先に、本発明に用いる重合性液晶化合物を溶解させて重合性液晶組成物とした上で、当該重合性液晶組成物中に本発明に用いる充填材を分散させた組成物としても良い。或いは、本発明に用いられる表示素子用封止材料組成物を作製する際に有機溶剤を用いる場合、本発明に用いる充填材を分散した分散液、及び、本発明に用いる重合性液晶化合物を溶解した重合性液晶組成物をそれぞれ作製した上で両者を混合し表示素子用封止材料組成物としても良い。 The sealing material composition for display elements used in the present invention can be applied to the substrate as a solution using an organic solvent, and the ratio of the organic solvent used for the sealing material composition for display elements was applied. There is no particular limitation as long as the state is not significantly impaired, but the total amount of the organic solvent contained in the sealing material composition for display elements is preferably 0 to 90% by mass, and preferably 0 to 85% by mass. Is more preferable, and 0 to 80% by mass is particularly preferable. When an organic solvent is used when producing the sealing material composition for display elements used in the present invention, first, the filler used in the present invention is dispersed in the organic solvent to obtain a dispersion, and then the dispersion A polymerizable liquid crystal compound or the like used in the present invention may be dissolved therein to form a composition. Moreover, when using the organic solvent when producing the sealing material composition for display elements used in the present invention, the polymerizable liquid crystal compound used in the present invention is first dissolved to obtain a polymerizable liquid crystal composition. A composition in which the filler used in the present invention is dispersed in the polymerizable liquid crystal composition may be used. Alternatively, when an organic solvent is used when producing the sealing material composition for display elements used in the present invention, the dispersion in which the filler used in the present invention is dispersed and the polymerizable liquid crystal compound used in the present invention are dissolved. Each of the prepared polymerizable liquid crystal compositions may be prepared and then mixed to form a sealing material composition for a display element.
　有機溶剤に重合性液晶化合物を溶解する際には、均一に溶解させるために、加熱攪拌することが好ましい。加熱攪拌時の加熱温度は、用いる組成物の有機溶剤に対する溶解性を考慮して適宜調節すればよいが、生産性の点から１５℃～１１０℃が好ましく、１５℃～１０５℃がより好ましく、１５℃～１００℃がさらに好ましく、２０℃～９０℃とするのが特に好ましい。 When dissolving the polymerizable liquid crystal compound in the organic solvent, it is preferable to stir with heating in order to dissolve it uniformly. The heating temperature at the time of heating and stirring may be appropriately adjusted in consideration of the solubility of the composition to be used in the organic solvent, but is preferably 15 ° C. to 110 ° C., more preferably 15 ° C. to 105 ° C. from the viewpoint of productivity. 15 to 100 ° C. is more preferable, and 20 to 90 ° C. is particularly preferable.
　また、有機溶剤に充填材及び／又は重合性液晶化合物を分散又は溶解させる際には分散攪拌機により攪拌混合することも可能である。分散攪拌機として具体的には、湿式ビーズミル、ディスパー、プロペラやタービン翼等攪拌翼を有する分散機、ペイントシェイカー、遊星式攪拌装置、振とう機、シェーカー又はロータリーエバポレーター等が使用できる。その他には、超音波照射装置が使用できる。特に充填材を有機溶剤中に分散させた分散液を作製する際には湿式ビーズミル、ディスパーを用いることが好ましく、重合性液晶化合物を有機溶剤中に溶解させた溶液を作製する際には攪拌翼を有する分散機、遊星式攪拌装置、振とう機を用いることが好ましい。 Further, when the filler and / or polymerizable liquid crystal compound is dispersed or dissolved in the organic solvent, it is also possible to stir and mix with a dispersion stirrer. Specifically, a dispersion machine having a stirring blade such as a wet bead mill, a disper, a propeller, or a turbine blade, a paint shaker, a planetary stirring device, a shaker, a shaker, or a rotary evaporator can be used as the dispersion stirrer. In addition, an ultrasonic irradiation apparatus can be used. In particular, wet bead mills and dispersers are preferably used when preparing a dispersion in which a filler is dispersed in an organic solvent, and stirring blades are used when preparing a solution in which a polymerizable liquid crystal compound is dissolved in an organic solvent. It is preferable to use a disperser, a planetary stirrer and a shaker.
　溶媒を添加する際の攪拌回転数は、用いる攪拌装置により適宜調整することが好ましいが、均一な表示素子用封止材料組成物溶液とするために攪拌回転数を１０ｒｐｍ～１０００ｒｐｍとするのが好ましく、５０ｒｐｍ～８００ｒｐｍとするのがより好ましく、１００ｒｐｍ～６００ｒｐｍとするのが特に好ましい。 The number of rotations of stirring when adding the solvent is preferably adjusted appropriately depending on the stirring device used, but the number of rotations of stirring is preferably 10 rpm to 1000 rpm in order to obtain a uniform sealing material composition solution for display elements. 50 rpm to 800 rpm is more preferable, and 100 rpm to 600 rpm is particularly preferable.
　本発明の表示素子用封止材料組成物には、その他の成分として、前記キラル化合物や以下の成分を含有していても良いが、前記キラル化合物や以下に記載の成分は、有機溶剤、充填材及び／又は重合性液晶化合物を分散或いは溶解させる時に適宜用いて組成物中に含有させることができる。
（重合禁止剤）
　本発明における表示素子用封止材料組成物には、重合禁止剤を添加することが好ましい。重合禁止剤としては、フェノール系化合物、キノン系化合物、アミン系化合物、チオエーテル系化合物、ニトロソ化合物、等が挙げられる。 The sealing material composition for display elements of the present invention may contain the chiral compound and the following components as other components, but the chiral compound and the components described below are organic solvents, packing The material and / or the polymerizable liquid crystal compound can be appropriately used when dispersed or dissolved in the composition.
(Polymerization inhibitor)
It is preferable to add a polymerization inhibitor to the sealing material composition for display elements in the present invention. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like.
　フェノール系化合物としては、ｐ－メトキシフェノール、クレゾール、ｔ－ブチルカテコール、３．５－ジ－ｔ－ブチル－４－ヒドロキシトルエン、２．２'－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２．２'－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４．４'－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４－メトキシ－１－ナフトール、４，４’－ジアルコキシ－２，２’－ビ－１－ナフトール、等が挙げられる。 Examples of phenolic compounds include p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol) 2.2′-methylenebis (4-ethyl-6-tert-butylphenol), 4.4′-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4′- Dialkoxy-2,2′-bi-1-naphthol, and the like.
　キノン系化合物としては、ヒドロキノン、メチルヒドロキノン（ＭＥＨＱ）、ｔｅｒｔ－ブチルヒドロキノン、ｐ－ベンゾキノン、メチル－ｐ－ベンゾキノン、ｔｅｒｔ－ブチル－ｐ－ベンゾキノン、２，５－ジフェニルベンゾキノン、２－ヒドロキシ－１，４－ナフトキノン、１，４－ナフトキノン、２，３－ジクロロ－１，４－ナフトキノン、アントラキノン、ジフェノキノン等が挙げられる。 Examples of quinone compounds include hydroquinone, methylhydroquinone (MEHQ), tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1, Examples include 4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, and diphenoquinone.
　アミン系化合物としては、ｐ－フェニレンジアミン、４－アミノジフェニルアミン、Ｎ．Ｎ'－ジフェニル－ｐ－フェニレンジアミン、Ｎ－ｉ－プロピル－Ｎ'－フェニル－ｐ－フェニレンジアミン、Ｎ－（１．３－ジメチルブチル）－Ｎ'－フェニル－ｐ－フェニレンジアミン、Ｎ．Ｎ'－ジ－２－ナフチル－ｐ－フェニレンジアミン、ジフェニルアミン、Ｎ－フェニル－β－ナフチルアミン、４．４'－ジクミル－ジフェニルアミン、４．４'－ジオクチル－ジフェニルアミン等が挙げられる。 Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N.I. N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I. N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine and the like.
　チオエーテル系化合物としては、フェノチアジン、ジステアリルチオジプロピオネート等が挙げられる。 Examples of thioether compounds include phenothiazine and distearyl thiodipropionate.
　ニトロソ系化合物としては、Ｎ－ニトロソジフェニルアミン、Ｎ－ニトロソフェニルナフチルアミン、Ｎ－ニトロソジナフチルアミン、ｐ－ニトロソフェノール、ニトロソベンゼン、ｐ－ニトロソジフェニルアミン、α－ニトロソ－β－ナフトール等、Ｎ、Ｎ－ジメチルｐ－ニトロソアニリン、ｐ－ニトロソジフェニルアミン、ｐ－ニトロンジメチルアミン、ｐ－ニトロン－Ｎ、Ｎ－ジエチルアミン、Ｎ－ニトロソエタノールアミン、Ｎ－ニトロソジ－ｎ－ブチルアミン、Ｎ－ニトロソ－Ｎ－ｎ－ブチル－４－ブタノールアミン、Ｎ－ニトロソ－ジイソプロパノールアミン、Ｎ－ニトロソ－Ｎ－エチル－４－ブタノールアミン、５－ニトロソ－８－ヒドロキシキノリン、Ｎ－ニトロソモルホリン、Ｎ－二トロソーＮ－フェニルヒドロキシルアミンアンモニウム塩、二トロソベンゼン、２，４．６－トリーｔｅｒｔ－ブチルニトロンベンゼン、Ｎ－ニトロソ－Ｎ－メチル－ｐ－トルエンスルホンアミド、Ｎ－ニトロソ－Ｎ－エチルウレタン、Ｎ－ニトロソ－Ｎ－ｎ－プロピルウレタン、１－ニトロソ－２－ナフトール、２－ニトロソー１－ナフトール、１－ニトロソ－２－ナフトール－３，６－スルホン酸ナトリウム、２－ニトロソ－１－ナフトール－４－スルホン酸ナトリウム、２－ニトロソ－５－メチルアミノフェノール塩酸塩、２－ニトロソ－５－メチルアミノフェノール塩酸塩等が挙げられる。 Examples of nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, and the like, N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl- 4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine Minammonium salt, ditrosobenzene, 2,4.6-tri-tert-butylnitronebenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N- n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso 1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol-4-sodium sulfonate, Examples include 2-nitroso-5-methylaminophenol hydrochloride and 2-nitroso-5-methylaminophenol hydrochloride.
　重合禁止剤の添加量は表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して０．０１～１．０質量部であることが好ましく、０．０５～０．５質量部であることがより好ましい。
（酸化防止剤）
　本発明における表示素子用封止材料組成物の安定性を高めるため、酸化防止剤等を添加することが好ましい。そのような化合物として、ヒドロキノン誘導体、ニトロソアミン系重合禁止剤、ヒンダードフェノール系酸化防止剤等が挙げられ、より具体的には、tert－ブチルハイドロキノン、メチルハイドロキノン、和光純薬工業株式会社製の「Ｑ－１３００」、「Ｑ－１３０１」、ＢＡＳＦ社の「ＩＲＧＡＮＯＸ１０１０」、「ＩＲＧＡＮＯＸ１０３５」、「ＩＲＧＡＮＯＸ１０７６」、「ＩＲＧＡＮＯＸ１０９８」、「ＩＲＧＡＮＯＸ１１３５」、「ＩＲＧＡＮＯＸ１３３０」、「ＩＲＧＡＮＯＸ１４２５」、「ＩＲＧＡＮＯＸ１５２０」、「ＩＲＧＡＮＯＸ１７２６」、「ＩＲＧＡＮＯＸ２４５」、「ＩＲＧＡＮＯＸ２５９」、「ＩＲＧＡＮＯＸ３１１４」、「ＩＲＧＡＮＯＸ３７９０」、「ＩＲＧＡＮＯＸ５０５７」、「ＩＲＧＡＮＯＸ５６５」等々があげられる。 The addition amount of the polymerization inhibitor is preferably 0.01 to 1.0 part by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used in the sealing material composition for display elements, and 0.05 to More preferably, it is 0.5 parts by mass.
(Antioxidant)
In order to improve the stability of the sealing material composition for display elements in the present invention, it is preferable to add an antioxidant or the like. Examples of such compounds include hydroquinone derivatives, nitrosamine polymerization inhibitors, hindered phenol antioxidants, and more specifically, tert-butyl hydroquinone, methyl hydroquinone, manufactured by Wako Pure Chemical Industries, Ltd. “IRGANOX1010”, “IRGANOX1035”, “IRGANOX1076”, “IRGANOX1098”, “IRGANOX1135”, “IRGANOX1330”, “IRGANOX1425”, “IRGANOX1520”, “IRGANOX1726”, BASF Corporation “IRGANOX245”, “IRGANOX259”, “IRGANOX3114”, “IRGANOX3790”, “IRGANOX5057”, “IRGANOX565” And so on.
