WO2019159889A1 - Stratifié, et procédé de fabrication de celui-ci - Google Patents

Stratifié, et procédé de fabrication de celui-ci Download PDF

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WO2019159889A1
WO2019159889A1 PCT/JP2019/004846 JP2019004846W WO2019159889A1 WO 2019159889 A1 WO2019159889 A1 WO 2019159889A1 JP 2019004846 W JP2019004846 W JP 2019004846W WO 2019159889 A1 WO2019159889 A1 WO 2019159889A1
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liquid crystal
cured film
film
crystal cured
group
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PCT/JP2019/004846
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English (en)
Japanese (ja)
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辰昌 葛西
伸行 幡中
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住友化学株式会社
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Priority claimed from JP2019007266A external-priority patent/JP2019139220A/ja
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020207024305A priority Critical patent/KR20200120652A/ko
Priority to CN201980011881.8A priority patent/CN111684328B/zh
Publication of WO2019159889A1 publication Critical patent/WO2019159889A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • 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
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light

Definitions

  • the present invention relates to a laminate including a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film, an elliptically polarizing plate including the laminate, and an organic EL display device.
  • the present invention also relates to a method for manufacturing the laminate.
  • An elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated.
  • a polarizing plate and a retardation plate are laminated.
  • a so-called ⁇ / 4 plate is used as a retardation plate constituting the elliptically polarizing plate.
  • the retardation plate constituting the elliptically polarizing plate is preferably one exhibiting reverse wavelength dispersion.
  • a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is polymerized and cured in a state where it is aligned in the horizontal direction with respect to the plane of the phase difference plate.
  • a phase difference plate is known.
  • Patent Document 1 describes a laminate including a vertical alignment liquid crystal cured film formed on a vertical alignment film and a horizontal alignment liquid crystal cured film formed on a horizontal alignment film. ing.
  • a laminate including a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film as described in the above-mentioned patent document has conventionally been produced after independently producing a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film. In many cases, it is produced by pasting them together with an adhesive or the like.
  • a vertical alignment liquid crystal cured film requires a vertical alignment film for aligning a polymerizable liquid crystal compound in the vertical direction, and the vertical alignment film needs to be formed before the vertical alignment liquid crystal cured film is formed. There is. For this reason, the manufacturing process of the conventional laminated body containing a vertical alignment liquid crystal cured film and a horizontal alignment liquid crystal cured film tends to become complicated, and there existed a problem that productivity fell easily.
  • the present invention is a novel solution to the above problem, that is, a laminate capable of continuously forming a vertically aligned liquid crystal cured film without forming a vertical aligned film on the horizontally aligned liquid crystal cured film, And it aims at providing the manufacturing method.
  • an object of the present invention is to improve liquid crystal alignment in a laminate including a vertical alignment liquid crystal cured film formed without a vertical alignment film on a horizontal alignment liquid crystal cured film.
  • a laminate including a horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film in this order The horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition cured in a state where the polymerizable liquid crystal compound is aligned in the horizontal direction with respect to the liquid crystal cured film plane, and the vertically aligned liquid crystal cured film is polymerized.
  • the vertical alignment liquid crystal cured film contains a vertical alignment accelerator and is opposite to the horizontal alignment liquid crystal cured film of the vertical alignment liquid crystal cured film from a surface opposite to the vertical alignment liquid crystal cured film of the horizontal alignment liquid crystal cured film.
  • the laminated body whose total film thickness to the surface of the side is 5 micrometers or less.
  • the vertically aligned liquid crystal cured film is a liquid crystal cured film obtained by curing a polymerizable liquid crystal compound having at least one radical polymerizable group in a state of being aligned perpendicular to the in-plane direction of the liquid crystal cured film.
  • the horizontally aligned liquid crystal cured film has the following formula (1): ReA (450) / ReA (550) ⁇ 1 (1)
  • ReA (450) represents an in-plane retardation value at a wavelength of 450 nm in the in-plane direction of the horizontally aligned liquid crystal cured film
  • ReA (550) represents a wavelength of 550 nm in the in-plane direction of the horizontally aligned liquid crystal cured film.
  • the cured vertical alignment liquid crystal film includes a nonionic silane compound as a vertical alignment accelerator, and the nonionic silane compound is a silane coupling agent. Laminated body.
  • the vertically aligned liquid crystal cured film has the following formula (2): RthC (450) / RthC (550) ⁇ 1 (2) [In Formula (2), RthC (450) represents the retardation value in the thickness direction at a wavelength of 450 nm of the vertically aligned liquid crystal cured film, and RthC (550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm.
  • [20] The method for producing a laminate according to any one of [1] to [16], Forming a coating film of a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a horizontal alignment liquid crystal cured film from the coating film; and vertical alignment liquid crystal curing including a polymerizable liquid crystal compound
  • the manufacturing method which includes the process of forming the coating film of the polymeric liquid crystal composition for film formation, and forming the vertical alignment liquid crystal cured film from this coating film in this order.
  • the method includes the step of forming a coating film of the composition for forming a horizontal alignment film and forming a horizontal alignment film from the coating film. 21].
  • a laminate capable of continuously forming a vertical alignment liquid crystal cured film without forming a vertical alignment film on the horizontal alignment liquid crystal cured film, in particular, the laminate excellent in liquid crystal alignment, And a method for manufacturing the same.
  • the laminate of the present invention includes a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film in this order.
  • a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film in this order.
  • a laminate 11 shown in FIG. 1 is formed by laminating a horizontal alignment liquid crystal cured film 1 and a vertical alignment liquid crystal cured film 2 in this order.
  • the vertical alignment liquid crystal cured film 2 is directly formed on the horizontal alignment liquid crystal cured film 1 without using a layer having a vertical alignment regulating force (hereinafter also referred to as “vertical alignment film”).
  • the horizontally aligned liquid crystal cured film 1 and the vertically aligned liquid crystal cured film 2 are adjacent to each other.
  • the laminate of the present invention may further include other layers.
  • Other layers include a base material, a horizontal alignment film, a cured resin layer such as a protective layer and a hard coat layer, a further vertical or horizontal alignment liquid crystal cured film, and an adhesive for bonding the laminate of the present invention to a polarizing film or the like. Examples thereof include an adhesive layer.
  • the horizontal alignment liquid crystal cured film 1 is formed on the horizontal alignment film 3
  • a vertically aligned liquid crystal cured film 2 is laminated on a horizontally aligned liquid crystal cured film 1.
  • the horizontal alignment film 3 is formed on the base material 5 on which the cured resin layer 4 is formed, and the horizontal alignment film 3 is formed on the horizontal alignment film 3.
  • a horizontal liquid crystal cured film 1 and a vertical alignment liquid crystal cured film 2 are laminated in this order.
  • An elliptically polarizing plate can be obtained by laminating the laminate 11 and the polarizing film through the adhesive layer.
  • either side of the horizontally aligned liquid crystal cured film 1 and the vertically aligned liquid crystal cured film 2 of the laminate 11 may be bonded to the polarizing film.
  • the polarizing film may be bonded via an adhesive layer, and after peeling the substrate 5 of the laminate 11 in FIG. 3, the cured resin layer 4 and the polarizing film are bonded to the adhesive layer. You may paste through.
  • the minimum layer configuration including the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film in this order is also referred to as “basic layer configuration (I)”.
  • the laminate of the present invention when the laminate of the present invention includes a plurality of horizontal or vertical alignment liquid crystal cured films and when another layer exists between the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film, A horizontal alignment liquid crystal cured film and a vertical alignment liquid crystal cured film in a close arrangement form the basic layer configuration (I).
  • the laminate of the present invention is configured by successively laminating a base material, a horizontal alignment film, a first horizontal alignment liquid crystal cured film, a second horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film in this order.
  • the basic layer configuration (I) of the laminate of the present invention is from the second horizontally aligned liquid crystal cured film to the vertically aligned liquid crystal cured film.
  • the total film thickness from the surface opposite to the vertically aligned liquid crystal cured film of the horizontally aligned liquid crystal cured film to the surface opposite to the horizontally aligned liquid crystal cured film of the vertically aligned liquid crystal cured film (hereinafter, The thickness between a and b in FIGS. 1 to 3 (also referred to as “total film thickness T1”) is 5 ⁇ m or less.
  • the laminate of the present invention can form a vertically aligned liquid crystal cured film directly on a horizontally aligned liquid crystal cured film, the horizontal aligned liquid crystal cured film and the vertically aligned liquid crystal cured film are separately prepared, Compared with the conventional laminated body obtained by bonding with an adhesive or an adhesive, the total film thickness T1 can be reduced.
  • the reduction in the total thickness T1 of the laminate can contribute to the reduction in thickness of the entire laminate and the elliptically polarizing plate including the laminate.
  • the total film thickness T1 in the laminate of the present invention is preferably 4.5 ⁇ m or less, more preferably 4 ⁇ m or less.
  • the lower limit value of the total film thickness T1 is not particularly limited, and is usually 1 ⁇ m or more, for example, 1.5 ⁇ m or more.
  • the laminated body of the present invention is on the side opposite to the vertical alignment liquid crystal cured film of the horizontal alignment liquid crystal cured film in the basic layer configuration (I) or on the side opposite to the horizontal alignment liquid crystal cured film of the vertical alignment liquid crystal cured film.
  • the total film thickness T1 is opposite to the vertical alignment liquid crystal cured film of the horizontal alignment liquid crystal cured film constituting the basic layer structure (I). Means the total film thickness from the surface of the vertical alignment liquid crystal cured film to the surface opposite to the horizontal alignment liquid crystal cured film.
  • the vertical alignment liquid crystal cured film is formed on the horizontal alignment liquid crystal cured film or a layer having no vertical alignment regulating force provided on the horizontal alignment liquid crystal cured film without passing through the vertical alignment film.
  • the vertically aligned liquid crystal cured film can be formed without the vertical alignment film, so that the number of manufacturing steps of the laminate is reduced and the laminate can be manufactured with high productivity.