　酸化防止剤の添加量は表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して０．０１～２．０質量部であることが好ましく、０．０５～１．０質量部であることがより好ましい。
（光重合開始剤）
　本発明における表示素子用封止材料組成物は光重合開始剤を含有することが好ましい。光重合開始剤は少なくとも１種類以上含有することが好ましい。具体的には、ＢＡＳＦジャパン株式会社製の「イルガキュア６５１」、「イルガキュア１８４」、「イルガキュア９０７」、「イルガキュア１２７」、「イルガキュア３６９」、「イルガキュア３７９」、「イルガキュア８１９」、「イルガキュア２９５９」、「イルガキュア１８００」、「イルガキュア２５０」、「イルガキュア７５４」、「イルガキュア７８４」、「イルガキュアＯＸＥ０１」、「イルガキュアＯＸＥ０２」、「ルシリンＴＰＯ」、「ダロキュア１１７３」、「ダロキュアＭＢＦ」やＬＡＭＢＳＯＮ社製の「エサキュア１００１Ｍ」、「エサキュアＫＩＰ１５０」、「スピードキュアＢＥＭ」、「スピードキュアＢＭＳ」、「スピードキュアＭＢＰ」、「スピードキュアＰＢＺ」、「スピードキュアＩＴＸ」、「スピードキュアＤＥＴＸ」、「スピードキュアＥＢＤ」、「スピードキュアＭＢＢ」、「スピードキュアＢＰ」や日本化薬株式会社製の「カヤキュアＤＭＢＩ」、日本シイベルヘグナー株式会社製(現ＤＫＳＨジャパン株式会社)の「ＴＡＺ－Ａ」、株式会社ＡＤＥＫＡ製の「アデカオプトマーＳＰ－１５２」、「アデカオプトマーＳＰ－１７０」、「アデカオプトマーＮ－１４１４」、「アデカオプトマーＮ－１６０６」、「アデカオプトマーＮ－１７１７」、「アデカオプトマーＮ－１９１９」等が挙げられる。 The addition amount of the antioxidant is preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements, and 0.05 to More preferably, it is 1.0 part by mass.
(Photopolymerization initiator)
It is preferable that the sealing material composition for display elements in this invention contains a photoinitiator. It is preferable to contain at least one photopolymerization initiator. Specifically, “Irgacure 651”, “Irgacure 184”, “Irgacure 907”, “Irgacure 127”, “Irgacure 369”, “Irgacure 379”, “Irgacure 819”, “Irgacure 2959” manufactured by BASF Japan Ltd. "Irgacure 1800", "Irgacure 250", "Irgacure 754", "Irgacure 784", "Irgacure OXE01", "Irgacure OXE02", "Lucirin TPO", "Darocure 1173", "Darocure MBF" and LAMBSON “Esacure 1001M”, “Esacure KIP150”, “Speed Cure BEM”, “Speed Cure BMS”, “Speed Cure MBP”, “Speed Cure PBZ”, “Speed Cure ITX”, “Speed” “Cure DETX”, “Speed Cure EBD”, “Speed Cure MBB”, “Speed Cure BP”, “Kayacure DMBI” manufactured by Nippon Kayaku Co., Ltd., “TAZ-” manufactured by Nippon Shibel Hegner Co., Ltd. (currently DKSH Japan Co., Ltd.) A ”,“ Adekaoptomer SP-152 ”,“ Adekaoptomer SP-170 ”,“ Adekaoptomer N-1414 ”,“ Adekaoptomer N-1606 ”,“ Adekaoptomer N- ”manufactured by ADEKA Corporation 1717 "," Adekaoptomer N-1919 "and the like.
　光重合開始剤の表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して０．１～１０質量部が好ましく、０．５～１０質量部が特に好ましい。これらは、単独で使用することもできるし、２種類以上混合して使用することもでき、また、増感剤等を添加しても良い。
（熱重合開始剤）
　本発明における表示素子用封止材料組成物には、光重合開始剤とともに、熱重合開始剤を併用してもよい。具体的には、和光純薬工業株式会社製の「Ｖ－４０」、「ＶＦ－０９６」、日本油脂株式会社（現日油株式会社）の「パーへキシルＤ」、「パーへキシルＩ」等が挙げられる。 The amount is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements of the photopolymerization initiator. These can be used alone or in combination of two or more, and a sensitizer or the like may be added.
(Thermal polymerization initiator)
A thermal polymerization initiator may be used in combination with the photopolymerization initiator in the sealing material composition for display elements in the present invention. Specifically, “V-40” and “VF-096” manufactured by Wako Pure Chemical Industries, Ltd., “Perhexyl D” and “Perhexyl I” of Nippon Oil & Fats Co., Ltd. (currently Nippon Oil Co., Ltd.) Etc.
　熱重合開始剤の使用量は表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して０．１～１０質量部が好ましく、０．５～５質量部が特に好ましい。これらは、単独で使用することもできるし、２種類以上混合して使用することもできる。
（界面活性剤）
　本発明における表示素子用封止材料組成物は、光学異方体とした場合の膜厚むらを低減させるために、本発明の効果を損なわない範囲で更に界面活性剤を少なくとも１種類以上含有してもよい。含有することができる界面活性剤としては、アルキルカルボン酸塩、アルキルリン酸塩、アルキルスルホン酸塩、フルオロアルキルカルボン酸塩、フルオロアルキルリン酸塩、フルオロアルキルスルホン酸塩、ポリオキシエチレン誘導体、フルオロアルキルエチレンオキシド誘導体、ポリエチレングリコール誘導体、アルキルアンモニウム塩、フルオロアルキルアンモニウム塩類等をあげることができ、特に含フッ素界面活性剤が好ましい。 The amount of the thermal polymerization initiator used is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements. Particularly preferred. These can be used alone or in combination of two or more.
(Surfactant)
The sealing material composition for display elements in the present invention further contains at least one surfactant in a range that does not impair the effects of the present invention in order to reduce film thickness unevenness in the case of an optical anisotropic body. May be. Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like, and fluorine-containing surfactants are particularly preferable.
　具体的には、「メガファック　Ｆ－２５１」、「メガファック　Ｆ－４４４」、「メガファック　Ｆ－４７７」、「メガファック　Ｆ－５１０」、「メガファック　Ｆ－５５２」、「メガファック　Ｆ－５５３」、「メガファック　Ｆ－５５４」、「メガファック　Ｆ－５５５」、「メガファック　Ｆ－５５６」、「メガファック　Ｆ－５５７」、「メガファック　Ｆ－５５８」、「メガファック　Ｆ－５５９」、「メガファック　Ｆ－５６０」、「メガファック　Ｆ－５６１」、「メガファック　Ｆ－５６２」、「メガファック　Ｆ－５６３」、「メガファック　Ｆ－５６５」、「メガファック　Ｆ－５６７」、「メガファック　Ｆ－５６８」、「メガファック　Ｆ－５６９」、「メガファック　Ｆ－５７０」、「メガファック　Ｆ－５７１」、「メガファック　Ｒ－４０」、「メガファック　Ｒ－４１」、「メガファック　Ｒ－４３」、「メガファック　Ｒ－９４」、「メガファック　ＲＳ－７２－Ｋ」、「メガファック　ＲＳ－７５」、「メガファック　ＲＳ－７６－Ｅ」、「メガファック　ＲＳ－９０」、（以上、ＤＩＣ株式会社製）、
「フタージェント１００」、「フタージェント１００Ｃ」、「フタージェント１１０」、「フタージェント１５０」、「フタージェント１５０ＣＨ」、「フタージェントＡ」、「フタージェント１００Ａ-Ｋ」、「フタージェント５０１」、「フタージェント３００」、「フタージェント３１０」、「フタージェント３２０」、「フタージェント４００ＳＷ」、「ＦＴＸ-４００Ｐ」、「フタージェント２５１」、「フタージェント２１５Ｍ」、「フタージェント２１２ＭＨ」、「フタージェント２５０」、「フタージェント２２２Ｆ」、「フタージェント２１２Ｄ」、「ＦＴＸ-２１８」、「ＦＴＸ-２０９Ｆ」、「ＦＴＸ-２１３Ｆ」、「ＦＴＸ-２３３Ｆ」、「フタージェント２４５Ｆ」、「ＦＴＸ-２０８Ｇ」、「ＦＴＸ-２４０Ｇ」、「ＦＴＸ-２０６Ｄ」、「ＦＴＸ-２２０Ｄ」、「ＦＴＸ-２３０Ｄ」、「ＦＴＸ-２４０Ｄ」、「ＦＴＸ-２０７Ｓ」、「ＦＴＸ-２１１Ｓ」、「ＦＴＸ-２２０Ｓ」、「ＦＴＸ-２３０Ｓ」、「ＦＴＸ-７５０ＦＭ」、「ＦＴＸ-７３０ＦＭ」、「ＦＴＸ-７３０ＦＬ」、「ＦＴＸ-７１０ＦＳ」、「ＦＴＸ-７１０ＦＭ」、「ＦＴＸ-７１０ＦＬ」、「ＦＴＸ-７５０ＬＬ」、「ＦＴＸ-７３０ＬＳ」、「ＦＴＸ-７３０ＬＭ」、「ＦＴＸ-７３０ＬＬ」、「ＦＴＸ-７１０ＬＬ」（以上、株式会社ネオス製）、
「ＢＹＫ－３００」、「ＢＹＫ－３０２」、「ＢＹＫ－３０６」、「ＢＹＫ－３０７」、「ＢＹＫ－３１０」、「ＢＹＫ－３１５」、「ＢＹＫ－３２０」、「ＢＹＫ－３２２」、「ＢＹＫ－３２３」、「ＢＹＫ－３２５」、「ＢＹＫ－３３０」、「ＢＹＫ－３３１」、「ＢＹＫ－３３３」、「ＢＹＫ－３３７」、「ＢＹＫ－３４０」、「ＢＹＫ－３４４」、「ＢＹＫ－３４４０」、「ＢＹＫ－３７０」、「ＢＹＫ－３７５」、「ＢＹＫ－３７７」、「ＢＹＫ－３５０」、「ＢＹＫ－３５２」、「ＢＹＫ－３５４」、「ＢＹＫ－３５５」、「ＢＹＫ－３５６」、「ＢＹＫ－３５８Ｎ」、「ＢＹＫ－３６１Ｎ」、「ＢＹＫ－３５７」、「ＢＹＫ－３９０」、「ＢＹＫ－３９２」、「ＢＹＫ－ＵＶ３５００」、「ＢＹＫ－ＵＶ３５１０」、「ＢＹＫ－ＵＶ３５７０」、「ＢＹＫ－Ｓｉｌｃｌｅａｎ３７００」（以上、ビックケミー・ジャパン社製）、
「ＴＥＧＯ Ｒａｄ２１００」、「ＴＥＧＯ Ｒａｄ２２００Ｎ」、「ＴＥＧＯ Ｒａｄ２２５０」、「ＴＥＧＯ Ｒａｄ２３００」、「ＴＥＧＯ Ｒａｄ２５００」、「ＴＥＧＯ Ｒａｄ２６００」、「ＴＥＧＯ Ｒａｄ２７００」（以上、テゴ社製）
「Ｎ２１５」、「Ｎ５３５」、「Ｎ６０５Ｋ」、「Ｎ９３５」（以上、ソルベイソレクシス社製）等の例をあげることができる。 Specifically, “Megafuck F-251”, “Megafuck F-444”, “Megafuck F-477”, “Megafuck F-510”, “Megafuck F-552”, “Megafuck F-” "553", "Megafuck F-554", "Megafuck F-555", "Megafuck F-556", "Megafuck F-557", "Megafuck F-558", "Megafuck F-559" , “Megafuck F-560”, “Megafuck F-561”, “Megafuck F-562”, “Megafuck F-563”, “Megafuck F-565”, “Megafuck F-567”, “ “Megafuck F-568”, “Megafuck F-569”, “Megafuck F-570”, “Megafuck F-571”, “Megafuck R-40” , “Megafuck R-41”, “Megafuck R-43”, “Megafuck R-94”, “Megafuck RS-72-K”, “Megafuck RS-75”, “Megafuck RS-76-” E "," Megafuck RS-90 "(above, manufactured by DIC Corporation),
“Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, “Furgent 150CH”, “Furgent A”, “Furgent 100A-K”, “Furgent 501”, "Factent 300", "Factent 310", "Factent 320", "Factent 400SW", "FTX-400P", "Factent 251", "Factent 215M", "Factent 212MH", "Footer Gent 250, Fategent 222F, Fategent 212D, FTX-218, FTX-209F, FTX-213F, FTX-233F, Fate 245F, FTX-208G ”,“ FTX-240G ”,“ FT -206D "," FTX-220D "," FTX-230D "," FTX-240D "," FTX-207S "," FTX-211S "," FTX-220S "," FTX-230S "," FTX-750FM " ”,“ FTX-730FM ”,“ FTX-730FL ”,“ FTX-710FS ”,“ FTX-710FM ”,“ FTX-710FL ”,“ FTX-750LL ”,“ FTX-730LS ”,“ FTX-730LM ”, "FTX-730LL", "FTX-710LL" (above, manufactured by Neos Corporation),
“BYK-300”, “BYK-302”, “BYK-306”, “BYK-307”, “BYK-310”, “BYK-315”, “BYK-320”, “BYK-322”, “BYK” -323 "," BYK-325 "," BYK-330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-340 "," BYK-344 "," BYK-3440 " ”,“ BYK-370 ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK-350 ”,“ BYK-352 ”,“ BYK-354 ”,“ BYK-355 ”,“ BYK-356 ”, “BYK-358N”, “BYK-361N”, “BYK-357”, “BYK-390”, “BYK-392”, “BYK-UV3500”, “BYK-UV3510”, “BYK” UV3570 "," BYK-Silclean3700 "(manufactured by BYK Japan KK),
“TEGO Rad2100”, “TEGO Rad2200N”, “TEGO Rad2250”, “TEGO Rad2300”, “TEGO Rad2500”, “TEGO Rad2600”, “TEGO Rad2700” (above, manufactured by TEGO)
Examples include “N215”, “N535”, “N605K”, “N935” (above, manufactured by Solvay Solexis).
　界面活性剤の添加量は表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して、０．０１～２質量部であることが好ましく、０．０５～０．５質量部であることがより好ましい。 The addition amount of the surfactant is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements, and 0.05 to 0 More preferably, it is 5 parts by mass.
　また、上記界面活性剤を使用することで、本発明の表示素子用封止材料組成物をフィルム状とした場合、空気界面のチルト角を効果的に減じることができる。 In addition, by using the above surfactant, when the sealing composition for a display element of the present invention is formed into a film, the tilt angle at the air interface can be effectively reduced.