  • the laminate of the present invention comprises a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film adjacent to each other. The laminate having such a layer structure can be formed into a laminate that can be manufactured with higher productivity because a vertically aligned liquid crystal cured film can be continuously formed on the horizontally aligned liquid crystal cured film without a vertical alignment film. .
  • the vertically aligned liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition that is cured in a state where the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the liquid crystal cured film.
  • the vertically aligned liquid crystal cured film contains a vertical alignment accelerator. That is, in the present invention, the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains a vertical alignment accelerator.
  • the vertical alignment promoter means a material that promotes the liquid crystal alignment of the polymerizable liquid crystal compound in the direction perpendicular to the film plane.
  • the vertical alignment liquid crystal cured film contains a vertical alignment accelerator, the vertical alignment liquid crystal cured film can be formed without the vertical alignment film.
  • the liquid crystal alignment of the polymerizable liquid crystal compound constituting the vertically aligned liquid crystal cured film is easily affected by the liquid crystal alignment of the horizontal aligned liquid crystal cured film. It becomes difficult for the polymerizable liquid crystal compound to be accurately aligned in the direction perpendicular to the film plane.
  • the vertical alignment of the polymerizable liquid crystal compound can be promoted by including a vertical alignment accelerator, and the accuracy of the liquid crystal alignment can be improved, the liquid crystal of the laminate including the vertical alignment liquid crystal cured film Orientation is easily improved.
  • Examples of the vertical alignment promoter for promoting the vertical alignment of the polymerizable liquid crystal compound include ionic compounds composed of nonmetallic atoms and nonionic silane compounds.
  • the vertically aligned liquid crystal cured film preferably contains at least one of a nonionic silane compound and an ionic compound composed of a nonmetallic atom, and includes both a nonionic silane compound and an ionic compound composed of a nonmetallic atom. It is more preferable.
  • the nonionic silane compound reduces the surface tension of the polymerizable liquid crystal composition and is formed from the polymerizable liquid crystal composition.
  • the nonionic silane compound tends to be unevenly distributed at the interface between the dried coating film and the air, and the vertical alignment control force on the polymerizable liquid crystal compound is enhanced. Tends to be oriented in the vertical direction. Thereby, the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.
  • the nonionic silane compound is a compound that is nonionic and contains Si element.
  • Nonionic silane compounds include, for example, silicon polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, and organic inorganic silane compounds such as silicone oligomers, silses siloxanes and alkoxy silanes (more specifically, Is a silane coupling agent or the like.
  • the nonionic silane compound may be a silicone monomer type or a silicone oligomer (polymer) type.
  • Silicone oligomers are shown in the form of (monomer)-(monomer) copolymer: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Mercaptopropyl group-containing copolymers such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetra Ethoxysilane copolymer, mercaptomethyltriethoxy
  • nonionic silane compounds may be used individually by 1 type, or may be used in combination of 2 or more type.
  • a silane coupling agent is preferable from the viewpoint of further improving the adhesion with an adjacent layer such as a horizontally aligned liquid crystal cured film.
  • Silane coupling agent is selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, isocyanate group, carboxy group, and hydroxyl group at the terminal.
  • the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the above functional group). Furthermore, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group.
  • the silane coupling agent has at least one alkoxysilyl group and at least one polar group in the molecule, the vertical alignment property of the polymerizable liquid crystal compound is more easily improved, and the vertical alignment promoting effect is remarkably obtained. There is a tendency.
  • the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxy group, and a hydroxy group.
  • the polar group may have a substituent or a protective group as appropriate in order to control the reactivity of the silane coupling agent.
  • silane coupling agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltri Meto Sis
  • silane coupling agents examples include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403. , KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as -9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 Is mentioned.
  • the content is usually preferably 100 parts by weight of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. Is 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass.
  • the content of the nonionic silane compound is within the above range, it is possible to effectively promote the vertical alignment of the polymerizable liquid crystal compound while maintaining good coating properties of the polymerizable liquid crystal composition.
  • the dry coating film formed from the polymerizable liquid crystal composition is polymerizable by electrostatic interaction.
  • the vertical alignment control force with respect to the liquid crystal compound is developed, and the polymerizable liquid crystal compound tends to be aligned in the direction perpendicular to the film plane in the dry coating film.
  • the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.
  • Examples of ionic compounds composed of nonmetallic atoms include onium salts (more specifically, quaternary ammonium salts, tertiary sulfonium salts in which the nitrogen atom has a positive charge, and phosphorus atoms have a positive charge. And quaternary phosphonium salts.
  • onium salts more specifically, quaternary ammonium salts, tertiary sulfonium salts in which the nitrogen atom has a positive charge, and phosphorus atoms have a positive charge.
  • quaternary phosphonium salts are preferable from the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, and from the viewpoint of improving availability and mass productivity, a quaternary phosphonium salt or a quaternary salt.
  • Ammonium salts are more preferred.
  • the onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.
  • the molecular weight of the ionic compound composed of a nonmetallic atom is 100 or more and 10,000 or less.
  • the molecular weight of the ionic compound is more preferably 5000 or less, and still more preferably 3000 or less.
  • Examples of the cation component of the ionic compound composed of a nonmetallic atom include inorganic cations and organic cations. Among these, an organic cation is preferable because it hardly causes alignment defects of the polymerizable liquid crystal compound.
  • Examples of the organic cation include an imidazolium cation, a pyridinium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation.
  • An ionic compound composed of a nonmetallic atom generally has a counter anion.
  • an anion component used as the counter ion of the said cation component an inorganic anion and an organic anion are mentioned, for example.
  • an organic anion is preferable because it hardly causes alignment defects of the polymerizable liquid crystal compound.
  • the cation and the anion do not necessarily have a one-to-one correspondence.
  • anion component examples include the following. Chloride anion [Cl ⁇ ], Bromide anion [Br ⁇ ], Iodide anion [I ⁇ ], Tetrachloroaluminate anion [AlCl 4 ⁇ ], Heptachlorodialuminate anion [Al 2 Cl 7 ⁇ ], Tetrafluoroborate anion [BF 4 ⁇ ], Hexafluorophosphate anion [PF 6 ⁇ ], Perchlorate anion [ClO 4 ⁇ ], Nitrate anion [NO 3 ⁇ ], Acetate anion [CH 3 COO ⁇ ], Trifluoroacetate anion [CF 3 COO ⁇ ], Fluorosulfonate anion [FSO 3 ⁇ ], Methanesulfonate anion [CH 3 SO 3 ⁇ ], Trifluoromethanesulfonate anion [CF 3 SO 3 ⁇ ], p-toluenesulfonate anion [p-CH 3
  • ionic compound composed of a nonmetallic atom can be appropriately selected from the combination of the cation component and the anion component.
  • Specific examples of the compound that is a combination of a cation component and an anion component include the following.
  • (Imidazolium salt) 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium methanesulfonate, etc.
  • the ionic compound preferably has an Si element and / or an F element in the molecular structure of the cation moiety.
  • the ionic compound has Si element and / or F element in the molecular structure of the cation moiety, the ionic compound is easily segregated on the surface of the vertically aligned liquid crystal cured film.
  • the following ionic compounds (i) to (iii) are preferred as the ionic compounds in which all of the constituent elements are nonmetallic elements.
  • the surface of a substrate is treated with a surfactant having an alkyl group having a long chain length to some extent to improve the orientation of the liquid crystal (for example, “Liquid Crystal Handbook”, Chapter 2, Liquid Crystal Orientation and Physical Properties (Maruzen)
  • a surfactant having an alkyl group having a long chain length for example, “Liquid Crystal Handbook”, Chapter 2, Liquid Crystal Orientation and Physical Properties (Maruzen)
  • the vertical alignment property of the polymerizable liquid crystal compound can be further improved by applying the above). That is, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved by treating the substrate surface with an ionic compound having an alkyl group having a long chain length to some extent.
  • an ionic compound composed of a nonmetallic atom satisfies the following formula (3). 5 ⁇ M ⁇ 16 (3)
  • M is represented by the following formula (4).
  • M (the number of covalent bonds from the positively charged atom to the end of the molecular chain of the substituent having the largest number of covalent bonds from the end of the molecular chain to the end of the molecular chain among the substituents directly bonded on the positively charged atom ) ⁇ (number of positively charged atoms) (4)
  • a positive charge considered as a base point for a substituent having two or more positively charged atoms is defined as “the number of covalent bonds from the positively charged atom to the end of the molecular chain” described in the definition of M above.
  • the ionic compound which consists of a nonmetallic atom is an oligomer or polymer which has two or more repeating units, a structural unit is considered as one molecule and M is calculated.
  • the number of covalent bonds leading to the atom having the same positive charge via the ring structure or the end of a substituent bonded to the ring structure Of the number of covalent bonds, the larger number of covalent bonds is defined as “the number of covalent bonds from the positively charged atom to the end of the molecular chain” described in the definition of M above.
  • the content thereof is usually 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. 0.01 to 5 parts by mass is preferable, 0.05 to 4 parts by mass is more preferable, and 0.1 to 3 parts by mass is even more preferable.
  • the content of the ionic compound is within the above range, the vertical alignment property of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coating property of the polymerizable liquid crystal composition.
  • the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains both a nonionic silane compound and an ionic compound comprising a nonmetallic atom.
  • the vertical alignment of the polymerizable liquid crystal compound is more easily promoted by the electrostatic interaction derived from the ionic compound and the surface tension reducing effect derived from the nonionic silane compound.
  • the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned more accurately.
  • the vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing the alignment accelerator and at least one polymerizable liquid crystal compound, and preferably a polymerizable liquid crystal compound having at least one radical polymerizable group. It is a liquid crystal cured film formed by curing in a state of being aligned perpendicular to the in-plane direction of the liquid crystal cured film.
  • the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film means a liquid crystal compound having a polymerizable group, and in particular, a liquid crystal compound having at least one radical polymerizable group. preferable.
  • the polymerizable liquid crystal compound is not particularly limited, and for example, a conventionally known polymerizable liquid crystal compound can be used in the field of retardation film.
  • the polymerizable group refers to a group that can participate in a polymerization reaction by an active radical or an acid generated from a polymerization initiator.
  • Examples of the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, oxetanyl group and the like.
  • a radical polymerizable group is preferable, an acryloyloxy group, a methacryloyloxy group, a vinyl group, and a vinyloxy group are more preferable, and an acryloyloxy group and a methacryloyloxy group are more preferable.
  • the vertical alignment liquid crystal cured film is present adjacent to the horizontal alignment liquid crystal cured film, the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are both cured products of a polymerizable liquid crystal compound having at least one radical polymerizable group. In some cases, the adhesion between the continuously formed horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film tends to be improved.
  • the liquid crystalline property of the polymerizable liquid crystal compound may be either a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferred in terms of enabling precise film thickness control.
  • the phase order structure in the thermotropic liquid crystal may be a nematic liquid crystal or a smectic liquid crystal.
  • the polymerizable liquid crystal compounds can be used alone or in combination of two or more.
  • Examples of the polymerizable liquid crystal compound generally include a polymerizable liquid crystal compound exhibiting positive wavelength dispersion and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion, and either one of the polymerizable liquid crystal compounds may be used. It is also possible to use a mixture of both types of polymerizable liquid crystal compounds. From the viewpoint of having a large effect of suppressing the oblique reflection hue during black display, it is preferable to include a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion.
  • the polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is preferably a compound having the following characteristics (A) to (D).
  • the major axis direction (a) and the number of ⁇ electrons N are defined as follows.
  • the major axis direction (a) is the major axis direction of a rod in the case of a compound having a rod-like structure, for example.
  • the number of ⁇ electrons N ( ⁇ a) existing on the major axis direction (a) does not include ⁇ electrons that disappear due to the polymerization reaction.
  • the number of ⁇ electrons N ( ⁇ a) existing on the major axis direction (a) is the total number of ⁇ electrons on the major axis and ⁇ electrons conjugated with this, for example, present on the major axis direction (a) And the number of ⁇ electrons present in the ring that satisfies the Hückel rule.
  • the number of ⁇ electrons N ( ⁇ b) existing in the cross direction (b) does not include ⁇ electrons that disappear due to the polymerization reaction.
  • the polymerizable liquid crystal compound satisfying the above has a mesogenic structure in the major axis direction. Due to this mesogenic structure, a liquid crystal phase (nematic phase, smectic phase) is expressed.
  • a nematic or smectic phase is formed by applying a polymerizable liquid crystal compound satisfying the above (A) to (D) onto a film (layer) that forms a liquid crystal cured film and heating it to a temperature higher than the phase transition temperature.
  • a polymerizable liquid crystal compound satisfying the above (A) to (D) onto a film (layer) that forms a liquid crystal cured film and heating it to a temperature higher than the phase transition temperature.
  • the major axis directions of the polymerizable liquid crystal compound are usually aligned parallel to each other, and this major axis direction is the alignment direction of the nematic phase. It becomes.
  • a polymer film made of a polymer polymerized in a state of being oriented in the major axis direction (a) can be formed.
  • This polymer film absorbs ultraviolet rays by ⁇ electrons in the major axis direction (a) and ⁇ electrons in the cross direction (b).
  • the absorption maximum wavelength of ultraviolet light absorbed by the ⁇ electrons in the intersecting direction (b) is ⁇ bmax.
  • ⁇ bmax is usually 300 nm to 400 nm.
  • the density of ⁇ electrons satisfies the above formula (iii), and the ⁇ electron density in the cross direction (b) is larger than the ⁇ electron density in the major axis direction (a).
  • the absorption of linearly polarized ultraviolet light having a wavelength ( ⁇ bmax) is larger than that of linearly polarized ultraviolet light having a vibration plane in the major axis direction (a) (wavelength is ⁇ bmax).
  • the ratio (ratio of absorbance in the crossing direction (b) of linearly polarized ultraviolet light / absorbance in the long axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, and usually 30 or less, for example, 10 or less. It is.
  • the polymerizable liquid crystal compound having the above characteristics often exhibits reverse wavelength dispersion.
  • Specific examples include compounds represented by the following formula (X).
  • Ar represents a divalent group having an aromatic group which may have a substituent.
  • the aromatic group as used herein refers to an aromatic group having [4n + 2] ⁇ electrons according to the Hückel rule, and is exemplified by (Ar-1) to (Ar-23) described later. You may have two or more such Ar groups through a bivalent coupling group.
  • n represents an integer.
  • a ring structure is formed including a heteroatom such as —N ⁇ or —S—, the case where the Huckel's rule is satisfied including the non-covalent electron pair on the heteroatom and the aromatic structure is included.
  • the aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
  • the divalent group Ar may contain one aromatic group or two or more aromatic groups.
  • the divalent group Ar may be a divalent aromatic group which may have a substituent.
  • the divalent group Ar contains two or more aromatic groups, the two or more aromatic groups are bonded to each other by a single bond, a divalent linking group such as —CO—O— or —O—. It may be.
  • G 1 and G 2 each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group.
  • the hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a carbon atom.
  • the carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group which may be substituted with an alkoxy group, cyano group or nitro group of formulas 1 to 4 is an oxygen atom, a sulfur atom Alternatively, it may be substituted with a nitrogen atom.
  • L 1 , L 2 , B 1 and B 2 are each independently a single bond or a divalent linking group.
  • E 1 and E 2 each independently represents an alkanediyl group having 1 to 17 carbon atoms, where an alkanediyl group having 4 to 12 carbon atoms is more preferable.
  • a hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and —CH 2 — contained in the alkanediyl group is —O—, —S—, —SiH 2 —, —C It may be substituted with ( ⁇ O) —.
  • P 1 and P 2 each independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.
  • G 1 and G 2 are each independently preferably a 1,4-phenylenediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group , 4-phenylenediyl group, unsubstituted 1,4-phenylenediyl group, or unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably unsubstituted 1,4-phenylenediyl group or Substituted 1,4-trans-cyclohexanediyl group.
  • At least one of a plurality of G 1 and G 2 is preferably a divalent alicyclic hydrocarbon group, and at least one of G 1 and G 2 bonded to L 1 or L 2 More preferably, it is a divalent alicyclic hydrocarbon group.
  • L 1 and L 2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R a1 OR a2 —, —R a3 COOR a4 —, —R a5 OCOR a6 —, R a7 OC ⁇ OOR a8 —, —N ⁇ N—, —CR c ⁇ CR d —, or —C ⁇ C—.
  • R a1 to R a8 each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms
  • R c and R d each represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.
  • L 1 and L 2 are each independently more preferably a single bond, —OR a2-1 —, —CH 2 —, —CH 2 CH 2 —, —COOR a4-1 —, or —OCOR a6-1 —. is there.
  • R a2-1 , R a4-1 , and R a6-1 each independently represent a single bond, —CH 2 —, or —CH 2 CH 2 —.
  • L 1 and L 2 are each independently a single bond, —O—, —CH 2 CH 2 —, —COO—, —COOCH 2 CH 2 —, or —OCO—.
  • B 1 and B 2 are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R a9 OR a10 —, —R a11 COOR a12 —, —R a13 OCOR a14 —, or R a15 OC ⁇ OOR a16 —.
  • R a9 to R a16 each independently represents a single bond or an alkylene group having 1 to 4 carbon atoms.
  • B 1 and B 2 are each independently more preferably a single bond, —OR a10-1 —, —CH 2 —, —CH 2 CH 2 —, —COOR a12-1 —, or —OCOR a14-1 —. is there.
  • R a10-1 , R a12-1 and R a14-1 each independently represents a single bond, —CH 2 — or —CH 2 CH 2 —.
  • B 1 and B 2 are each independently more preferably a single bond, -O -, - CH 2 CH 2 -, - COO -, - COOCH 2 CH 2 -, - OCO-, or -OCOCH 2 CH 2 - in is there.
  • Examples of the polymerizable group represented by P 1 or P 2 include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, and oxiranyl group. And an oxetanyl group.
  • an acryloyloxy group, a methacryloyloxy group, a vinyl group and a vinyloxy group are preferable, and an acryloyloxy group and a methacryloyloxy group are more preferable.
  • Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron-withdrawing group.
  • aromatic hydrocarbon ring examples include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable.
  • aromatic heterocycle examples include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring, imidazole ring, pyrazole ring. , Thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, phenanthrolin ring, and the like.
  • a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferable, and a benzothiazole group is more preferable.
  • Ar includes a nitrogen atom
  • the nitrogen atom preferably has ⁇ electrons.
  • the total number N of ⁇ electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, particularly Preferably it is 16 or more. Moreover, Preferably it is 30 or less, More preferably, it is 26 or less, More preferably, it is 24 or less.
  • Examples of the aromatic group represented by Ar include the following groups.
  • Z 0 , Z 1 and Z 2 are each independently a hydrogen atom, a halogen atom or an alkyl having 1 to 12 carbon atoms.
  • Q 1 and Q 2 each independently represent —CR 2 ′ R 3 ′ —, —S—, —NH—, —NR 2 ′ —, —CO— or —O—, wherein R 2 ′ and R 3 'each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • J 1 and J 2 each independently represent a carbon atom or a nitrogen atom.
  • Y 1 , Y 2 and Y 3 each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.
  • W 1 and W 2 each independently represents a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.
  • Examples of the aromatic hydrocarbon group in Y 1 , Y 2 and Y 3 include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group.
  • a naphthyl group is preferred, and a phenyl group is more preferred.
  • the aromatic heterocyclic group has 4 to 20 carbon atoms and contains at least one hetero atom such as a nitrogen atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, or a benzothiazolyl group, an oxygen atom, or a sulfur atom.