　本発明における表示素子用封止材料組成物は、本発明の効果を損なわない範囲でフィルムとした場合の空気界面のチルト角を効果的に減じる効果を持つ、下記一般式（７）で表される繰り返し単位を有する重量平均分子量が１００以上である化合物が挙げられる。 The sealing material composition for display elements in the present invention is represented by the following general formula (7), which has the effect of effectively reducing the tilt angle of the air interface when it is used as a film without impairing the effects of the present invention. And a compound having a repeating unit having a weight average molecular weight of 100 or more.
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
　式中、Ｒ１１、Ｒ１２、Ｒ１３及びＲ１４はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１～２０の炭化水素基を表し、該炭化水素基中の水素原子は１つ以上のハロゲン原子で置換されていても良い。 In the formula, each of R 11 , R 12 , R 13 and R 14 independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group It may be substituted with a halogen atom.
　一般式（７）で表される好適な化合物として、例えばポリエチレン、ポリプロピレン、ポリイソブチレン、パラフィン、流動パラフィン、塩素化ポリプロピレン、塩素化パラフィン、塩素化流動パラフィン等を挙げることができる。 Examples of suitable compounds represented by the general formula (7) include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin.
　一般式（７）で表される化合物の添加量は表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して、０．０１～１質量部であることが好ましく、０．０５～０．５質量部であることがより好ましい。
（その他の添加剤）
　更に物性調整のため、目的に応じて、液晶性のない重合性化合物、チキソ剤、分散剤、連鎖移動剤等の添加剤を本発明の表示素子用封止材料組成物の性質を損なわない程度添加することができる。詳しくは、表示素子用封止材料組成物に用いる重合性液晶化合物の合計含有量１００質量部に対して、０．０１～１質量部であることが好ましく、０．０５～０．５質量部であることがより好ましい。（表示素子用封止材料組成物の製造方法）
　本発明の表示素子用封止材料組成物は、少なくとも１種以上の充填材、及び、２種以上の重合性液晶化合物を混合して製造することができる。具体的には、撹拌又は超音波照射により、重合性液晶化合物を液晶状態にすると共に充填材を分散させた表示素子用封止材料組成物を得ることができる。なお、撹拌方法としては、遊星式撹拌装置、振とう機、ラボミキサー、撹拌プロペラ、シェーカー又はロータリーエバポレーター等が使用できる。表示素子用封止材料組成物の製造に前記撹拌方法又は超音波照射方法を用いる場合、製造中の温度は上昇することもあるが、外部からの加熱は任意であり、加熱しても加熱しなくても良い。製造中の温度は、１５℃以上７０℃以下とすることが好ましく、２０℃以上５０℃以下とすることがより好ましく、２５℃以上４５℃以下とすることが特に好ましい。なお、本発明の表示素子用封止材料組成物を撹拌又は超音波照射により製造する場合、用いる２種以上の重合性液晶化合物からなる組成物は室温で液晶性を維持ことが好ましい。 The addition amount of the compound represented by the general formula (7) is 0.01 to 1 part by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compounds used in the sealing material composition for display elements. Preferably, the amount is 0.05 to 0.5 parts by mass.
(Other additives)
Furthermore, for the purpose of adjusting physical properties, depending on the purpose, additives such as polymerizable compounds having no liquid crystallinity, thixotropic agents, dispersants, chain transfer agents and the like are not impaired in the properties of the sealing material composition for display elements of the present invention. Can be added. Specifically, the content is preferably 0.01 to 1 part by mass, and 0.05 to 0.5 part by mass with respect to 100 parts by mass of the total content of the polymerizable liquid crystal compound used in the sealing material composition for display elements. It is more preferable that (Method for producing sealing material composition for display element)
The sealing material composition for display elements of the present invention can be produced by mixing at least one or more fillers and two or more polymerizable liquid crystal compounds. Specifically, a sealing material composition for a display element in which a polymerizable liquid crystal compound is brought into a liquid crystal state and a filler is dispersed can be obtained by stirring or ultrasonic irradiation. In addition, as a stirring method, a planetary stirring apparatus, a shaker, a laboratory mixer, a stirring propeller, a shaker, a rotary evaporator, or the like can be used. When the stirring method or the ultrasonic irradiation method is used for the production of the sealing material composition for display elements, the temperature during the production may rise, but the heating from the outside is arbitrary, and the heating is performed even when heated. It is not necessary. The temperature during production is preferably 15 ° C. or higher and 70 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, and particularly preferably 25 ° C. or higher and 45 ° C. or lower. In addition, when manufacturing the sealing material composition for display elements of this invention by stirring or ultrasonic irradiation, it is preferable that the composition consisting of 2 or more types of polymeric liquid crystal compounds to be used maintains liquid crystallinity at room temperature.
　本発明に用いられる表示素子用封止材料組成物を作製する際に有機溶剤を用いる場合、先に、本発明に用いる充填材を有機溶剤中に分散させ分散液とした上で、本発明に用いる重合性液晶化合物等を溶解させて組成物としても良い。また、本発明に用いられる表示素子用封止材料組成物を作製する際に有機溶剤を用いる場合、先に、本発明に用いる重合性液晶化合物を溶解させて重合性液晶組成物とした上で、本発明に用いる充填材を分散させた組成物としても良い。或いは、本発明に用いられる表示素子用封止材料組成物を作製する際に有機溶剤を用いる場合、本発明に用いる充填材を分散した分散液、及び、本発明に用いる重合性液晶化合物を溶解した重合性液晶組成物をそれぞれ作製した上で混合し表示素子用封止材料組成物としても良い。表示素子用封止材料組成物の製造に有機溶剤を用いる場合、製造中の外部からの加熱は任意であり、加熱しても加熱しなくても良い。製造中の温度は、１５℃以上７０℃以下とすることが好ましく、２０℃以上５０℃以下とすることがより好ましく、２５℃以上４５℃以下とすることが特に好ましい。 When an organic solvent is used when producing the sealing material composition for a display element used in the present invention, the filler used in the present invention is first dispersed in the organic solvent to obtain a dispersion, and then the present invention is applied. A polymerizable liquid crystal compound to be used may be dissolved to form a composition. Moreover, when using the organic solvent when producing the sealing material composition for display elements used in the present invention, the polymerizable liquid crystal compound used in the present invention is first dissolved to obtain a polymerizable liquid crystal composition. A composition in which the filler used in the present invention is dispersed may be used. Alternatively, when an organic solvent is used when producing the sealing material composition for display elements used in the present invention, the dispersion in which the filler used in the present invention is dispersed and the polymerizable liquid crystal compound used in the present invention are dissolved. The prepared polymerizable liquid crystal composition may be prepared and mixed to form a sealing material composition for a display element. When an organic solvent is used for the production of the sealing material composition for display elements, heating from the outside during production is optional, and it may be heated or not heated. The temperature during production is preferably 15 ° C. or higher and 70 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, and particularly preferably 25 ° C. or higher and 45 ° C. or lower.
　本発明の表示素子用封止材料組成物は、１種又は２種以上の重合性液晶化合物を加熱溶融した液体状態物に対し、充填材を添加撹拌し製造することもできる。この場合、重合性化合物を溶融させるため加熱することが必要となるが、加熱温度は、用いる全ての重合性化合物が溶融する温度から±１０℃の温度にすることが好ましい。
（表示素子）
　本発明の表示素子用封止材料組成物は、表示素子の基材封止保護剤やシール剤として用いられる。表示素子としては、液晶材料を用いた液晶表示素子、有機発光ダイオードを用いた有機発光表示素子、量子ドットを用いた量子ドット表示素子等が挙げられ、各表示素子の基材や基質の封止保護剤や、各表示素子の額縁部分のシール剤として好適に用いることができる。 The sealing material composition for a display element of the present invention can also be produced by adding and stirring a filler to a liquid state product obtained by heating and melting one or more polymerizable liquid crystal compounds. In this case, heating is required to melt the polymerizable compound, but the heating temperature is preferably set to a temperature of ± 10 ° C. from the temperature at which all the polymerizable compounds used melt.
(Display element)
The sealing material composition for display elements of the present invention is used as a base material sealing protective agent or a sealing agent for display elements. Examples of the display element include a liquid crystal display element using a liquid crystal material, an organic light emitting display element using an organic light emitting diode, a quantum dot display element using a quantum dot, etc., and sealing a substrate and a substrate of each display element It can be suitably used as a protective agent or a sealing agent for the frame portion of each display element.
　本発明の表示素子は、基材層、本発明の表示素子用封止材料組成物を用いた基材封止保護層、及び、無機層等のその他の層を必要に応じて積層した積層体であることが好ましい。
（無機層）
　本発明においては、より高いガスバリア性及び水蒸気バリア性を発現させるために、基材上に無機層を積層してもよい。前記無機層は、Ａｌ、Ｓｉ、Ｚｎ、Ｓｎ、Ｔｉ、Ｃｒ、ＮｉおよびＩｎからなる群から選択される少なくとも１つ以上の金属の酸化物、当該金属の窒化物または当該金属の酸化窒化物であることが好ましい。上記無機層は、Ａｌ、Ｓｉ、Ｚｎ、Ｓｎ、Ｔｉ、Ｃｒ、ＮｉおよびＩｎの酸化物あるいは複酸化物により形成されることがより好ましい。上記無機層は、基材の片面のみに設けられていてもよいし、基材の両面に設けられてもよい。 The display element of the present invention is a laminate in which a base material layer, a base material sealing protective layer using the display element sealing material composition of the present invention, and other layers such as an inorganic layer are laminated as necessary. It is preferable that
(Inorganic layer)
In the present invention, an inorganic layer may be laminated on the substrate in order to develop higher gas barrier properties and water vapor barrier properties. The inorganic layer is an oxide of at least one metal selected from the group consisting of Al, Si, Zn, Sn, Ti, Cr, Ni, and In, a nitride of the metal, or an oxynitride of the metal. Preferably there is. The inorganic layer is more preferably formed of an oxide or a double oxide of Al, Si, Zn, Sn, Ti, Cr, Ni, and In. The inorganic layer may be provided only on one side of the substrate, or may be provided on both sides of the substrate.
　複酸化物中におけるＳｉの含有量は、特に限定されないが、２０質量部～８０質量部であることが好ましく、３０質量部～７０質量部であることがより好ましい。Ｓｉの含有量が上記範囲内にある場合、より一層透明性が高く、かつガスバリア性能に優れたバリア膜を提供することができる。 The content of Si in the double oxide is not particularly limited, but is preferably 20 parts by mass to 80 parts by mass, and more preferably 30 parts by mass to 70 parts by mass. When the Si content is within the above range, a barrier film having higher transparency and excellent gas barrier performance can be provided.
　また、複酸化物中におけるＺｎのＺｎとＳｎとの総量に対する重量比（Ｚｎ／Ｚｎ＋Ｓｎ）は、０．３～０．９９であることが好ましく、０．５～０．９であることがより好ましい。上記範囲内にある場合、ガスバリア性をより一層高めることができる。 The weight ratio of Zn to the total amount of Zn and Sn (Zn / Zn + Sn) in the double oxide is preferably 0.3 to 0.99, more preferably 0.5 to 0.9. preferable. When it exists in the said range, gas barrier property can be improved further.
　上記無機層の膜厚としては特に限定されないが、３０ｎｍ～３０００ｎｍであることが好ましく、５０ｎｍ～１０００ｎｍであることがより好ましい。膜厚が上記範囲にある場合、より一層ガスバリア性能を高めることができる。 The film thickness of the inorganic layer is not particularly limited, but is preferably 30 nm to 3000 nm, and more preferably 50 nm to 1000 nm. When the film thickness is in the above range, the gas barrier performance can be further enhanced.
　無機層の屈折率としては、特に限定されないが、１．９以下であることが望ましく、１．８以下であることがより望ましい。基材として用いられるポリエチレンナフタレートや、ポリエチレンテレフタレート等のプラスチックフィルムの屈折率は、１．６～１．７５程度であるため、無機層の屈折率を１．９以下にすることにより、基材と無機層との界面での光の反射をより一層抑制することができる。すなわち、バリア層の透明性がより一層高められる。
（基材）
　本発明の表示素子用封止材料組成物は、表示素子の基材封止保護剤として用いられるが、当該表示素子に用いられる基材は、液晶デバイス、ディスプレイ、光学部品や光学フィルムに通常使用する基材であって、本発明の表示素子用封止材料組成物の塗布後の乾燥時における必要に応じた加熱に耐えうる耐熱性を有する材料であれば、特に制限はない。そのような基材としては、ガラス基材、金属基材、セラミックス基材やプラスチック基材等の有機材料が挙げられるが、ガスバリア性や水蒸気バリア性に優れる本発明の表示素子用封止材料組成物は以下の有機材料の基材を用いた場合のガスバリア性や水蒸気バリア性の改善に特に効果的である。基材が有機材料の場合、セルロース誘導体、ポリオレフィン、ポリエステル、ポリカーボネート、ポリアクリレート（アクリル樹脂）、ポリアリレート、ポリエーテルサルホン、ポリイミド、ポリフェニレンスルフィド、ポリフェニレンエーテル、ナイロン又はポリスチレン等が挙げられる。中でもポリエステル、ポリスチレン、ポリアクリレート、ポリオレフィン、セルロース誘導体、ポリアリレート、ポリカーボネート等のプラスチック基材が好ましく、ポリアクリレート、ポリオレフィン、セルロース誘導体等の基材がさらに好ましく、ポリオレフィンとしてＣＯＰ（シクロオレフィンポリマー）を用い、セルロース誘導体としてＴＡＣ（トリアセチルセルロース）を用い、ポリアクリレートとしてＰＭＭＡ（ポリメチルメタクリレート）を用いることが特に好ましい。基材の形状としては、平板の他、曲面を有するものであっても良い。これらの基材は、必要に応じて、電極層、反射防止機能、反射機能を有していてもよい。 The refractive index of the inorganic layer is not particularly limited, but is preferably 1.9 or less, and more preferably 1.8 or less. Since the refractive index of a plastic film such as polyethylene naphthalate or polyethylene terephthalate used as the substrate is about 1.6 to 1.75, the refractive index of the inorganic layer can be reduced to 1.9 or less. The reflection of light at the interface between the inorganic layer and the inorganic layer can be further suppressed. That is, the transparency of the barrier layer is further enhanced.