  • a furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.
  • Y 1 , Y 2 and Y 3 may each independently be an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group.
  • the polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aggregate of aromatic rings.
  • the polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.
  • Z 0 , Z 1 and Z 2 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms.
  • 0 is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group
  • Z 1 and Z 2 are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group.
  • Z 0 , Z 1 and Z 2 may contain a polymerizable group.
  • Q 1 and Q 2 are preferably —NH—, —S—, —NR 2 ′ —, —O—, and R 2 ′ is preferably a hydrogen atom. Of these, —S—, —O—, and —NH— are particularly preferable.
  • the formulas (Ar-1) to (Ar-23) are preferable from the viewpoint of molecular stability.
  • Y 1 may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z 0 .
  • the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring that Ar may have, for example, pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrazine ring, pyrimidine ring, indole Ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like.
  • This aromatic heterocyclic group may have a substituent.
  • Y 1 may be the above-described optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z 0 .
  • a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. are mentioned.
  • polymerizable liquid crystal compound (Y) for example, a compound containing a group represented by the following formula (Y) (hereinafter also referred to as “polymerizable liquid crystal compound (Y)”). It may be used.
  • the polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersion.
  • the polymerizable liquid crystal compounds can be used alone or in combination of two or more.
  • P11 represents a polymerizable group.
  • A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group.
  • the hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group.
  • a hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
  • B11 is —O—, —S—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NR 16 —, —NR 16 —CO—, —CO—, — Represents CS- or a single bond.
  • R 16 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • E11 represents an alkanediyl group having 1 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and a hydrogen atom contained in the alkoxy group May be substituted with a halogen atom.
  • —CH 2 — constituting the alkanediyl group may be replaced by —O— or —CO—.
  • the carbon number of the aromatic hydrocarbon group and alicyclic hydrocarbon group of A11 is preferably in the range of 3 to 18, more preferably in the range of 5 to 12, and particularly preferably 5 or 6. preferable.
  • A11 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.
  • E11 is preferably a linear alkanediyl group having 1 to 12 carbon atoms.
  • —CH 2 — constituting the alkanediyl group may be replaced by —O—.
  • a linear alkanediyl group having 1 to 12 carbon atoms such as a diyl group; —CH 2 —CH 2 —O—CH 2 —CH 2 —, —CH 2 —CH 2 —
  • B11 is preferably —O—, —S—, —CO—O— or —O—CO—, and more preferably —CO—O—.
  • B12 and B13 are each independently —O—, —S—, —C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —, —O—C. ( ⁇ O) —O— is preferable, and —O— or —O—C ( ⁇ O) —O— is more preferable.
  • the polymerizable group represented by P11 is preferably a radical polymerizable group or a cationic polymerizable group in view of high polymerization reactivity, particularly photopolymerization reactivity, and is easy to handle and easy to produce a liquid crystal compound. Therefore, the polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15). [In the formulas (P-11) to (P-15), R 17 to R 21 each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. ]
  • P11 is preferably a group represented by formula (P-14) to formula (P-20), and more preferably a vinyl group, a p-stilbene group, an epoxy group or an oxetanyl group. More preferably, the group represented by P11-B11- is an acryloyloxy group or a methacryloyloxy group.
  • Examples of the polymerizable liquid crystal compound (Y) include compounds represented by the formula (I), the formula (II), the formula (III), the formula (IV), the formula (V), or the formula (VI).
  • P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12 I) P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11
  • II P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12
  • III P11-B11-E11-B12-A11-B13-A12-B14-A13-F11
  • P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12 V) P11-B11-E11-B12-
  • F11 is a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxy group, a methylol group, a formyl group, or a sulfo group.
  • —SO 3 H a carboxy group, an alkoxycarbonyl group having 1 to 10 carbon atoms or a halogen atom, and —CH 2 — constituting the alkyl group and alkoxy group may be replaced by —O—. Good.
  • polymerizable liquid crystal compound (Y) “3.8.6 Network (fully crosslinked type)” of Liquid Crystal Handbook (Edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. October 30, 2000)
  • Y polymerizable liquid crystal compound
  • Polymerizable nematic liquid crystal material compounds having a polymerizable group, JP 2010-31223 A, JP 2010-270108 A, JP Examples thereof include polymerizable liquid crystals described in JP2011-6360A and JP2011-207765A.
  • polymerizable liquid crystal compound (Y) examples include the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), and formulas (III-1) to (III-26), formula (IV-1) to formula (IV-26), formula (V-1) to formula (V-2) and formula (VI-1) to formula (VI-6) Compounds.
  • k1 and k2 each independently represents an integer of 2 to 12.
  • a vertically aligned liquid crystal cured film having a high degree of alignment order By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity, a vertically aligned liquid crystal cured film having a high degree of alignment order can be formed.
  • the polymerizable liquid crystal compound when a polymerizable liquid crystal compound exhibiting a smectic liquid crystal property is used as the polymerizable liquid crystal compound for forming a vertically aligned liquid crystal cured film, the polymerizable liquid crystal compound has a higher order from the viewpoint of achieving a higher degree of alignment order.
  • the smectic phase (higher order smectic liquid crystal state) is more preferable.
  • the higher-order smectic phase means a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase.
  • the smectic B phase, the smectic F phase, and the smectic I phase are more preferable.
  • the thermic liquid crystal may be either a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferred in terms of enabling precise film thickness control.
  • the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity may be a monomer, but may be an oligomer or a polymer in which a polymerizable group is polymerized.
  • the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity is a liquid crystal compound having at least one polymerizable group, and is a liquid crystal compound having two or more polymerizable groups from the viewpoint of improving the heat resistance of the vertically aligned liquid crystal cured film. It is preferable.
  • the polymerizable group include (meth) acryloyloxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, oxiranyl group, oxetanyl group and the like.
  • (Meth) acryloyloxy group because it is easy to improve, the heat resistance of the vertical alignment liquid crystal cured film is easy to improve, and the adhesion between the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film is easy to adjust and improve. It is preferable to contain.
  • Examples of the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity include a compound represented by the following formula (Z) (hereinafter sometimes referred to as “polymerizable liquid crystal compound (Z)”).
  • Z polymerizable liquid crystal compound
  • X 1z and X 2z each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or 2
  • the hydrogen atom contained in the valent alicyclic hydrocarbon group includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group
  • X 1z and X 2z are a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
  • Y 1z is a single bond or a divalent linking group.
  • nz is 1 to 3, and when nz is 2 or more, the plurality of X 1z may be the same as or different from each other.
  • X 2z may be the same as or different from any or all of the plurality of X 1z .
  • the plurality of Y 1z may be the same as or different from each other. From the viewpoint of liquid crystallinity, nz is preferably 2 or more.
  • U 1z represents a hydrogen atom or a (meth) acryloyloxy group.
  • U 2z represents a polymerizable group.
  • W 1z and W 2z are each independently a single bond or a divalent linking group.
  • V 1z and V 2z each independently represent an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group is —O—, It may be replaced by —CO—, —S— or NH—. ]
  • X 1z and X 2z are preferably independently of each other, preferably a 1,4-phenylene group which may have a substituent, or a substituent.
  • a cyclohexane-1,4-diyl group, and at least one of X 1z and X 2z may have a 1,4-phenylene group which may have a substituent, or a substituent. It may be a cyclohexane-1,4-diyl group, preferably a trans-cyclohexane-1,4-diyl group.
  • Examples of the substituent that the optionally substituted 1,4-phenylene group or the optionally substituted cyclohexane-1,4-diyl group include a methyl group, an ethyl group, And alkyl groups having 1 to 4 carbon atoms such as a butyl group and a cyano group, and halogen atoms such as a chlorine atom and a fluorine atom. Preferably it is unsubstituted.
  • the polymerizable liquid crystal compound (Z) is represented by the formula (Z1): - (X 1z -Y 1z -) nz -X 2z - (Z1) [ Wherein , X 1z , Y 1z , X 2z and nz each have the same meaning as described above. ] [Hereinafter referred to as a partial structure (Z1). ] Is preferably an asymmetric structure in that it easily exhibits smectic liquid crystallinity. Examples of the polymerizable liquid crystal compound (Z) in which the partial structure (Z1) is an asymmetric structure include a polymerizable liquid crystal compound (Z) in which nz is 1 and one X 1z and X 2z are different from each other.
  • nz is 2 and two Y 1z have the same structure, two X 1z have the same structure, and one X 2z has a structure different from these two X 1z the polymerizable liquid crystal compound (Z), X 1z that binds to W 1z of the two X 1z is, the other of X 1z and X 2z are different structures, the other of X 1z and X 2z mutually the same structure
  • the polymerizable liquid crystal compound (Z) which is also mentioned.
  • R az and R bz each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Y 1z is, -CH 2 CH 2 -, - more preferably COO- or a single bond, when a plurality of Y 1z is present, Y 1z that binds X 2z is, -CH 2 CH 2 - or CH More preferably, it is 2 O-.
  • X 1z and X 2z all have the same structure, it is preferable that two or more Y 1z having different bonding methods exist. In the case where a plurality of Y 1z having different coupling methods are present, an asymmetric structure is formed, and thus smectic liquid crystal properties tend to be easily exhibited.
  • U 2z is the aforementioned polymerizable group.
  • U 1z is a hydrogen atom or a polymerizable group. Since it is easy to manufacture, the heat resistance of the vertically aligned liquid crystal cured film is easily improved, and the adhesion between the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film is easily adjusted and improved, the polymerizable group is ( It is preferably a (meth) acryloyloxy group.
  • the polymerizable group may be in a polymerized state or an unpolymerized state, but is preferably in an unpolymerized state.
  • Examples of the alkanediyl group represented by V 1z and V 2z include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl Group and icosane-1,20-diyl group and the like.
  • V 1z and V 2z are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.
  • alkanediyl group optionally has include a cyano group and a halogen atom.