(Base material)
The sealing material composition for display elements of the present invention is used as a base material sealing protective agent for display elements, but the base material used for the display elements is usually used for liquid crystal devices, displays, optical components and optical films. There is no particular limitation as long as it is a base material that has heat resistance that can withstand heating as needed during drying after application of the sealing material composition for display elements of the present invention. Examples of such a base material include organic materials such as a glass base material, a metal base material, a ceramic base material, and a plastic base material, but the sealing material composition for a display element of the present invention having excellent gas barrier properties and water vapor barrier properties. The product is particularly effective in improving gas barrier properties and water vapor barrier properties when the following organic material base is used. When the substrate is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polycarbonates, polyacrylates (acrylic resins), polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, and polystyrene. Among them, plastic base materials such as polyester, polystyrene, polyacrylate, polyolefin, cellulose derivative, polyarylate, and polycarbonate are preferable, and base materials such as polyacrylate, polyolefin, and cellulose derivative are more preferable, and COP (cycloolefin polymer) is used as the polyolefin. It is particularly preferable to use TAC (triacetyl cellulose) as the cellulose derivative and PMMA (polymethyl methacrylate) as the polyacrylate. As a shape of a base material, you may have a curved surface other than a flat plate. These base materials may have an electrode layer, an antireflection function, and a reflection function as needed.
　本発明の表示素子用封止材料組成物の塗布性や接着性向上のために、これらの基材の表面処理を行っても良い。表面処理として、オゾン処理、プラズマ処理、コロナ処理、シランカップリング処理などが挙げられる。また、光の透過率や反射率を調節するために、基材表面に有機薄膜、無機酸化物薄膜や金属薄膜等を蒸着など方法によって設ける、あるいは、光学的な付加価値をつけるために、基材がピックアップレンズ、ロッドレンズ、光ディスク、位相差フィルム、光拡散フィルム、カラーフィルター、等であっても良い。中でも付加価値がより高くなるピックアップレンズ、位相差フィルム、光拡散フィルム、カラーフィルターは好ましい。
（基材の配向処理）
　また、上記基材には、本発明の表示素子用封止材料組成物を塗布乾燥した際に表示素子用封止材料組成物が配向するように、通常配向処理が施されている、あるいは配向膜が設けられていても良い。配向処理としては、延伸処理、ラビング処理、偏光紫外可視光照射処理、イオンビーム処理等が挙げられる。配向膜を用いる場合、配向膜は公知慣用のものが用いられる。そのような配向膜としては、ポリイミド、ポリシロキサン、ポリアミド、ポリビニルアルコール、ポリカーボネート、ポリスチレン、ポリフェニレンエーテル、ポリアリレート、ポリエチレンテレフタレート、ポリエーテルサルホン、エポキシ樹脂、エポキシアクリレート樹脂、アクリル樹脂、クマリン化合物、カルコン化合物、シンナメート化合物、フルギド化合物、アントラキノン化合物、アゾ化合物、アリールエテン化合物等の化合物が挙げられる。ラビングにより配向処理する化合物は、配向処理、もしくは配向処理の後に加熱工程を入れることで材料の結晶化が促進されるものが好ましい。ラビング以外の配向処理を行う化合物の中では光配向材料を用いることが好ましい。 In order to improve the applicability and adhesion of the sealing material composition for display elements of the present invention, these substrates may be subjected to surface treatment. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.
(Substrate orientation treatment)
In addition, the substrate is usually subjected to an orientation treatment so that the display element sealing material composition is oriented when the display element sealing material composition of the present invention is applied and dried, or the orientation is applied. A film may be provided. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.
　本発明において、上記基材や、配向膜等を用いた配向処理した膜を合わせて基質と呼ぶことがある。
（被シール材）
　本発明の表示素子用封止材料組成物は、表示素子のシール剤として用いられる。具体的には、発光性の有機化合物を含む層を覆うバリア層の側面を封止する層として使用される。
（表示素子用封止材料組成物の塗布）
　本発明の表示素子用封止材料組成物の基材、基質又は被シール材への塗布法としては、アプリケーター法、バーコーティング法、スピンコーティング法、ロールコーティング法、ダイレクトグラビアコーティング法、リバースグラビアコーティング法、フレキソコーティング法、インクジェット法、ダイコーティング法、キャップコーティング法、ディップコーティング法、スリットコーティング法及びディスペンサーを用いた吐出法等、公知慣用の方法を行うことができる。前記ディスペンサ法等は有機溶剤を用いなくても使用可能であるが、有機溶剤を用いている場合は、表示素子用封止材料組成物を基質に塗布後、有機溶剤を揮発等のため必要に応じて乾燥させる。
（重合工程）
　本発明の表示素子用封止材料組成物の重合操作については、有機溶剤を用いている場合は、有機溶剤を揮発後、表示素子用封止材料組成物中の液晶化合物が基質に対して水平配向、垂直配向、又はハイブリッド配向、あるいはコレステリック配向（平面配向）した状態で一般に紫外線等の光照射、あるいは加熱によって行われる。重合を光照射で行う場合は、具体的には３９０ｎｍ以下の紫外光を照射することが好ましく、２５０～３７０ｎｍの波長の光を照射することが最も好ましい。但し、３９０ｎｍ以下の紫外光により表示素子用封止材料組成物が分解などを引き起こす場合は、３９０ｎｍ以上の紫外光で重合処理を行ったほうが好ましい場合もある。この光は、拡散光で、かつ偏光していない光であることが好ましい。
（重合方法）
　本発明の表示素子用封止材料組成物を重合させる方法としては、活性エネルギー線を照射する方法や熱重合法等が挙げられるが、加熱を必要とせず、室温で反応が進行することから活性エネルギー線を照射する方法が好ましく、中でも、操作が簡便なことから、紫外線等の光を照射する方法が好ましい。 In the present invention, the substrate and the alignment-treated film using an alignment film may be collectively referred to as a substrate.
(Seal material)
The sealing material composition for display elements of the present invention is used as a sealant for display elements. Specifically, it is used as a layer for sealing the side surface of the barrier layer covering the layer containing a light-emitting organic compound.
(Application of sealing material composition for display element)
As a method for applying the sealing material composition for display elements of the present invention to a substrate, a substrate or a material to be sealed, an applicator method, bar coating method, spin coating method, roll coating method, direct gravure coating method, reverse gravure coating Known and commonly used methods such as a method, a flexo coating method, an ink jet method, a die coating method, a cap coating method, a dip coating method, a slit coating method, and a discharge method using a dispenser can be performed. The dispenser method and the like can be used without using an organic solvent. However, when an organic solvent is used, the organic solvent is required for volatilization after the display element sealing material composition is applied to the substrate. Dry accordingly.
(Polymerization process)
For the polymerization operation of the sealing material composition for display elements of the present invention, when an organic solvent is used, the liquid crystal compound in the sealing material composition for display elements is horizontal with respect to the substrate after volatilizing the organic solvent. In general, the alignment, vertical alignment, hybrid alignment, or cholesteric alignment (planar alignment) is performed by irradiation with light such as ultraviolet rays or heating. When the polymerization is performed by light irradiation, specifically, irradiation with ultraviolet light of 390 nm or less is preferable, and irradiation with light having a wavelength of 250 to 370 nm is most preferable. However, when the sealing material composition for a display element causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light.
(Polymerization method)
Examples of the method for polymerizing the sealing material composition for a display device of the present invention include a method of irradiating active energy rays and a thermal polymerization method. However, it does not require heating and is active because the reaction proceeds at room temperature. A method of irradiating energy rays is preferable, and among them, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple.
　照射時の温度は、本発明の表示素子用封止材料組成物が液晶相を保持できる温度とし、表示素子用封止材料組成物の熱重合の誘起を避けるため、可能な限り４０℃以下とすることが好ましい。尚、液晶組成物は、通常、昇温過程において、Ｃ（固相）－Ｎ（ネマチック）転移温度（以下、Ｃ－Ｎ転移温度と略す。）から、Ｎ－Ｉ転移温度範囲内で液晶相を示す。一方、降温過程においては、熱力学的に非平衡状態を取るため、Ｃ－Ｎ転移温度以下でも凝固せず液晶状態を保つ場合がある。この状態を過冷却状態という。本発明においては、過冷却状態にある液晶組成物も液晶相を保持している状態に含めるものとする。具体的には３９０ｎｍ以下の紫外光を照射することが好ましく、２５０～３７０ｎｍの波長の光を照射することが最も好ましい。但し、３９０ｎｍ以下の紫外光により表示素子用封止材料組成物が分解などを引き起こす場合は、３９０ｎｍ以上の紫外光で重合処理を行ったほうが好ましい場合もある。この光は、拡散光で、かつ偏光していない光であることが好ましい。紫外線照射強度は、０．０５ｋＷ／ｍ２～１０ｋＷ／ｍ２の範囲が好ましい。特に、０．２ｋＷ／ｍ２～２ｋＷ／ｍ２の範囲が好ましい。紫外線強度が０．０５ｋＷ／ｍ２未満の場合、重合を完了させるのに多大な時間がかかる。一方、２ｋＷ／ｍ２を超える強度では、表示素子用封止材料組成物中の液晶分子が光分解する傾向にあることや、重合熱が多く発生して重合中の温度が上昇し、重合性液晶のオーダーパラメーターが変化して、重合後のフィルムのリタデーションに狂いが生じる可能性がある。 The temperature at the time of irradiation is set to 40 ° C. or less as much as possible in order to avoid the induction of thermal polymerization of the sealing material composition for display elements, so that the sealing material composition for display elements of the present invention can maintain the liquid crystal phase. It is preferable to do. The liquid crystal composition usually has a liquid crystal phase within a range from the C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as the CN transition temperature) to the NI transition temperature in the temperature rising process. Indicates. On the other hand, in the temperature lowering process, since the thermodynamically non-equilibrium state is obtained, there is a case where the liquid crystal state is not solidified even at a temperature below the CN transition temperature. This state is called a supercooled state. In the present invention, the liquid crystal composition in a supercooled state is also included in the state in which the liquid crystal phase is retained. Specifically, irradiation with ultraviolet light of 390 nm or less is preferable, and irradiation with light having a wavelength of 250 to 370 nm is most preferable. However, when the sealing material composition for a display element causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light. Ultraviolet irradiation intensity in the range of 0.05kW / m 2 ~ 10kW / m 2 is preferred. In particular, the range of 0.2 kW / m 2 to 2 kW / m 2 is preferable. When the ultraviolet intensity is less than 0.05 kW / m 2 , it takes a lot of time to complete the polymerization. On the other hand, when the strength exceeds 2 kW / m 2 , liquid crystal molecules in the sealing material composition for display elements tend to be photodecomposed, and a large amount of polymerization heat is generated, resulting in an increase in temperature during the polymerization. The order parameter of the liquid crystal changes, and there is a possibility that the retardation of the film after polymerization is distorted.
　マスクを使用して特定の部分のみを紫外線照射で重合させた後、該未重合部分の配向状態を、電場、磁場又は温度等をかけて変化させ、その後該未重合部分を重合させると、異なる配向方向をもった複数の領域を有する光学異方体を得ることもできる。 After only a specific part is polymerized by UV irradiation using a mask, the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field or temperature, and then the unpolymerized part is polymerized. An optical anisotropic body having a plurality of regions having orientation directions can also be obtained.
　また、マスクを使用して特定の部分のみを紫外線照射で重合させる際に、予め未重合状態の表示素子用封止材料組成物に電場、磁場又は温度等をかけて配向を規制し、その状態を保ったままマスク上から光を照射して重合させることによっても、異なる配向方向をもった複数の領域を有するフィルムを得ることができる。
（表示素子用シール剤）
　本発明の表示素子用封止材料組成物は、上述のとおり、液晶表示素子や有機発光表示素子のシール剤として好適に用いることができる。具体的には、液晶ディスプレイ、有機ＥＬディスプレイ、無機ＥＬディスプレイ、量子ドットディスプレイ、量子ロッドディスプレイ等の表示素子等のシール剤として好適に用いることができる。当該表示素子用封止材料組成物の塗工量は限定されてないが、通常は乾燥後のシール剤からなる層厚は、被シール材上の厚さが、５０μｍ～２００μｍとすることが好ましく、５０μｍ～１５０μｍとすることがより好ましく、５０μｍ～１２０μｍとすることが特に好ましい。
（表示素子に用いる基材封止保護剤）
　本発明の表示素子用封止材料組成物は、上述のとおり、表示素子に用いる基材封止保護剤として好適に用いることができる。具体的には、有機ＥＬディスプレイ、無機ＥＬディスプレイ、量子ドットディスプレイ、量子ロッドディスプレイ等の表示素子等に用いることができ、基材上に用いて基材封止保護層として好適に用いることができる。当該表示素子用封止材料組成物の塗工量は限定されてないが、通常は乾燥後の当該基材封止保護剤からなる層厚は、基材上の厚さが、４０μｍ～８０μｍとすることが好ましく、４０μｍ～７０μｍとすることがより好ましく、４０μｍ～６０μｍとすることが特に好ましい。 Further, when only a specific portion is polymerized by ultraviolet irradiation using a mask, the orientation is regulated by applying an electric field, a magnetic field, or temperature to the display element sealing material composition in an unpolymerized state in advance. A film having a plurality of regions having different orientation directions can also be obtained by polymerizing by irradiating light from above the mask while maintaining.
(Sealant for display element)
As described above, the sealing material composition for display elements of the present invention can be suitably used as a sealing agent for liquid crystal display elements and organic light emitting display elements. Specifically, it can be suitably used as a sealing agent for display elements such as liquid crystal displays, organic EL displays, inorganic EL displays, quantum dot displays, and quantum rod displays. The coating amount of the sealing material composition for display elements is not limited, but it is usually preferable that the layer thickness of the sealing agent after drying is 50 μm to 200 μm on the sealing material. 50 μm to 150 μm is more preferable, and 50 μm to 120 μm is particularly preferable.
(Substrate sealing protectant used for display element)
As described above, the sealing material composition for a display element of the present invention can be suitably used as a substrate sealing protective agent used for a display element. Specifically, it can be used for display elements such as an organic EL display, an inorganic EL display, a quantum dot display, and a quantum rod display, and can be suitably used as a base material sealing protective layer when used on a base material. . Although the coating amount of the display element sealing material composition is not limited, the layer thickness of the base material sealing protective agent after drying is usually 40 μm to 80 μm on the base material. It is preferably 40 μm to 70 μm, more preferably 40 μm to 60 μm.
　以下に本発明を合成例、実施例、及び、比較例によって説明するが、もとより本発明はこれらに限定されるものではない。なお、特に断りのない限り、「部」及び「％」は質量基準である。
（表示素子用封止材料組成物の作製）
（分散液Ａの調整）
　ジメチルステアリルベンジルアンモニウムで有機化された有機化層状ケイ酸塩（エスベンＮＺ、株式会社ホージュン製）１００部にシリル化剤として３－メタクリロキシプロピルトリメトキシシラン（ＫＢＭ－５０３、信越化学工業株式会社製）を３部混合し、窒素雰囲気下でボールミル処理することにより充填材ａを得た。この充填材ａ１０部にトルエン２８９部を加え、２５℃２時間攪拌して充填材ａが均一に分散した分散液Ａを得た。
（重合性液晶組成物（Ｕ―１）の調整）
　式（Ｂ－１）で表される化合物４５部、式（Ｂ－２）で表される化合物４５部、式（Ｃ－１）で表される化合物１０部、ｐ－メトキシフェノール(ＭＥＨＱ)０．１部をトルエン１５９部に加えた後、７０℃に加温、撹拌して溶解させ、溶解が確認された後、５０℃にてイルガキュア９０７（Irg.907：ＢＡＳＦジャパン株式会社製）３部、イルガキュアＴＰＯ（ＴＰＯ：ＢＡＳＦジャパン株式会社製）３部、及びメガファックＦ－５５４（F-554：ＤＩＣ株式会社製）０．２部を加えてさらに撹拌し、溶液（Ｕ－１）を得た。
（重合性液晶組成物（Ｕ－２）～（Ｕ－１５）の調製）
　本発明の重合性液晶組成物（Ｕ－１）の調製と同様に、表１に示す（Ｂ－１）～式（Ｂ－１１）で表される化合物、式（Ｃ－１）～式（Ｃ－１３）で表される化合物、式（Ｄ－１）で表される化合物の各化合物をそれぞれ表１～表２に示す割合に変更した以外は重合性液晶組成物（Ｕ－１）の調製と同一条件で、それぞれ、重合性液晶組成物（Ｕ－２）～（Ｕ－１５）を得た。
（重合性液晶組成物（Ｕ―１６）の調整）
　式（Ｂ－１）で表される化合物４５部、式（Ｂ－２）で表される化合物４５部、式（Ｃ－１）で表される化合物１０部、ｐ－メトキシフェノール(MEHQ)０．１部を、１００℃に加温、撹拌して溶解させ、溶解が確認された後、５０℃にてイルガキュア９０７（Irg.907：ＢＡＳＦジャパン株式会社製）３部、イルガキュアＴＰＯ（ＴＰＯ：ＢＡＳＦジャパン株式会社製）３部、及びメガファックＦ－５５４（F-554：ＤＩＣ株式会社製）０．２部を加えてさらに撹拌し、溶液（Ｕ－１６）を得た。
（重合性液晶組成物（Ｕ－１７）の調製）
　本発明の重合性液晶組成物（Ｕ－１６）の調製と同様に、表１に示す（Ｂ－１）～式（Ｂ－１１）で表される化合物、式（Ｃ－１）～式（Ｃ－１３）で表される化合物の各化合物をそれぞれ表３に示す割合に変更し、１２０℃で加温攪拌溶解させた以外は重合性液晶組成物（Ｕ－１６）の調製と同一条件で、重合性液晶組成物（Ｕ－１７）を得た。 Hereinafter, the present invention will be described with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.
(Preparation of sealing material composition for display element)
(Preparation of dispersion A)
3-Methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silylating agent was added to 100 parts of an organically modified layered silicate (Esben NZ, manufactured by Hojun Co., Ltd.) that was organized with dimethylstearylbenzylammonium. ) Was mixed and ball milled in a nitrogen atmosphere to obtain a filler a. 289 parts of toluene was added to 10 parts of this filler a and stirred at 25 ° C. for 2 hours to obtain a dispersion A in which the filler a was uniformly dispersed.
(Adjustment of polymerizable liquid crystal composition (U-1))
45 parts of the compound represented by formula (B-1), 45 parts of the compound represented by formula (B-2), 10 parts of the compound represented by formula (C-1), p-methoxyphenol (MEHQ) 0 .1 part is added to 159 parts of toluene, heated to 70 ° C. and dissolved by stirring. After dissolution is confirmed, 3 parts of Irgacure 907 (Irg.907: manufactured by BASF Japan Ltd.) at 50 ° C. , 3 parts of Irgacure TPO (TPO: manufactured by BASF Japan Ltd.) and 0.2 part of MegaFuck F-554 (F-554: manufactured by DIC Corporation) were added and further stirred to obtain a solution (U-1). It was.
(Preparation of polymerizable liquid crystal compositions (U-2) to (U-15))
Similar to the preparation of the polymerizable liquid crystal composition (U-1) of the present invention, the compounds represented by the formulas (B-1) to (B-11) shown in Table 1, formulas (C-1) to ( The polymerizable liquid crystal composition (U-1) was used except that the compounds represented by C-13) and the compound represented by formula (D-1) were changed to the ratios shown in Tables 1 and 2, respectively. Polymeric liquid crystal compositions (U-2) to (U-15) were obtained under the same conditions as in the preparation.
(Adjustment of polymerizable liquid crystal composition (U-16))
45 parts of the compound represented by formula (B-1), 45 parts of the compound represented by formula (B-2), 10 parts of the compound represented by formula (C-1), p-methoxyphenol (MEHQ) 0 .1 part was heated and stirred at 100 ° C. and dissolved, and after dissolution was confirmed, 3 parts Irgacure 907 (Irg.907: manufactured by BASF Japan Ltd.), Irgacure TPO (TPO: BASF) 3 parts of Japan Co., Ltd.) and 0.2 part of MegaFuck F-554 (F-554: manufactured by DIC Corporation) were added and further stirred to obtain a solution (U-16).
(Preparation of polymerizable liquid crystal composition (U-17))
Similar to the preparation of the polymerizable liquid crystal composition (U-16) of the present invention, the compounds represented by the formulas (B-1) to (B-11) shown in Table 1, formulas (C-1) to (B) The compounds represented by C-13) were changed to the ratios shown in Table 3, and were heated and dissolved at 120 ° C. under the same conditions as in the preparation of the polymerizable liquid crystal composition (U-16). A polymerizable liquid crystal composition (U-17) was obtained.
　表１～表３に、本発明の重合性液晶組成物（Ｕ－１）～（Ｕ－１７）の具体的な組成を示す。 Tables 1 to 3 show specific compositions of the polymerizable liquid crystal compositions (U-1) to (U-17) of the present invention.
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
パラメトキシフェノール（和光純薬工業株式会社社製）（Ｅ－１）
イルガキュア９０７（ＢＡＳＦジャパン株式会社製）（Ｆ－１）
ルシリンＴＰＯ（ＢＡＳＦジャパン株式会社製）（Ｆ－２）
メガファックＦ－５５４（ＤＩＣ株式会社製）（Ｇ－１）
（重合性液晶組成物の相転移温度）
　重合性液晶組成物（Ｕ－１）をスピンコーターでガラス基板上に塗布し８０℃で溶剤乾燥させ、ガラス基板上に重合性液晶組成物（Ｕ－１）が塗布された膜を形成した。この膜をホットステージ上で１４０℃まで昇温した後、降温時の相転移を偏光顕微鏡にて観察して測定したところ５８℃でネマチック相に相転移した。 Paramethoxyphenol (Wako Pure Chemical Industries, Ltd.) (E-1)
Irgacure 907 (manufactured by BASF Japan Ltd.) (F-1)
Lucillin TPO (BASF Japan Ltd.) (F-2)
Megafuck F-554 (manufactured by DIC Corporation) (G-1)
(Phase transition temperature of polymerizable liquid crystal composition)
The polymerizable liquid crystal composition (U-1) was applied onto a glass substrate with a spin coater and dried in a solvent at 80 ° C. to form a film on which the polymerizable liquid crystal composition (U-1) was applied on the glass substrate. The film was heated to 140 ° C. on a hot stage, and the phase transition at the time of cooling was measured by observing with a polarizing microscope. As a result, the phase transition to a nematic phase was performed at 58 ° C.
　重合性液晶組成物（Ｕ－２）～（Ｕ－１３）の相転移温度は、（Ｕ－１）と同一条件で、又、（Ｕ－１４）～（Ｕ－１５）の相転移温度は１９０℃まで昇温してから（Ｕ－１）と同一条件にて観察し測定した。 The phase transition temperatures of the polymerizable liquid crystal compositions (U-2) to (U-13) are the same as those of (U-1), and the phase transition temperatures of (U-14) to (U-15) are After raising the temperature to 190 ° C., the measurement was performed under the same conditions as (U-1).
　重合性液晶組成物（Ｕ－１６）および（Ｕ－１７）の相転移温度は、重合性液晶組成物をガラス基板上にスパチュラで薄く展ばしたものを作製し、（Ｕ－１）と同一条件で乾燥、昇温した後に、観察し測定した。 The phase transition temperature of the polymerizable liquid crystal compositions (U-16) and (U-17) is the same as (U-1), which is obtained by thinly spreading the polymerizable liquid crystal composition on a glass substrate with a spatula. It was observed and measured after drying and heating up under conditions.
　重合性液晶組成物（Ｕ－１）～（Ｕ－１７）の相転移温度を以下表４に示す。 The phase transition temperatures of the polymerizable liquid crystal compositions (U-1) to (U-17) are shown in Table 4 below.
Figure JPOXMLDOC01-appb-T000082
Figure JPOXMLDOC01-appb-T000082
表中のＳＢはスメクチックＢ、ＳＡはスメクチックＡ、Ｎはネマチック、Ｎｄはディスコチックネマチック、Ｉは等方的をそれぞれ意味する。
（封止材料組成物の調整）
　重合性液晶組成物（Ｕ－１）７５ｇ中に分散液Ａ１００ｇを添加し室温で撹拌することにより充填材ａが均一分散した封止材料組成物（１）を得た。
（封止材料組成物（２）～（１５）の調製）
　重合性液晶組成物（Ｕ－１）を（Ｕ－２）～（Ｕ－１５）に変更した以外は封止材料組成物（Ｕ－１）の調製と同一条件で、それぞれ、封止材料組成物（２）～（１５）を得た。
（封止材料組成物（１６）の調製）
重合性液晶組成物（Ｕ－１６）９５ｇ中に充填材ａ ５ｇを添加し５０℃で撹拌することにより充填材ａが均一分散した封止材料組成物（１６）を得た。
（封止材料組成物（１７）の調製）
重合性液晶組成物（Ｕ－１７）９５ｇ中に充填材ａ ５ｇを添加し５０℃で撹拌することにより充填材ａが均一分散した封止材料組成物（１７）を得た。
（実施例１）
（封止材料積層体（１）の作製）
　ナイロン布でラビング処理した１２μｍ厚のＰＥＴ基材フィルム（４０℃９０％ＲＨでの水蒸気透過度５０ｇ／ｍ２・ｄａｙ（１００μｍ換算））上に、封止材料組成物（１）を、ワイヤーバーを用いて塗布し、８０℃で溶剤乾燥したのち、コンベア式の高圧水銀ランプを使用して５００ｍＪ／ｃｍ２でＵＶ照射し、ＰＥＴ上に封止材料層が積層された封止材料積層体（１）を得た。
（水蒸気透過度の測定および計算）
　得られた封止材料積層体（１）について、４０℃９０％ＲＨカップ法（ＪＩＳ　Ｚ０２０８－１９７６）により水蒸気透過度を測定した。式（１）から封止材料層の水蒸気透過度を算出したところ、３．２ｇ／ｍ２・ｄａｙ（１００μｍ換算）であった。
Ｐ（水蒸気透過率）＝｛Ｐ（積層体）×Ｐ（ＰＥＴ基材）｝／｛Ｐ（ＰＥＴ基材）－Ｐ（積層体）｝：　式（１）
（式（１）中、Ｐは、各層の水蒸気透過率を表す。）
（屈曲性評価）
　曲率半径６ミリメートルのマンドレル型屈曲試験機を用いて、上記封止材料積層体（１）の屈曲性を評価した（ＪＩＳ　ＳＫ５６００－５－１）ところ、クラック等の欠陥は発生しなかった。また、屈曲性はクラックの発生状況により以下評価を行った。 S B in the table smectic B, S A = smectic A, N = nematic, N d is a discotic nematic, I is meant isotropic, respectively.