  • the alkanediyl group is preferably unsubstituted, and is an unsubstituted linear alkanediyl group. Is more preferable.
  • W 1z and W 2z are each independently preferably a single bond, —O—, —S—, —COO— or OCOO—, and more preferably a single bond or —O—.
  • the polymerizable liquid crystal compound (Z) preferably has an asymmetric molecular structure in the molecular structure.
  • the polymerizable liquid crystal compound (Z) is a polymerizable liquid crystal compound having the following partial structures (Aa) to (Ai): More preferably. From the viewpoint of easily exhibiting high-order smectic liquid crystallinity, it is more preferable to have a partial structure of (Aa), (Ab) or (Ac). In the following (Aa) to (Ai), * represents a bond (single bond).
  • polymerizable liquid crystal compound (Z) examples include compounds represented by formulas (A-1) to (A-25).
  • the polymerizable liquid crystal compound (Z) has a cyclohexane-1,4-diyl group
  • the cyclohexane-1,4-diyl group is preferably a trans isomer.
  • formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7), formula (A- 8) at least one selected from the group consisting of compounds represented by formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) Species are preferred.
  • the polymerizable liquid crystal compound (Z) one type may be used alone, or two or more types may be used in combination.
  • Polymerizable liquid crystal compound (Z) is, for example, Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or a known method described in Japanese Patent No. 4719156.
  • the vertically aligned liquid crystal cured film preferably has at least one maximum absorption at a wavelength of 300 to 400 nm, and the polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film has a maximum at a wavelength of 300 to 400 nm.
  • a polymerizable liquid crystal compound having an absorption wavelength is preferred.
  • the polymerizable liquid crystal composition contains a photopolymerization initiator, the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage.
  • the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even when ultraviolet light is exposed during storage, generation of reactive species from the photopolymerization initiator and the polymerization of the polymerizable liquid crystal compound due to the reactive species The progress of polymerization reaction and gelation can be effectively suppressed. Therefore, it is advantageous in terms of long-term stability of the polymerizable liquid crystal composition, and the orientation and film thickness uniformity of the obtained liquid crystal cured film can be improved.
  • the maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer.
  • the solvent is a solvent that can dissolve the polymerizable liquid crystal compound, and examples thereof include chloroform.
  • the vertically aligned liquid crystal cured film is formed from a polymerizable liquid crystal composition including a polymerizable liquid crystal compound having a maximum absorption wavelength between wavelengths of 300 to 400 nm, formation of a laminate including the vertically aligned liquid crystal cured film Since the vertically aligned liquid crystal cured film exhibits absorption in the above wavelength range, the vertically aligned liquid crystal cured film is converted into the horizontally aligned liquid crystal cured film using an ultraviolet curable adhesive that is cured by light in the above wavelength range (ultraviolet light). It is difficult to laminate with other layers such as high adhesion.
  • an ultraviolet curable adhesive that is cured by light in the above wavelength range (ultraviolet light). It is difficult to laminate with other layers such as high adhesion.
  • the vertically aligned liquid crystal cured film can be continuously formed on the horizontally aligned liquid crystal cured film without using an adhesive layer.
  • a polymerizable liquid crystal compound that often has a maximum absorption in the wavelength region of 300 to 400 nm without exhibiting the above-mentioned problem relating to the property, and that exhibits so-called reverse wavelength dispersion can be used for the structure of the laminate. This is also advantageous in that a thin laminate having optical properties can be obtained.
  • the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition.
  • the amount is preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and still more preferably 90 to 95 parts by mass.
  • the solid content of the polymerizable liquid crystal composition means all components excluding volatile components such as organic solvents from the polymerizable liquid crystal composition.
  • the polymerizable liquid crystal composition used for forming the vertically aligned liquid crystal cured film includes additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, and a photosensitizer. May further be included. Each of these components may be used alone or in combination of two or more.
  • the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film is usually applied on a horizontal liquid crystal cured film or the like in a state dissolved in a solvent, it preferably contains a solvent.
  • a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable.
  • the solvent include alcohols such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether.
  • Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, etc.
  • Ketone solvent aliphatic hydrocarbon solvent such as pentane, hexane and heptane; ethylcyclohexa Aliphatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvents such as chloroform and chlorobenzene; Dimethylacetamide, dimethylformi Examples include amide solvents such as amide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferable.
  • the content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by weight, more preferably 70 to 95 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal composition. Accordingly, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition becomes low, so that the thickness of the film becomes substantially uniform and unevenness tends not to occur. The solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.
  • the polymerization initiator is a compound capable of generating a reactive species by the contribution of heat or light and initiating a polymerization reaction such as a polymerizable liquid crystal compound.
  • reactive species include active species such as radicals, cations, and anions.
  • active species such as radicals, cations, and anions.
  • a photopolymerization initiator that generates radicals by light irradiation is preferable.
  • photopolymerization initiator examples include benzoin compounds, benzophenone compounds, benzyl ketal compounds, ⁇ -hydroxy ketone compounds, ⁇ -amino ketone compounds, oxime compounds, triazine compounds, iodonium salts and sulfonium salts.
  • Irgacure registered trademark
  • Irgacure 184 Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (Inc.
  • the maximum absorption wavelength is preferably from 300 nm to 400 nm, more preferably from 300 nm to 380 nm, and among them, ⁇ -acetophenone series A polymerization initiator and an oxime photopolymerization initiator are preferred.
  • Examples of ⁇ -acetophenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1 -One and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like, more preferably 2-methyl-2-morpholino-1- ( 4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one.
  • Examples of commercially available ⁇ -acetophenone compounds include Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Ltd.), Sequol BEE (manufactured by Seiko Chemical Co., Ltd.), and the like.
  • the oxime photopolymerization initiator generates radicals such as phenyl radicals and methyl radicals when irradiated with light. Polymerization of the polymerizable liquid crystal compound proceeds favorably by this radical, and among them, an oxime photopolymerization initiator that generates a methyl radical is preferable in terms of high polymerization reaction initiation efficiency. From the viewpoint of allowing the polymerization reaction to proceed more efficiently, it is preferable to use a photopolymerization initiator that can efficiently use ultraviolet rays having a wavelength of 350 nm or more.
  • a photopolymerization initiator capable of efficiently using ultraviolet rays having a wavelength of 350 nm or more
  • a triazine compound or a carbazole compound containing an oxime structure is preferable, and a carbazole compound containing an oxime ester structure is more preferable from the viewpoint of sensitivity.
  • the carbazole compound containing an oxime structure include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.
  • oxime ester photopolymerization initiators examples include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (manufactured by BASF Japan Ltd.), Adekaoptomer N-1919, Adeka Arcles NCI-831. (Above, manufactured by ADEKA Corporation).
  • the content of the photopolymerization initiator is usually 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal compound. It is. If it is in the said range, reaction of a polymeric group will fully advance and it will be hard to disturb the orientation of a polymeric liquid crystal compound.
  • the leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the coating film obtained by applying the composition.
  • Fluoroalkyl leveling agents can be mentioned.
  • Commercially available products may be used as the leveling agent, specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.) , KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4446, TSF-4442, TSF4442, TSF6045 (All above, Momentive Performance Materials Japan GK), Fluorinert (registered trademark) FC-72, FC-
  • the content of the leveling agent is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. It is preferable for the content of the leveling agent to be within the above-mentioned range since it is easy to align the polymerizable liquid crystal compound and the obtained liquid crystal cured film tends to be smoother.
  • the polymerization reaction of the polymerizable liquid crystal compound can be controlled by adding an antioxidant.
  • the antioxidant may be a primary antioxidant selected from phenolic antioxidants, amine antioxidants, quinone antioxidants, nitroso antioxidants, phosphorus antioxidants and sulfur. It may be a secondary antioxidant selected from system antioxidants.
  • the content of the antioxidant is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Yes, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.
  • Antioxidants can be used alone or in combination of two or more.
  • the photopolymerization initiator can be made highly sensitive by using a photosensitizer.
  • the photosensitizer include xanthones such as xanthone and thioxanthone; anthracene having a substituent such as anthracene and alkyl ether; phenothiazine; and rubrene.
  • a photosensitizer can be used individually or in combination of 2 or more types.
  • the content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. 3 parts by mass.
  • a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film comprises a vertical alignment accelerator and a polymerizable liquid crystal compound, and components other than the vertical alignment accelerator such as a solvent and a photopolymerization initiator and the polymerizable liquid crystal compound at a predetermined temperature. Can be obtained by stirring or the like.
  • the vertically aligned liquid crystal cured film preferably satisfies the following formula (2).
  • RthC (450) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm.
  • RthC (550) represents a retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm.
  • RthC (450) / RthC (550) in the vertically aligned liquid crystal cured film is more preferably 0.95 or less, further preferably 0.92 or less, particularly preferably 0.9 or less, and preferably Is 0.7 or more, more preferably 0.75 or more, and still more preferably 0.8 or more.
  • the retardation value RthC ( ⁇ ) in the film thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film.
  • nzC ( ⁇ ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of ⁇ nm.
  • nxC ( ⁇ ) nyC ( ⁇ )
  • nxC ( ⁇ ) is arbitrary in the film plane.
  • the refractive index in the direction can be set, and dC represents the thickness of the vertically aligned liquid crystal cured film) Therefore, in order to obtain a desired retardation value RthC ( ⁇ ) in the film thickness direction, the three-dimensional refractive index and the film thickness dC may be adjusted.
  • the three-dimensional refractive index depends on the molecular structure and orientation state of the polymerizable liquid crystal compound described above.
  • the vertically aligned liquid crystal cured film is preferably aligned with a high degree of order in the vertical direction of the liquid crystal cured film.
  • the oblique direction during black display It tends to be excellent in the effect of suppressing changes in the reflected hue.
  • the vertically aligned liquid crystal cured film satisfies the following formula (5) as an index indicating the degree of oblique optical compensation effect at the time of black display, indicating the high alignment state of the polymerizable liquid crystal compound in the vertically aligned liquid crystal cured film.
  • formula (5) RthC (550) has the same meaning as described above.
  • the retardation value RthC (550) in the thickness direction of the vertically aligned liquid crystal cured film is more preferably ⁇ 100 nm or more, further preferably ⁇ 90 nm or more, particularly It is preferably ⁇ 80 nm or more, more preferably ⁇ 40 nm or less, and further preferably ⁇ 50 nm or less.
  • the horizontally aligned liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition cured in a state where the polymerizable liquid crystal compound is aligned in the horizontal direction with respect to the liquid crystal cured film plane, preferably A liquid crystal cured film obtained by curing a polymerizable liquid crystal compound having at least one radical polymerizable group in a state of being aligned horizontally with respect to the in-plane direction of the liquid crystal cured film.
  • the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition forming the horizontally aligned liquid crystal cured film means a liquid crystal compound having a polymerizable group, and in particular, a liquid crystal compound having at least one radical polymerizable group. preferable.
  • the horizontal alignment liquid crystal cured film is present adjacent to the vertical alignment liquid crystal cured film, the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are both cured products of polymerizable liquid crystal compounds having at least one radical polymerizable group. If it exists, the adhesiveness of the horizontal alignment liquid crystal cured film and vertical alignment liquid crystal cured film formed continuously will be easy to improve.
  • the polymerizable liquid crystal compound constituting the horizontally aligned liquid crystal cured film and the polymerizable liquid crystal compound constituting the vertically aligned liquid crystal cured film are preferably similar or have the same polymerizable group, and both the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film are composed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a (meth) acryloyl group. It is more preferable.
  • the polymerizable liquid crystal compound constituting the horizontally aligned liquid crystal cured film is not particularly limited, and for example, a conventionally known polymerizable liquid crystal compound can be used in the field of retardation film.
  • a conventionally known polymerizable liquid crystal compound can be used in the field of retardation film.
  • compounds represented by the formula (X), (Y) or (Z) exemplified as polymerizable liquid crystal compounds that can be used for forming a vertically aligned liquid crystal cured film can be used.
  • a polymerizable liquid crystal compound exhibiting wavelength dispersion is preferred, and for example, a compound represented by the above formula (X) can be suitably used.
  • the polymerizable liquid crystal compounds can be used alone or in combination of two or more.
  • the content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used for forming the horizontally aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition.
  • the amount is preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and still more preferably 90 to 95 parts by mass. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film.
  • the polymerizable liquid crystal composition used for forming the horizontally aligned liquid crystal cured film further contains additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound. Also good.
  • additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound. Also good. Examples of these components include the same components as those exemplified above as components that can be used in the vertically aligned liquid crystal cured film. Each of these components may be used alone or in combination of two or more. .
  • the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film can be obtained by stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as a solvent and a photopolymerization initiator at a predetermined temperature. .
  • the horizontal alignment liquid crystal cured film has a wavelength of 300 to 400 nm for the same reason as that when the vertical alignment liquid crystal cured film has at least one maximum absorption between wavelengths of 300 to 400 nm. It is preferred to have at least one maximum absorption in between.
  • the liquid crystal cured film is arranged at a position irradiated with light when the vertical liquid crystal cured film and the vertical liquid crystal cured film are laminated or stacked. Both horizontally aligned liquid crystal cured films have at least one maximum absorption between wavelengths of 300 to 400 nm.
  • the horizontally aligned liquid crystal cured film preferably satisfies the following formula (1).
  • ReA ( ⁇ ) represents the in-plane retardation value of the horizontally aligned liquid crystal cured film at a wavelength of ⁇ nm
  • ReA ( ⁇ ) (nxA ( ⁇ ) ⁇ nyA ( ⁇ )) ⁇ dA
  • nxA ( ⁇ ) represents a main refractive index at a wavelength ⁇ nm in the horizontally aligned liquid crystal cured film surface
  • nyA ( ⁇ ) is a wavelength ⁇ nm in a direction orthogonal to the direction of nxA in the same plane as nxA.
  • DA represents the thickness of the horizontally aligned liquid crystal cured film)
  • the horizontally aligned liquid crystal cured film When the horizontally aligned liquid crystal cured film satisfies the formula (1), the horizontally aligned liquid crystal cured film has a so-called reverse wavelength dispersion in which an in-plane retardation value at a short wavelength is smaller than an in-plane retardation value at a long wavelength. Showing gender.
  • ReA (450) / ReA (550) is preferably 0.70 or more, more preferably because reverse wavelength dispersion is improved and the effect of improving the reflection hue in the front direction of the horizontally aligned liquid crystal cured film can be further enhanced. Is 0.78 or more, preferably 0.95 or less, more preferably 0.92 or less.
  • a horizontal alignment liquid crystal cured film satisfy
  • a laminate (elliptical polarizing plate) including the horizontally aligned liquid crystal cured film is applied to an organic EL display device. The effect of improving the front reflection hue during black display becomes remarkable.
  • a more preferable range of the in-plane retardation value is 130 nm ⁇ ReA (550) ⁇ 150 nm.
  • the laminate of the present invention is, for example, A step of forming a coating film of a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a horizontally aligned liquid crystal cured film from the coated film (hereinafter referred to as “horizontal aligned liquid crystal cured film forming step”).
  • a step of forming a coating film of a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a vertically aligned liquid crystal cured film from the coating film (hereinafter referred to as “vertical aligned liquid crystal cured film forming step”). (Also called) In this order. When the vertically aligned liquid crystal cured film and the horizontal aligned liquid crystal cured film are adjacent to each other in the laminate of the present invention, the horizontal aligned liquid crystal cured film forming step and the vertical aligned liquid crystal cured film forming step are sequentially performed in this order. It is preferable.
  • a step of forming a coating film of the composition for forming a horizontal alignment film and forming a horizontal alignment film from the coating film (hereinafter also referred to as “horizontal alignment film forming step”). ), And the horizontal alignment film forming step, the horizontal alignment liquid crystal cured film forming step, and the vertical alignment liquid crystal cured film forming step are preferably sequentially performed in this order.
  • a laminate including a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film is obtained by a manufacturing method including a horizontal alignment film forming step.
  • the horizontal alignment liquid crystal cured film is, for example, Applying a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film on a substrate or alignment film to obtain a coating film; Drying the coating film to form a dry coating film; and It can be produced by a method including a step of irradiating the dried coating film with active energy rays to form a horizontally aligned liquid crystal cured film.
  • the coating film of the polymerizable liquid crystal composition can be formed, for example, by applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a substrate or an alignment film described later.
  • the substrate include a glass substrate and a film substrate, and a resin film substrate is preferable from the viewpoint of processability.
  • Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; Examples include cellulose esters such as diacetylcellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; and plastics such as polyphenylene sulfide and polyphenylene oxide.
  • Such a resin can be formed into a substrate by a known method such as a solvent casting method or a melt extrusion method.
  • the substrate surface may have a protective layer formed from acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., release treatment such as silicone treatment, corona treatment, Surface treatment such as plasma treatment may be performed.
  • a commercially available product may be used as the base material.
  • a commercially available cellulose ester base material for example, a cellulose ester base material manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film; manufactured by Konica Minolta Opto Co., Ltd. such as “KC8UX2M”, “KC8UY”, and “KC4UY” And cellulose ester base materials.
  • Examples of commercially available cyclic olefin resins include cyclic olefin resins manufactured by Ticona (Germany) such as “Topas (registered trademark); cyclic olefins manufactured by JSR Corporation such as“ Arton (registered trademark) ”.
  • cyclic olefin resin made by ZEON Corporation such as “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; Mitsui like “APEL” (registered trademark)
  • Examples include cyclic olefin-based resins manufactured by Chemical Co., Ltd.
  • Commercially available cyclic olefin resin base materials can also be used.
  • Examples of commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Co., Ltd., such as “ESCINA (registered trademark)” and “SCA40 (registered trademark)”; “ZEONOR FILM (registered trademark)”.
  • the cyclic olefin resin substrate made by JSR Corporation such as “Arton Film (registered trademark)”.
  • the thickness of the substrate is usually from 5 to 300 ⁇ m, preferably from 10 to 150 ⁇ m, from the viewpoint of thinning the laminate, easy peeling of the substrate, handling properties of the substrate, and the like.
  • a spin coating method As a method for applying the polymerizable liquid crystal composition to a substrate or the like, a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, a coating method such as an applicator method, or a printing method such as a flexo method.
  • Known methods such as
  • a dry coating film is formed by removing the solvent by drying or the like.
  • drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying.
  • the heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material such as the base material on which the coating film is formed.
  • liquid crystal In order to cause the polymerizable liquid crystal compound to transition to the liquid crystal phase, liquid crystal It is usually necessary that the temperature be higher than the phase transition temperature.
  • the liquid crystal phase transition temperature (smectic phase transition of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition). It can be heated to a temperature equal to or higher than the temperature or nematic phase transition temperature.
  • the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature adjustment stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like.
  • the phase transition temperature is a polymerization in which all polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition are mixed in the same ratio as the composition in the polymerizable liquid crystal composition.
  • the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition may be lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound alone.
  • the heating time can be appropriately determined according to the heating temperature, the type of polymerizable liquid crystal compound to be used, the type of solvent, the boiling point and the amount thereof, and is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.
  • Removal of the solvent from the coating film may be performed simultaneously with heating to a temperature higher than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound or may be performed separately, but is preferably performed simultaneously from the viewpoint of improving productivity.
  • the solvent in the coating film is appropriately adjusted under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize.
  • the drying temperature (heating temperature) in the drying step is the kind of the polymerizable liquid crystal compound to be used, the solvent It can be appropriately determined according to the type, the boiling point and the amount thereof.
  • the polymerizable liquid crystal compound is polymerized while maintaining the horizontal alignment state of the polymerizable liquid crystal compound, thereby forming a horizontally aligned liquid crystal cured film.