(Adjustment of sealing material composition)
100 g of the dispersion A was added to 75 g of the polymerizable liquid crystal composition (U-1) and stirred at room temperature to obtain a sealing material composition (1) in which the filler a was uniformly dispersed.
(Preparation of sealing material compositions (2) to (15))
Except for changing the polymerizable liquid crystal composition (U-1) to (U-2) to (U-15), under the same conditions as the preparation of the sealing material composition (U-1), Products (2) to (15) were obtained.
(Preparation of sealing material composition (16))
5 g of filler a was added to 95 g of the polymerizable liquid crystal composition (U-16) and stirred at 50 ° C. to obtain a sealing material composition (16) in which the filler a was uniformly dispersed.
(Preparation of sealing material composition (17))
5 g of filler a was added to 95 g of the polymerizable liquid crystal composition (U-17) and stirred at 50 ° C. to obtain a sealing material composition (17) in which the filler a was uniformly dispersed.
Example 1
(Preparation of sealing material laminate (1))
A sealing material composition (1) is placed on a 12 μm-thick PET base film rubbed with a nylon cloth (water vapor transmission rate at 40 ° C. and 90% RH 50 g / m 2 · day (100 μm conversion)) After applying the solvent and drying at 80 ° C. with a solvent, UV irradiation is performed at 500 mJ / cm 2 using a conveyor-type high-pressure mercury lamp, and a sealing material laminate in which a sealing material layer is laminated on PET ( 1) was obtained.
(Measurement and calculation of water vapor permeability)
With respect to the obtained sealing material laminate (1), the water vapor transmission rate was measured by a 40 ° C. 90% RH cup method (JIS Z0208-1976). When the water vapor permeability of the sealing material layer was calculated from the formula (1), it was 3.2 g / m 2 · day (100 μm conversion).
P (water vapor transmission rate) = {P (laminate) × P (PET base material)} / {P (PET base material) −P (laminate)}: Formula (1)
(In formula (1), P represents the water vapor transmission rate of each layer.)
(Flexibility evaluation)
Using a mandrel type bending tester having a curvature radius of 6 mm, the bending property of the sealing material laminate (1) was evaluated (JIS SK5600-5-1), and no defects such as cracks were generated. The flexibility was evaluated as follows according to the occurrence of cracks.
　○：クラックなど欠陥の発生なし。 ○: No defects such as cracks occurred.
　△：ごく僅かにクラックが発生する。 △: A slight crack is generated.
　×：多数クラックが発生する。
（実施例２～１５）
（封止材料積層体（２）～（１５）の作製）
　封止材料組成物（１）を封止材料組成物（２）～（１５）に変更した以外は封止材料積層体（１）の作製と同一条件で、それぞれ、封止材料積層体（２）～（１５）を得た。
（封止材料積層体（１６）の作製）
　ナイロン布でラビング処理した１２μｍ厚のＰＥＴフィルム（４０℃９０％ＲＨでの水蒸気透過度５０ｇ／ｍ２・ｄａｙ（１００μｍ換算）上に、アプリケーターを用いて封止材料組成物（１６）を塗布し、コンベア式の高圧水銀ランプを使用して５００ｍＪ／ｃｍ２でＵＶ照射し、ＰＥＴ上に封止材料層が積層された封止材料積層体（１６）を得た。
（封止材料積層体（１７）の作製）
　封止材料組成物（１６）を封止材料組成物（１７）に変更した以外は封止材料積層体（１６）の作製と同一条件で封止材料積層体（１７）を得た。 X: Many cracks occur.
(Examples 2 to 15)
(Preparation of sealing material laminates (2) to (15))
Except for changing the sealing material composition (1) to the sealing material compositions (2) to (15), under the same conditions as the production of the sealing material laminate (1), the sealing material laminate (2 ) To (15) were obtained.
(Preparation of sealing material laminate (16))
A sealing material composition (16) was applied to a PET film having a thickness of 12 μm rubbed with a nylon cloth (water vapor permeability of 50 g / m 2 · day (100 μm conversion) at 40 ° C. and 90% RH) using an applicator. Then, UV irradiation was performed at 500 mJ / cm 2 using a conveyor type high-pressure mercury lamp to obtain a sealing material laminate (16) in which a sealing material layer was laminated on PET.
(Preparation of sealing material laminate (17))
A sealing material laminate (17) was obtained under the same conditions as in the production of the sealing material laminate (16) except that the sealing material composition (16) was changed to the sealing material composition (17).
　得られた封止材料積層体（２）～（１７）の水蒸気透過率測定および屈曲性評価は、実施例１と同様に行った。 The water vapor transmission rate measurement and the flexibility evaluation of the obtained sealing material laminates (2) to (17) were performed in the same manner as in Example 1.
　得られた結果を表５に示す。 Table 5 shows the obtained results.
Figure JPOXMLDOC01-appb-T000083
Figure JPOXMLDOC01-appb-T000083
（比較例１）
　重合性液晶組成物（Ｕ－４）７５ｇ中にトルエン８２．５ｇを添加し室温で撹拌することにより、比較用封止材料組成物（Ｃ１）を得た。 (Comparative Example 1)
By adding 82.5 g of toluene to 75 g of the polymerizable liquid crystal composition (U-4) and stirring at room temperature, a comparative sealing material composition (C1) was obtained.
　ナイロン布でラビング処理した厚さ１２ミクロンのＰＥＴフィルム（４０℃９０％ＲＨでの水蒸気透過度５０ｇ／ｍ２・ｄａｙ（１００μｍ換算））上に、ワイヤーバーを用いて比較用封止材料組成物（Ｃ１）を塗布し、８０℃で溶剤乾燥した後、コンベア式の高圧水銀ランプを使用して５００ｍＪ／ｃｍ２でＵＶ照射し、ＰＥＴ上に封止材料層が積層された比較用積層体（Ｃ１）を得た。 A sealing material composition for comparison using a wire bar on a PET film having a thickness of 12 microns rubbed with a nylon cloth (water vapor transmission rate at 40 ° C. and 90% RH of 50 g / m 2 · day (100 μm conversion)). (C1) was applied, and after solvent drying at 80 ° C., UV irradiation was performed at 500 mJ / cm 2 using a conveyor-type high-pressure mercury lamp, and a comparative laminate in which a sealing material layer was laminated on PET ( C1) was obtained.
　得られた比較用積層体について、４０℃９０％ＲＨカップ法（ＪＩＳ　Ｚ０２０８－１９７６）により水蒸気透過度を測定した。上記式（１）から封止材料層の水蒸気透過度を算出したところ１０４ｇ／ｍ２・ｄａｙ（１００μｍ換算）であった。 With respect to the obtained comparative laminate, the water vapor transmission rate was measured by a 40 ° C. 90% RH cup method (JIS Z0208-1976). The water vapor permeability of the sealing material layer calculated from the above formula (1) was 104 g / m 2 · day (100 μm conversion).
　曲率半径６ミリメートルのマンドレル型屈曲試験機を用いて、上記比較用積層体の屈曲性を評価した（ＪＩＳ　ＳＫ５６００－５－１）ところ、クラックなど何の欠陥も発生しなかった。
（実施例１８）
（無機膜の積層）
　封止材料積層体（１）をスパッタ装置の成膜室中の基板ホルダーに取り付け、さらに第１のカソードにＺｎＳｎ合金ターゲット（重量比Ｚｎ：Ｓｎ＝９５：５）を、第２のカソードにＳｉターゲットを取り付けた。次に、成膜室を真空ポンプにより排気し５．０×１０－４Ｐａまで減圧した。その後、下記成膜条件Ａに示す条件でスパッタリングし、上記積層体（１）上に無機膜として厚み１５０ｎｍのＳｉＺｎＳｎＯ膜を形成し、蒸着積層体（１８）を得た。 The bending property of the comparative laminate was evaluated using a mandrel type bending tester having a curvature radius of 6 mm (JIS SK5600-5-1), and no defects such as cracks were generated.
(Example 18)
(Lamination of inorganic film)
The sealing material laminate (1) is attached to the substrate holder in the film forming chamber of the sputtering apparatus, and further, a ZnSn alloy target (weight ratio Zn: Sn = 95: 5) is used for the first cathode, and Si is used for the second cathode. A target was attached. Next, the film forming chamber was evacuated by a vacuum pump and the pressure was reduced to 5.0 × 10 −4 Pa. Thereafter, sputtering was performed under the conditions shown in the following film formation condition A to form a SiZnSnO film having a thickness of 150 nm as an inorganic film on the laminate (1) to obtain a vapor deposition laminate (18).
　［成膜条件Ａ]
　　アルゴンガス流量：５０ｓｃｃｍ、酸素ガス流量：５０ｓｃｃｍ
　　電源出力：第一のカソード＝５００Ｗ、第二のカソード＝１５００Ｗ
　得られた蒸着積層体（１８）の水蒸気透過度は、差圧式透湿度測定装置（ＧＴＲ－３００ＸＡＳＣ、ＧＴＲテック株式会社製）により、ＪＩＳ　Ｋ　７１２６　Ａ法（差圧法）に準拠して、温度４０℃、湿度９０％の条件で測定したところ、７．０×１０－４ｇ／ｍ２・ｄａｙあった。 [Film formation conditions A]
Argon gas flow rate: 50 sccm, oxygen gas flow rate: 50 sccm
Power output: first cathode = 500 W, second cathode = 1500 W
The water vapor permeability of the obtained vapor-deposited laminate (18) was measured at a temperature of 40 according to the JIS K 7126 A method (differential pressure method) using a differential pressure type moisture permeability measuring device (GTR-300XASC, manufactured by GTR Tech Co., Ltd.). When measured under the conditions of ° C. and humidity of 90%, it was 7.0 × 10 −4 g / m 2 · day.
　得られた蒸着積層体（１８）の屈曲性評価は、実施例１と同様に行った。
（実施例１９～２２）
　封止材料積層体（１）を封止材料積層体（２）、（８）、（１０）および（１４）に変更した以外は、蒸着積層体（１）の作製と同一条件で、それぞれ、蒸着積層体（１９）～（２２）を得た。 Flexibility evaluation of the obtained vapor-deposited laminate (18) was performed in the same manner as in Example 1.
(Examples 19 to 22)
Except for changing the sealing material laminate (1) to the sealing material laminate (2), (8), (10) and (14), respectively, under the same conditions as the production of the vapor deposition laminate (1), Vapor deposited laminates (19) to (22) were obtained.
　得られた蒸着積層体（１９）～（２２）の水蒸気透過率測定および屈曲性評価は、実施例１８と同様に行った。
（実施例２３）
　第２のカソードにＡｌを取り付け、下記成膜条件Ｂに示す条件でスパッタリングし、封止材料積層体（１）上に無機膜として厚み１５０ｎｍのＡｌ２Ｏ３膜を形成し、蒸着積層体（２３）を得た。
［成膜条件Ｂ]
　　アルゴンガス流量：５０ｓｃｃｍ、酸素ガス流量：５０ｓｃｃｍ
　　電源出力：第一のカソード＝０Ｗ、第二のカソード＝１５００Ｗ
　得られた蒸着積層体（２３）の水蒸気透過率測定および屈曲性評価は、実施例１８と同様に行った。
（比較例２）
　封止材料層（１）を厚さ１２ミクロンのＰＥＴフィルムに変更した以外は、実施例１８と同様にして、比較用蒸着積層体（Ｃ２）を得た。 The vapor-deposited laminates (19) to (22) thus obtained were measured for water vapor permeability and evaluated for flexibility as in Example 18.
(Example 23)
Al is attached to the second cathode, and sputtering is performed under the conditions shown in the following film formation condition B to form an Al 2 O 3 film having a thickness of 150 nm as an inorganic film on the sealing material stack (1). 23) was obtained.
[Film formation condition B]
Argon gas flow rate: 50 sccm, oxygen gas flow rate: 50 sccm
Power output: 1st cathode = 0W, 2nd cathode = 1500W
The water vapor transmission rate measurement and the flexibility evaluation of the obtained vapor-deposited laminate (23) were carried out in the same manner as in Example 18.
(Comparative Example 2)
A comparative vapor deposition laminate (C2) was obtained in the same manner as in Example 18 except that the sealing material layer (1) was changed to a PET film having a thickness of 12 microns.
　得られた比較用蒸着積層体（Ｃ２）の水蒸気透過率測定および屈曲性評価は、実施例１８と同様に行った。 The water vapor permeability measurement and the flexibility evaluation of the comparative vapor deposition laminate (C2) obtained were performed in the same manner as in Example 18.
　得られた結果を表６に示す。 Table 6 shows the obtained results.