  • the polymerization method include a thermal polymerization method and a photopolymerization method, and the photopolymerization method is preferable from the viewpoint of easily controlling the polymerization reaction.
  • the light applied to the dried coating film includes the type of polymerization initiator contained in the dried coating film, the type of polymerizable liquid crystal compound (particularly the type of polymerizable group possessed by the polymerizable liquid crystal compound), and It is suitably selected according to the amount.
  • ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction, and that widely used in the field as a photopolymerization apparatus can be used. It is preferable to select the kind of the polymerizable liquid crystal compound and the polymerization initiator contained in the polymerizable liquid crystal composition. Moreover, at the time of superposition
  • a horizontally aligned liquid crystal cured film can be appropriately formed even if a substrate having relatively low heat resistance is used.
  • the polymerization reaction can be promoted by increasing the polymerization temperature within a range that does not cause problems due to heat during light irradiation (such as deformation due to heat of the base material).
  • a patterned cured film can be obtained by masking or developing.
  • Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, and a wavelength range.
  • Examples include LED light sources that emit light of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.
  • the ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm 2 .
  • the ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the photopolymerization initiator.
  • the irradiation time is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and further preferably 0.1 second to 1 minute. is there.
  • the integrated light quantity is 10 to 3,000 mJ / cm 2 , preferably 50 to 2,000 mJ / cm 2 , more preferably 100 to 1,000 mJ / cm 2. 2 .
  • the thickness of the horizontally aligned liquid crystal cured film can be appropriately selected depending on the display device to be applied, and is preferably 0.2 to 5 ⁇ m, more preferably 0.2 to 4 ⁇ m, and further preferably 0.2 to 3 ⁇ m. .
  • the coating film of the polymerizable liquid crystal composition for forming the horizontally aligned liquid crystal cured film is in a horizontal direction with respect to the obtained liquid crystal cured film plane. It is preferably formed on a horizontal alignment film having an alignment regulating force. Therefore, the laminate of the present invention preferably includes a horizontal alignment film, and a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film are preferably included in this order. More preferably, the vertically aligned liquid crystal cured films are adjacent to each other in this order.
  • the alignment regulating force of the alignment film can be arbitrarily adjusted depending on the type of the alignment film, the surface state, the rubbing conditions, and the like.
  • the alignment film is formed of a photoalignable polymer, the polarization irradiation condition It is possible to adjust arbitrarily by such as.
  • the horizontal alignment film preferably has a solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied, and also has a heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound described below.
  • the orientation film include an orientation film containing an orientation polymer, a photo-alignment film, a groove orientation film having a concavo-convex pattern and a plurality of grooves on the surface, a stretched film stretched in the orientation direction, and the like.
  • a photo-alignment film is preferable from the viewpoint of quality.
  • orientation polymer examples include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule, and polyamic acid, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyacrylamide which are hydrolysates thereof.
  • examples include oxazole, polyethyleneimine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid and polyacrylic acid esters.
  • polyvinyl alcohol is preferable.
  • Alignment polymers can be used alone or in combination of two or more.
  • the alignment film containing the alignment polymer is usually applied to a substrate with a composition in which the alignment polymer is dissolved in a solvent (hereinafter sometimes referred to as “alignment polymer composition”), and the solvent is removed, or It is obtained by applying the orientation polymer composition to a substrate, removing the solvent, and rubbing (rubbing method).
  • a solvent the thing similar to the solvent illustrated previously as a solvent which can be used for a polymeric liquid crystal composition is mentioned.
  • the concentration of the orienting polymer in the orienting polymer composition may be within a range in which the orienting polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content with respect to the solution, About 1 to 10% is more preferable.
  • a commercially available alignment film material may be used as it is as the alignment polymer composition.
  • Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optmer (registered trademark, manufactured by JSR).
  • Examples of the method for applying the alignment polymer composition to the substrate include the same methods as those exemplified above as the method for applying the polymerizable liquid crystal composition to the substrate.
  • Examples of the method for removing the solvent contained in the oriented polymer composition include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • rubbing treatment can be performed as necessary (rubbing method).
  • a method for imparting alignment regulating force by the rubbing method a rubbing cloth was wound, and the orientation polymer composition was applied to the rotating rubbing roll and annealed and formed on the substrate surface.
  • the method of making the film of an orientation polymer contact is mentioned. If masking is performed when the rubbing treatment is performed, a plurality of regions (patterns) having different orientation directions can be formed in the alignment film.
  • the horizontal alignment film is a photo-alignment film formed from a polymer having a (meth) acryloyl group.
  • the horizontal alignment film is similar to the polymerizable liquid crystal compound constituting the horizontal alignment liquid crystal cured film or has the same polymerizable group, the adhesion between the horizontal alignment film and the horizontal alignment liquid crystal cured film tends to be further increased.
  • the film is preferably formed from a polymer having a (meth) acryloyl group, and the horizontally aligned liquid crystal cured film is formed from a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a (meth) acryloyl group.
  • both the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film are formed from a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a (meth) acryloyl group. It is more preferable.
  • the photo-alignment film is usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as “photo-alignment film-forming composition”) to a substrate, removing the solvent and then polarizing the photo-alignment film. It is obtained by irradiating (preferably polarized UV).
  • the photo-alignment film is advantageous in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.
  • the photoreactive group refers to a group that produces liquid crystal alignment ability when irradiated with light.
  • groups involved in photoreactions that are the origin of liquid crystal alignment ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction caused by light irradiation.
  • a group involved in the dimerization reaction or the photocrosslinking reaction is preferable in terms of excellent orientation.
  • an unsaturated bond particularly a group having a double bond is preferable, and a carbon-carbon double bond (C ⁇ C bond), a carbon-nitrogen double bond (C ⁇ N bond), or a nitrogen-nitrogen two-bond.
  • a group having at least one selected from the group consisting of a heavy bond (N ⁇ N bond) and a carbon-oxygen double bond (C ⁇ O bond) is particularly preferred.
  • Examples of the photoreactive group having a C ⁇ C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group.
  • Examples of the photoreactive group having a C ⁇ N bond include groups having a structure such as an aromatic Schiff base and an aromatic hydrazone.
  • Examples of the photoreactive group having a C ⁇ O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.
  • a photoreactive group involved in the photodimerization reaction is preferable, the amount of polarized light irradiation necessary for photoalignment is relatively small, and a photoalignment film excellent in thermal stability and temporal stability can be easily obtained.
  • An azo group, a cinnamoyl group and a chalcone group are preferred.
  • the polymer having a photoreactive group a polymer having an azo group or a cinnamoyl group is preferable, and a polymer having a cinnamoyl group in which a terminal portion of the polymer side chain has a cinnamic acid structure is used as a horizontal alignment film and a horizontal alignment liquid crystal. This is particularly preferable from the viewpoint of improving the adhesion with the cured film.
  • a photo-alignment inducing layer can be formed on a substrate by applying the composition for forming a photo-alignment film on the substrate.
  • the solvent contained in the composition include those similar to the solvents exemplified above as solvents that can be used in the polymerizable liquid crystal composition, and are appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group. can do.
  • the content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the desired photoalignment film.
  • the mass is preferably at least 0.2 mass%, more preferably in the range of 0.3 to 10 mass%.
  • the composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer.
  • Examples of the method for applying the composition for forming a photo-alignment film to a substrate include the same methods as those for applying the alignment polymer composition to a substrate.
  • Examples of the method for removing the solvent from the applied composition for forming a photo-alignment film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.
  • polarized light In order to irradiate polarized light, it is possible to irradiate polarized light from the substrate side and transmit the polarized light even in the form of irradiating polarized UV directly to the composition from which the solvent is removed from the composition for forming a photo-alignment film applied on the substrate. It is also possible to irradiate.
  • the polarized light is particularly preferably substantially parallel light.
  • the wavelength of the polarized light to be irradiated is preferably in a wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferable.
  • Examples of the light source used for the polarized light irradiation include xenon lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and high pressure mercury lamps, ultra high pressure mercury lamps and metal halide lamps. preferable.
  • a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp are preferable because of high emission intensity of ultraviolet rays having a wavelength of 313 nm.
  • polarized UV light can be irradiated.
  • a polarizing prism such as a polarizing filter, Glan Thompson, or Grand Taylor, or a wire grid type polarizer can be used.
  • a plurality of regions (patterns) having different directions of liquid crystal alignment can be formed by performing masking during rubbing or polarized light irradiation.
  • the groove alignment film is a film having a concavo-convex pattern or a plurality of grooves (grooves) on the film surface.
  • a polymerizable liquid crystal compound is applied to a film having a plurality of linear grooves arranged at equal intervals, liquid crystal molecules are aligned in a direction along the groove.
  • a method for obtaining a groove alignment film a method of forming a concavo-convex pattern by performing development and rinsing after exposure through an exposure mask having a pattern-shaped slit on the photosensitive polyimide film surface, a plate having grooves on the surface A layer of a pre-curing UV curable resin is formed on the original master, a method of curing the resin layer after transferring the formed resin layer to the base material, and a pre-curing UV curable resin film formed on the base material, Examples include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.
  • the thickness of the alignment film is usually 100 to 5000 nm, preferably 100 to 1000 nm, more preferably 100 to 500 nm, still more preferably 100 to 300 nm, and particularly preferably 100. ⁇ 250 nm.
  • the thickness of the alignment film is within the above range, it has a sufficient horizontal alignment regulating force and hardly causes cohesive failure in the alignment film in the laminate.
  • the vertical alignment liquid crystal cured film is, for example, Applying a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film on a horizontally aligned liquid crystal cured film to obtain a coating film; Drying the coating film to form a dry coating film; and
  • the dry coating film can be produced by a method including a step of irradiating an active energy ray to form a vertically aligned liquid crystal cured film.
  • Formation of the coating film of the polymerizable liquid crystal composition can be performed, for example, by applying a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film on the horizontally aligned liquid crystal cured film.