Figure JPOXMLDOC01-appb-T000084
Figure JPOXMLDOC01-appb-T000084

（分散液Ｂの調整）
　ジメチルステアリルベンジルアンモニウムで有機化された有機化層状ケイ酸塩（エスベンＮＺ、株式会社ホージュン製）１００部にシリル化剤として３－メタクリロキシプロピルトリメトキシシラン（ＫＢＭ－５０３、信越化学工業株式会社製）を３部混合し、窒素雰囲気下でボールミル処理することにより充填材ｂを得た。この充填材ｂ１５部に、ヒドロキシエチルアクリルアミド２０部、アセトン８０部を加え、２５℃２時間攪拌して充填材ｂが均一に分散した分散液Ｂを得た。
（重合性液晶組成物（Ｕ―１８）の調整）
　式（Ｂ－１）で表される化合物４５部、式（Ｂ－２）で表される化合物４５部、式（Ｃ－１）で表される化合物１０部、ｐ－メトキシフェノール（ＭＥＨＱ）０．１部を７０℃に加温、撹拌して溶解させ、溶解が確認された後、イルガキュア９０７（Irg.907：ＢＡＳＦジャパン株式会社製）２部、イルガキュアＴＰＯ（ＴＰＯ：ＢＡＳＦジャパン株式会社製）２部、及びメガファックＦ－５５４（F-554：ＤＩＣ株式会社製）０．２部を加えてさらに撹拌し、溶液（Ｕ－１８）を得た。
（封止材料組成物（１８）の調整）
　重合性液晶組成物（Ｕ－１８）９０ｇ中に分散液Ｂ１００ｇを添加し室温で撹拌した後、プラネタリミキサー中で溶剤脱気することにより充填材ｂが均一分散した封止材料組成物（１８）を得た。
（実施例２４）
　ナイロン布でラビング処理した５０μｍ厚のＰＥＴ基材フィルム上に、封止材料組成物（１８）を、アプリケーターを用いて塗布し、コンベア式の高圧水銀ランプを使用して５００ｍＪ／ｃｍ２でＵＶ照射し、封止材料組成物（１８）の硬化物を得た。その後ＰＥＴ基材上から硬化物を剥離することにより、厚み５０μｍの封止シート（１８）を得た。得られた封止シート（１８）について、４０℃９０％ＲＨカップ法（ＪＩＳ　Ｚ０２０８－１９７６）により水蒸気透過度を測定したところ、１５．２ｇ／ｍ２・ｄａｙ（１００μｍ換算）であった。

上記の結果のとおり、重合性液晶組成物中に充填材を含有する本発明の封止材料組成物を用いた封止材料層は、バリア性に優れ、また、無機蒸着層の屈曲性を付与できる蒸着アンカー層としても優れることが明らかとなった。
(Adjustment of dispersion B)
3-Methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silylating agent was added to 100 parts of an organically modified layered silicate (Esben NZ, manufactured by Hojun Co., Ltd.) that was organized with dimethylstearylbenzylammonium. ) Was mixed and ball milled under a nitrogen atmosphere to obtain a filler b. To 15 parts of this filler b, 20 parts of hydroxyethylacrylamide and 80 parts of acetone were added and stirred for 2 hours at 25 ° C. to obtain a dispersion B in which the filler b was uniformly dispersed.
(Adjustment of polymerizable liquid crystal composition (U-18))
45 parts of the compound represented by formula (B-1), 45 parts of the compound represented by formula (B-2), 10 parts of the compound represented by formula (C-1), p-methoxyphenol (MEHQ) 0 .1 part was heated to 70 ° C. and dissolved by stirring, and after dissolution was confirmed, 2 parts of Irgacure 907 (Irg.907: manufactured by BASF Japan), Irgacure TPO (TPO: manufactured by BASF Japan) 2 parts and 0.2 part of Megafac F-554 (F-554: manufactured by DIC Corporation) were added and further stirred to obtain a solution (U-18).
(Adjustment of sealing material composition (18))
100 g of dispersion B was added to 90 g of the polymerizable liquid crystal composition (U-18), stirred at room temperature, and then degassed with a solvent in a planetary mixer to thereby uniformly disperse the filler b (18) Got.
(Example 24)
A sealing material composition (18) is applied on a PET substrate film having a thickness of 50 μm rubbed with a nylon cloth using an applicator, and UV irradiation is performed at 500 mJ / cm 2 using a conveyor type high-pressure mercury lamp. Then, a cured product of the sealing material composition (18) was obtained. Thereafter, the cured product was peeled off from the PET substrate to obtain a sealing sheet (18) having a thickness of 50 μm. With respect to the obtained sealing sheet (18), the water vapor transmission rate was measured by the 40 ° C. 90% RH cup method (JIS Z0208-1976), and it was 15.2 g / m 2 · day (100 μm conversion).

As described above, the sealing material layer using the sealing material composition of the present invention containing a filler in the polymerizable liquid crystal composition has excellent barrier properties and imparts flexibility to the inorganic vapor deposition layer. It became clear that it was excellent also as a vapor deposition anchor layer which can be performed.

Claims (14)

  1. 　少なくとも１種以上の充填材、及び、１種又は２種以上の重合性液晶化合物を含有する表示素子用封止材料組成物。 A sealing material composition for a display element containing at least one filler and one or more polymerizable liquid crystal compounds.
  2. 　前記充填材が粉末状である請求項１に記載の表示素子用封止材料組成物。 The sealing material composition for a display element according to claim 1, wherein the filler is in a powder form.
  3. 　前記粉末状充填材として層状充填材を用いる請求項２に記載の表示素子用封止材料組成物。 The sealing material composition for a display element according to claim 2, wherein a layered filler is used as the powdery filler.
  4. 　前記粉末状充填材として球状或いは無定形状材を用いた請求項２に記載の表示素子用封止材料組成物。 3. A sealing material composition for a display element according to claim 2, wherein a spherical or amorphous material is used as the powder filler.
  5. 　前記重合性液晶化合物が一般式（ＩＩ）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｐ２１は重合性官能基を表し、
    Ｓｐ２１は炭素原子数１～１８のアルキレン基を表し（該アルキレン基中の水素原子は、１つ以上のハロゲン原子、ＣＮ基、又は重合性官能基を有する基により置換されていても良く、このアルキレン基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）、
    Ｘ２１は－Ｏ－、－Ｓ－、－ＯＣＨ２－、－ＣＨ２Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＳＣＨ２－、－ＣＨ２Ｓ－、－ＣＦ２Ｏ－、－ＯＣＦ２－、－ＣＦ２Ｓ－、－ＳＣＦ２－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＯＯ－ＣＨ２ＣＨ２－、－ＯＣＯ－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２－ＣＯＯ－、－ＣＨ２ＣＨ２－ＯＣＯ－、－ＣＯＯ－ＣＨ２－、－ＯＣＯ－ＣＨ２－、－ＣＨ２－ＣＯＯ－、－ＣＨ２－ＯＣＯ－、－ＣＨ＝ＣＨ－、－Ｎ＝Ｎ－、－ＣＨ＝Ｎ－Ｎ＝ＣＨ－、－ＣＦ＝ＣＦ－、－Ｃ≡Ｃ－又は単結合を表し（ただし、Ｐ２１－Ｓｐ２１、及びＳｐ２１－Ｘ２１は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－結合を含まない。）、
    ｑ２１は０又は１を表し、
    ＭＧはメソゲン基を表し、
    Ｒ２１は、水素原子、ハロゲン原子、シアノ基、又は炭素原子数１から１２の直鎖又は分岐アルキル基を表し、該アルキル基は直鎖状であっても分岐していてもよく、該アルキル基は１個の－ＣＨ２－又は隣接していない２個以上の－ＣＨ２－が各々独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯＯ－、－ＣＨ＝ＣＨ－ＯＣＯ－、－ＣＯＯ－ＣＨ＝ＣＨ－、－ＯＣＯ－ＣＨ＝ＣＨ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－又は－Ｃ≡Ｃ－によって置換されても良く、あるいはＲ２１は、一般式（ＩＩ－ａ）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｐ２２は重合性官能基を表し、
    Ｓｐ２２は、Ｓｐ２１で定義されたものと同一のものを表し、
    Ｘ２２は、Ｘ２１で定義されたものと同一のものを表し（ただし、Ｐ２２－Ｓｐ２２、及びＳｐ２２－Ｘ２２は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－結合を含まない。）、ｑ２２は０又は１を表す。）で表される基を表す。）で表される化合物である、請求項１～請求項４のいずれか一項に記載の表示素子用封止材料組成物。     The polymerizable liquid crystal compound has the general formula (II)
    Figure JPOXMLDOC01-appb-C000001
     (Wherein P 21 represents a polymerizable functional group,
    Sp 21 represents an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group may be substituted with one or more halogen atoms, a CN group, or a group having a polymerizable functional group, each of the two or more CH 2 groups not one CH 2 group or adjacent existing in the alkylene group independently of one another, -O -, - COO -, - OCO- or --OCO-O-by May be replaced).
    X 21 represents —O—, —S—, —OCH 2 —, —CH 2 O—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO. —O—, —CO—NH—, —NH—CO—, —SCH 2 —, —CH 2 S—, —CF 2 O—, —OCF 2 —, —CF 2 S—, —SCF 2 —, — CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH 2 CH 2 —, —OCO—CH 2 CH 2 —, — CH 2 CH 2 —COO—, —CH 2 CH 2 —OCO—, —COO—CH 2 —, —OCO—CH 2 —, —CH 2 —COO—, —CH 2 —OCO—, —CH═CH— , —N═N—, —CH═N—N═CH—, —CF═CF—, —C≡C— or a single bond (where P 21 —Sp 21 and Sp 21 —X 21 do not include —O—O—, —O—NH—, —S—S— and —O—S— bonds.
    q21 represents 0 or 1,
    MG represents a mesogenic group,
    R 21 represents a hydrogen atom, a halogen atom, a cyano group, or a linear or branched alkyl group having 1 to 12 carbon atoms, and the alkyl group may be linear or branched. In the group, one —CH 2 — or two or more non-adjacent —CH 2 — 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—CH═ CH—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C— may be substituted, or R 21 may have the general formula (II-a)
    Figure JPOXMLDOC01-appb-C000002
     (Wherein P 22 represents a polymerizable functional group,
    Sp 22 represents the same as defined in Sp 21 ;
    X 22 represents the same as defined for X 21 (provided that P 22 -Sp 22 and Sp 22 -X 22 are —O—O—, —O—NH—, —S—S). -And -O-S- bond are not included.), Q22 represents 0 or 1. ) Represents a group represented by The sealing material composition for a display device according to any one of claims 1 to 4, which is a compound represented by
  6. 　前記一般式（ＩＩ）において、ＭＧが一般式（ＩＩ－ｂ）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｂ１、Ｂ２及びＢ３はそれぞれ独立的に、１，４－フェニレン基、１，４－シクロヘキシレン基、１，４－シクロヘキセニル基、テトラヒドロピラン－２，５－ジイル基、１，３－ジオキサン－２，５－ジイル基、テトラヒドロチオピラン－２，５－ジイル基、１，４－ビシクロ（２，２，２）オクチレン基、デカヒドロナフタレン－２，６－ジイル基、ピリジン－２，５－ジイル基、ピリミジン－２，５－ジイル基、ピラジン－２，５－ジイル基、チオフェン－２，５－ジイル基－、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、２，６－ナフチレン基、フェナントレン－２，７－ジイル基、９，１０－ジヒドロフェナントレン－２，７－ジイル基、１，２，３，４，４ａ，９，１０ａ－オクタヒドロフェナントレン－２，７－ジイル基、１，４－ナフチレン基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジチオフェン－２，６－ジイル基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジセレノフェン－２，６－ジイル基、［１］ベンゾチエノ［３，２－ｂ］チオフェン－２，７－ジイル基、［１］ベンゾセレノフェノ［３，２－ｂ］セレノフェン－２，７－ジイル基、又はフルオレン－２，７－ジイル基を表し、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基（当該アルキル基中の水素原子は、１つ以上のフェニル基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、及び／又は、炭素原子数２～８のアルケノイル基、及び／又は一般式（ＩＩ－ｃ）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｐ２３は重合性官能基を表し、
    Ｓｐ２３は、上記Ｓｐ２１で定義されたものと同一のものを表し、
    Ｘ２３は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、又は単結合を表し、ｑ２３は０又は１を表し、ｑ２４は０又は１を表す。（ただし、Ｐ２３－Ｓｐ２３、及びＳｐ２３－Ｘ２３は、－Ｏ－Ｏ－、－Ｏ－ＮＨ－、－Ｓ－Ｓ－及び－Ｏ－Ｓ－基を含まない。））を有していても良く、
    Ｚ１及びＺ２はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－Ｃ（ＣＦ３）２－、ハロゲン原子を有してもよい炭素原子数２～１０のアルキル基又は単結合を表すが、Ｚ１、Ｚ２が単結合を表す場合、上記Ｂ１、Ｂ２、Ｂ３のうち、隣接して存在する２つの環構造がそれぞれ有する置換基が結合して環状基を形成しても良く、
    ｒ１は０、１、２又は３を表し、Ｂ１、及びＺ１が複数存在する場合は、それぞれ、同一であっても、異なっていても良い。）で表される化合物である、請求項５に記載の表示素子用封止材料組成物。     In the general formula (II), MG represents the general formula (II-b)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, B1, B2 and B3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophene Nantes -2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group, or fluorene-2,7-diyl group, and one or more F, Cl, CF 3 , OCF 3 , CN groups, or an alkyl group having 1 to 8 carbon atoms (the alkyl group) hydrogen atom in the group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent existing independently of one another during this group Placed by -O-, -COO-, -OCO- or -OCO-O- Or an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 1 to 8 carbon atoms. An alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms, and / or the general formula (II-c)
    Figure JPOXMLDOC01-appb-C000004
     (Wherein P 23 represents a polymerizable functional group,
    Sp 23 represents the same as defined in Sp 21 above,
    X 23 represents —O—, —COO—, —OCO—, —OCH 2 —, —CH 2 O—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, or A single bond is represented, q23 represents 0 or 1, and q24 represents 0 or 1. (However, P 23 -Sp 23 and Sp 23 -X 23 do not include —O—O—, —O—NH—, —S—S— and —O—S— groups.) You may,
    Z1 and Z2 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH—, —C≡C—, —CH═ CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, —C═N—, —N═C— , —CONH—, —NHCO—, —C (CF 3 ) 2 —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom or a single bond, Z1 and Z2 each represent a single bond In this case, among the above B1, B2, and B3, the substituents each having two adjacent ring structures may combine to form a cyclic group,
    r1 represents 0, 1, 2, or 3, and when there are a plurality of B1 and Z1, they may be the same or different. The sealing material composition for display elements of Claim 5 which is a compound represented by this.
  7. 　前記一般式（ＩＩ）で表される化合物として、一般式（ＩＩ－２）
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｐ２２１、Ｘ２１１、ｑ２２１、Ｘ２２２、ｑ２２２、Ｐ２２２は、それぞれ、一般式（ＩＩ）又は一般式（ＩＩ－ａ）中のＰ２１、Ｘ２１、ｑ２１、Ｘ２２、ｑ２２、Ｐ２２の定義と同じものを表し、
    Ｓｐ２２１及びＳｐ２２２はそれぞれ独立して、炭素原子数１～１８のアルキレン基を表し（該アルキレン基中の水素原子は、１つ以上のハロゲン原子、又はＣＮ基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）を表し、
    ＭＧ２はメソゲン基を表し、当該メソゲン基としては、一般式（ＩＩ－２－ｂ）
    Figure JPOXMLDOC01-appb-C000006
     （上記式中、Ｂ１１、Ｂ２１及びＢ３１はそれぞれ独立的に、１，４－フェニレン基、１，４－シクロヘキシレン基、１，４－シクロヘキセニル基、テトラヒドロピラン－２，５－ジイル基、１，３－ジオキサン－２，５－ジイル基、テトラヒドロチオピラン－２，５－ジイル基、１，４－ビシクロ（２，２，２）オクチレン基、デカヒドロナフタレン－２，６－ジイル基、ピリジン－２，５－ジイル基、ピリミジン－２，５－ジイル基、ピラジン－２，５－ジイル基、チオフェン－２，５－ジイル基－、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、２，６－ナフチレン基、フェナントレン－２，７－ジイル基、９，１０－ジヒドロフェナントレン－２，７－ジイル基、１，２，３，４，４ａ，９，１０ａ－オクタヒドロフェナントレン－２，７－ジイル基、１，４－ナフチレン基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジチオフェン－２，６－ジイル基、ベンゾ［１，２－ｂ：４，５－ｂ‘］ジセレノフェン－２，６－ジイル基、［１］ベンゾチエノ［３，２－ｂ］チオフェン－２，７－ジイル基、［１］ベンゾセレノフェノ［３，２－ｂ］セレノフェン－２，７－ジイル基、又はフルオレン－２，７－ジイル基を表し、置換基として１個以上のＦ、Ｃｌ、ＣＦ3、ＯＣＦ3、ＣＮ基、炭素原子数１～８のアルキル基（当該アルキル基中の水素原子は、１つ以上のフェニル基により置換されていても良く、この基中に存在する１つのＣＨ2基又は隣接していない２つ以上のＣＨ2基はそれぞれ相互に独立して、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－又は－ＯＣＯ－Ｏ－により置き換えられていても良い。）、炭素原子数１～８のアルコキシ基、炭素原子数１～８のアルカノイル基、炭素原子数１～８のアルカノイルオキシ基、炭素原子数１～８のアルコキシカルボニル基、炭素原子数２～８のアルケニル基、炭素原子数２～８のアルケニルオキシ基、及び／又は、炭素原子数２～８のアルケノイル基を有していても良く、
    上記式中、Ｚ１１及びＺ２１はそれぞれ独立して、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ2 ＣＨ2－、－ＯＣＨ2－、－ＣＨ2Ｏ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ2ＣＨ2ＣＯＯ－、－ＣＨ2ＣＨ2ＯＣＯ－、－ＣＯＯＣＨ2ＣＨ2－、－ＯＣＯＣＨ2ＣＨ2－、－Ｃ＝Ｎ－、－Ｎ＝Ｃ－、－ＣＯＮＨ－、－ＮＨＣＯ－、－Ｃ（ＣＦ３）２－、ハロゲン原子を有してもよい炭素原子数２～１０のアルキル基又は単結合を表し、ｒ１１は０、１、２又は３を表し、Ｂ１１、及びＺ１１が複数存在する場合は、それぞれ、同一であっても、異なっていても良いが、Ｚ１１、Ｚ２１が単結合を表す場合、上記Ｂ１１、Ｂ２１、Ｂ３１のうち、隣接して存在する２つの環構造がそれぞれ有する置換基が結合して環状基を形成しても良い。）で表される。）で表される化合物からなる群より選ばれる少なくとも１種の化合物を含有する請求項６に記載の表示素子用封止材料組成物。     As the compound represented by the general formula (II), the general formula (II-2)
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, P 221 , X 211 , q 221 , X 222 , q 222 , and P 222 are P 21 , X 21 , q 21 , X 22 , q 22 in general formula (II) or general formula (II-a), respectively. represent the same as the definition of P 22,
    Sp 221 and Sp 222 each independently represent an alkylene group having 1 to 18 carbon atoms (the hydrogen atom in the alkylene group may be substituted with one or more halogen atoms or a CN group; the two or more CH 2 groups not one CH 2 group or adjacent present in groups independently of one another each, -O -, - COO -, - OCO- or replaced by --OCO-O- May be)
    MG 2 represents a mesogenic group, and the mesogenic group has the general formula (II-2-b)
    Figure JPOXMLDOC01-appb-C000006
     (In the above formula, B11, B21 and B31 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, , 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine -2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6 -Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydro Enanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group, or fluorene-2,7-diyl group, and one or more F, Cl, CF 3 , OCF 3 , CN groups, or an alkyl group having 1 to 8 carbon atoms (the alkyl group) hydrogen atom in the group may be substituted with one or more phenyl groups, each of two or more CH 2 groups not one CH 2 group or adjacent existing independently of one another during this group -O-, -COO-, -OCO- or -OCO-O- Or an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, an alkanoyloxy group having 1 to 8 carbon atoms, or an alkoxycarbonyl having 1 to 8 carbon atoms. Group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and / or an alkenoyl group having 2 to 8 carbon atoms,
    In the above formula, Z11 and Z21 are each independently —COO—, —OCO—, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —CH═CH—, —C≡C—. , —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —OCOCH 2 CH 2 —, —C═N—, — N═C—, —CONH—, —NHCO—, —C (CF 3 ) 2 —, an alkyl group having 2 to 10 carbon atoms which may have a halogen atom, or a single bond; 2 or 3 and when there are a plurality of B11 and Z11, they may be the same or different, but when Z11 and Z21 represent a single bond, the above B11, B21 and B31 Of these, the positions of two adjacent ring structures A substituent may be bonded to form a cyclic group. ). The sealing material composition for display elements of Claim 6 containing the at least 1 sort (s) of compound chosen from the group which consists of a compound represented by this.
  8. 　前記重合性液晶化合物が一般式（ＩＩＩ）
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｒ７はそれぞれ独立して一般式（ＩＩＩ－ａ）で表される置換基を表す。
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｒ９及びＲ１０はそれぞれ独立的に水素原子、ハロゲン原子又はメチル基を表し、Ｒ８は炭素原子数１～２０のアルコキシ基を表すが、該アルコキシ基中の水素原子は一般式（ＩＩＩ－ｂ）、一般式（ＩＩＩ－ｃ）、又は一般式（ＩＩＩ－ｄ）で表される置換基によって置換されていても良く、一般式（ＩＩＩ）中に存在するＲ８の少なくとも１つは、一般式（ＩＩＩ－ｂ）、一般式（ＩＩＩ－ｃ）、又は一般式（ＩＩＩ－ｄ）で表される置換基によって置換されている。）
    Figure JPOXMLDOC01-appb-C000009
     （式中、Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４、Ｒ８５、Ｒ８６、Ｒ８７、Ｒ８８及びＲ８９はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１～５のアルキル基を表し、ｎは０又は１を表す。））で表される化合物である、請求項１～請求項４のいずれか一項に記載の表示素子用封止材料組成物。     The polymerizable liquid crystal compound has the general formula (III)
    Figure JPOXMLDOC01-appb-C000007
     (In the formula, each R 7 independently represents a substituent represented by the general formula (III-a).
    Figure JPOXMLDOC01-appb-C000008
     (In the formula, R 9 and R 10 each independently represents a hydrogen atom, a halogen atom or a methyl group, and R 8 represents an alkoxy group having 1 to 20 carbon atoms. May be substituted by a substituent represented by the formula (III-b), the general formula (III-c), or the general formula (III-d), and at least R 8 present in the general formula (III) One is substituted by a substituent represented by general formula (III-b), general formula (III-c), or general formula (III-d).)
    Figure JPOXMLDOC01-appb-C000009
     (Wherein R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 , R 88 and R 89 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. And n represents 0 or 1.) The sealing material composition for a display element according to any one of claims 1 to 4, which is a compound represented by the following formula:
  9. 　請求項１～請求項８のいずれか一項に記載の表示素子用封止材料組成物を用いた表示素子用シール剤。 A sealant for a display element using the display element sealing material composition according to any one of claims 1 to 8.
  10. 　請求項１～請求項８のいずれか一項に記載の表示素子用封止材料組成物を用いた表示素子に用いる基材封止保護剤。 A base material sealing protective agent used for a display device using the sealing material composition for a display device according to any one of claims 1 to 8.
  11. 　請求項１～請求項８のいずれか一項に記載の表示素子用封止材料組成物でシールされた液晶表示素子。 A liquid crystal display device sealed with the sealing material composition for a display device according to any one of claims 1 to 8.
  12. 　請求項１～請求項８のいずれか一項に記載の表示素子用封止材料組成物でシールされた有機発光表示素子。 An organic light-emitting display element sealed with the display element sealing material composition according to any one of claims 1 to 8.
  13. 　基材層上に、請求項１～請求項８のいずれか一項に記載の表示素子用封止材料組成物を用いた基材封止保護層及び無機層を有する液晶表示素子。 A liquid crystal display element having a base material sealing protective layer and an inorganic layer using the display element sealing material composition according to any one of claims 1 to 8 on a base material layer.
  14. 　基材層上に、請求項１～請求項８のいずれか一項に記載の表示素子用封止材料組成物を用いた基材封止保護層及び無機層を有する有機発光表示素子。 An organic light emitting display device having a base material sealing protective layer and an inorganic layer using the sealing material composition for a display device according to any one of claims 1 to 8 on a base material layer.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6414368B2 (en) * 2016-06-28 2018-10-31 Dic株式会社 Polymerizable liquid crystal composition
JP2020068203A (en) * 2018-10-22 2020-04-30 エルジー ディスプレイ カンパニー リミテッド Display device
WO2020162104A1 (en) * 2019-02-04 2020-08-13 セントラル硝子株式会社 Composition for sealing organic light-emitting element, and organic light-emitting element-sealing film using said composition, and formation method therefor
WO2022075030A1 (en) * 2020-10-08 2022-04-14 Dic株式会社 Resin composition, molded object, layered product, gas-barrier material, coating material, and adhesive
US11697666B2 (en) 2021-04-16 2023-07-11 Gilead Sciences, Inc. Methods of preparing carbanucleosides using amides
US11767337B2 (en) 2020-02-18 2023-09-26 Gilead Sciences, Inc. Antiviral compounds
US12030903B2 (en) 2020-02-18 2024-07-09 Gilead Sciences, Inc. Antiviral compounds
US12054507B2 (en) 2020-02-18 2024-08-06 Gilead Sciences, Inc. Antiviral compounds

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003113141A (en) * 2001-10-05 2003-04-18 Fuji Photo Film Co Ltd Method for producing discotic compound
JP2007163552A (en) * 2005-12-09 2007-06-28 Seiko Epson Corp Electrooptical device, liquid crystal device, manufacturing method of electrooptical device, manufacturing method of liquid crystal device, and projector
JP2012084355A (en) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd Electronic device
WO2016016156A1 (en) * 2014-07-31 2016-02-04 Rolic Ag Encapsulation structure for an oled display incorporating antireflection properties

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003113141A (en) * 2001-10-05 2003-04-18 Fuji Photo Film Co Ltd Method for producing discotic compound
JP2007163552A (en) * 2005-12-09 2007-06-28 Seiko Epson Corp Electrooptical device, liquid crystal device, manufacturing method of electrooptical device, manufacturing method of liquid crystal device, and projector
JP2012084355A (en) * 2010-10-08 2012-04-26 Sumitomo Chemical Co Ltd Electronic device
WO2016016156A1 (en) * 2014-07-31 2016-02-04 Rolic Ag Encapsulation structure for an oled display incorporating antireflection properties

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6414368B2 (en) * 2016-06-28 2018-10-31 Dic株式会社 Polymerizable liquid crystal composition
JPWO2018003515A1 (en) * 2016-06-28 2018-12-20 Dic株式会社 Polymerizable liquid crystal composition
JP2020068203A (en) * 2018-10-22 2020-04-30 エルジー ディスプレイ カンパニー リミテッド Display device
US11075347B2 (en) 2018-10-22 2021-07-27 Lg Display Co., Ltd. Flexible display device
WO2020162104A1 (en) * 2019-02-04 2020-08-13 セントラル硝子株式会社 Composition for sealing organic light-emitting element, and organic light-emitting element-sealing film using said composition, and formation method therefor
US11767337B2 (en) 2020-02-18 2023-09-26 Gilead Sciences, Inc. Antiviral compounds
US12030903B2 (en) 2020-02-18 2024-07-09 Gilead Sciences, Inc. Antiviral compounds
US12054507B2 (en) 2020-02-18 2024-08-06 Gilead Sciences, Inc. Antiviral compounds
WO2022075030A1 (en) * 2020-10-08 2022-04-14 Dic株式会社 Resin composition, molded object, layered product, gas-barrier material, coating material, and adhesive
US11697666B2 (en) 2021-04-16 2023-07-11 Gilead Sciences, Inc. Methods of preparing carbanucleosides using amides

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