  • Examples of the method for applying the polymerizable liquid crystal composition include the same methods as those that can be adopted in the method for producing a horizontally aligned liquid crystal cured film.
  • the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film are interposed through layers (excluding the adhesive layer) having no vertical alignment regulating force. May be laminated.
  • layers excluding the adhesive layer
  • Such a layer that does not have a vertical alignment regulating force include a cured resin layer and a hard coat layer intended to increase or reinforce the mechanical strength of the liquid crystal cured film.
  • the thickness of the other layer is preferably 0.1 to 4 ⁇ m, more preferably Is 0.5 to 3 ⁇ m.
  • the laminate of the present invention includes other layers as described above between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film, after forming the horizontally aligned liquid crystal cured film, the other layers are formed, and then A coating film of a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film may be formed on the other layer.
  • the cured resin layer can be formed of, for example, an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a urethane resin, a melamine resin, or the like.
  • an acrylic resin for example, an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a urethane resin, a melamine resin, or the like.
  • a dry paint film is formed by removing the solvent by drying or the like.
  • drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying. From the viewpoint of productivity, heat drying is preferable.
  • the heating temperature is preferably equal to or higher than the phase transition temperature of the polymerizable liquid crystal compound so that the solvent can be removed.
  • the procedures and conditions in this step are the same as those that can be adopted in the method for producing a horizontally aligned liquid crystal cured film.
  • the obtained dried coating film is irradiated with active energy rays (more specifically, ultraviolet rays or the like), and the polymerizable liquid crystal compound is maintained in a state in which the polymerizable liquid crystal compound is aligned in a direction perpendicular to the coating plane.
  • active energy rays more specifically, ultraviolet rays or the like
  • the polymerizable liquid crystal compound is maintained in a state in which the polymerizable liquid crystal compound is aligned in a direction perpendicular to the coating plane.
  • active energy rays more specifically, ultraviolet rays or the like
  • the thickness of the vertically aligned liquid crystal cured film can be appropriately selected depending on the display device to be applied, and is preferably 0.2 to 3 ⁇ m, more preferably 0.2 to 2 ⁇ m.
  • the vertically aligned liquid crystal cured film is positive wavelength dispersive, it is more preferably 0.2 to 1 ⁇ m, and when it is reverse wavelength dispersive, 0.4 to 2 ⁇ m is more preferable.
  • the vertical alignment liquid crystal cured film is formed from a polymerizable liquid crystal composition containing a vertical alignment accelerator, and thereby a vertical alignment liquid crystal cured film having no or few alignment defects can be obtained without using an alignment film.
  • the laminate of the present invention including such a vertically aligned liquid crystal cured film in combination with a horizontally aligned liquid crystal cured film tends to have excellent optical characteristics, and particularly when applied to an organic EL display device, the front and oblique directions when displaying black Excellent suppression effect of reflected hue. Further, since a step of forming an alignment film is not required, it is advantageous in terms of production efficiency and production cost.
  • the present invention includes an elliptically polarizing plate including the laminate of the present invention and a polarizing film.
  • the polarizing film is a film having a polarizing function, and examples thereof include a stretched film in which a dye having absorption anisotropy is adsorbed and a film including a film coated with a dye having absorption anisotropy as a polarizer. Examples of the dye having absorption anisotropy include a dichroic dye.
  • a film containing a stretched film adsorbed with a dye having absorption anisotropy as a polarizer is usually a step of uniaxially stretching a polyvinyl alcohol resin film, by dyeing the polyvinyl alcohol resin film with a dichroic dye, At least a polarizer produced through a step of adsorbing a dichroic dye, a step of treating a polyvinyl alcohol resin film adsorbed with a dichroic dye with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution It is produced by sandwiching it with a transparent protective film via an adhesive on one surface.
  • the polyvinyl alcohol resin is obtained by saponifying a polyvinyl acetate resin.
  • a polyvinyl acetate-based resin in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith are used.
  • examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
  • the degree of saponification of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more.
  • the polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used.
  • the degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, and preferably in the range of 1,500 to 5,000.
  • a film obtained by forming such a polyvinyl alcohol resin is used as an original film of a polarizing film.
  • the method for forming a polyvinyl alcohol-based resin is not particularly limited, and can be formed by a known method.
  • the film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 ⁇ m.
  • Uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with the dichroic dye, simultaneously with dyeing, or after dyeing.
  • the uniaxial stretching may be performed before boric acid treatment or during boric acid treatment.
  • it is also possible to perform uniaxial stretching in these several steps.
  • uniaxial stretching it may be uniaxially stretched between rolls having different peripheral speeds, or may be uniaxially stretched using a hot roll.
  • the uniaxial stretching may be dry stretching in which stretching is performed in the air, or may be wet stretching in which stretching is performed in a state where a solvent is used and a polyvinyl alcohol-based resin film is swollen.
  • the draw ratio is usually about 3 to 8 times.
  • the dyeing of the polyvinyl alcohol resin film with the dichroic dye is performed, for example, by a method of immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichroic dye.
  • dichroic pigment iodine or a dichroic organic dye is used as the dichroic pigment.
  • dichroic organic dyes include C.I. I.
  • dichroic direct dyes composed of disazo compounds such as DIRECT RED 39
  • dichroic direct dyes composed of compounds such as trisazo and tetrakisazo.
  • the polyvinyl alcohol-based resin film is preferably subjected to an immersion treatment in water before the dyeing treatment.
  • iodine When iodine is used as the dichroic dye, a method of dyeing a polyvinyl alcohol resin film by immersing it in an aqueous solution containing iodine and potassium iodide is usually employed.
  • the iodine content in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water.
  • the content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water.
  • the temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C.
  • the immersion time (dyeing time) in this aqueous solution is usually about 20 to 1,800 seconds.
  • a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed.
  • the content of the dichroic organic dye in this aqueous solution is usually about 1 ⁇ 10 ⁇ 4 to 10 parts by mass, preferably 1 ⁇ 10 ⁇ 3 to 1 part by mass, more preferably 100 parts by mass of water. Is 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 2 parts by mass.
  • This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant.
  • the temperature of the aqueous dichroic dye solution used for dyeing is usually about 20 to 80 ° C.
  • the immersion time (dyeing time) in this aqueous solution is usually about 10 to 1,800 seconds.
  • the boric acid treatment after dyeing with a dichroic dye can usually be performed by a method in which a dyed polyvinyl alcohol resin film is immersed in an aqueous boric acid solution.
  • the boric acid content in this aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass per 100 parts by mass of water.
  • this boric acid aqueous solution preferably contains potassium iodide.
  • the content of potassium iodide is usually 0.1 to 100 parts by mass of water.
  • the amount is about 15 parts by mass, preferably 5 to 12 parts by mass.
  • the immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds.
  • the temperature of boric acid treatment is usually 50 ° C. or higher, preferably 50 to 85 ° C., more preferably 60 to 80 ° C.
  • the polyvinyl alcohol resin film after the boric acid treatment is usually washed with water.
  • the water washing treatment can be performed, for example, by a method of immersing a boric acid-treated polyvinyl alcohol resin film in water.
  • the temperature of water in the water washing treatment is usually about 5 to 40 ° C.
  • the immersion time is usually about 1 to 120 seconds.
  • a drying process is performed to obtain a polarizer.
  • the drying process can be performed using, for example, a hot air dryer or a far infrared heater.
  • the temperature for the drying treatment is usually about 30 to 100 ° C., preferably 50 to 80 ° C.
  • the drying treatment time is usually about 60 to 600 seconds, preferably 120 to 600 seconds.
  • the moisture content of the polarizer is reduced to a practical level.
  • the moisture content is usually about 5 to 20% by mass, preferably 8 to 15% by mass.
  • the moisture content is less than 5% by mass, the flexibility of the polarizer is lost, and the polarizer may be damaged or broken after drying.
  • the thermal stability of the polarizer may be deteriorated.
  • the thickness of the polarizer obtained by uniaxial stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying on the polyvinyl alcohol resin film is preferably 5 to 40 ⁇ m.
  • Examples of the film coated with a dye having absorption anisotropy include a composition containing a dichroic dye having liquid crystallinity or a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal. Can be mentioned.
  • the film preferably has a protective film on one side or both sides. As the said protective film, the same thing as the resin film illustrated previously as a base material which can be used for manufacture of a horizontal alignment liquid crystal cured film is mentioned.
  • the film coated with the pigment having absorption anisotropy is preferably thin, but if it is too thin, the strength is lowered and the processability tends to be inferior.
  • the thickness of the film is usually 20 ⁇ m or less, preferably 5 ⁇ m or less, and more preferably 0.5 to 3 ⁇ m.
  • film coated with the dye having absorption anisotropy include films described in JP 2012-33249 A and the like.
  • a transparent protective film may be laminated on, for example, an adhesive layer on at least one surface of the polarizer thus obtained.
  • the transparent film similar to the resin film illustrated previously as a base material which can be used for manufacture of a horizontal alignment liquid crystal cured film can be used.
  • the elliptically polarizing plate of the present invention includes the laminate of the present invention and a polarizing film. For example, by laminating the laminate of the present invention and a polarizing film via an adhesive layer or the like. The elliptically polarizing plate of the present invention can be obtained.
  • the slow axis (optical axis) of the horizontally aligned liquid crystal cured film constituting the laminate and the absorption axis of the polarizing film when the laminate of the present invention and the polarizing film are laminated, the slow axis (optical axis) of the horizontally aligned liquid crystal cured film constituting the laminate and the absorption axis of the polarizing film.
  • Lamination is preferably performed so that the angle formed is 45 ⁇ 5 °.
  • the elliptically polarizing plate of the present invention may have a configuration that a conventional general elliptically polarizing plate, or a polarizing film and a retardation film are provided.
  • a configuration for example, it is used for the purpose of protecting the surface of an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element such as organic EL, a polarizing film or a liquid crystal cured film from scratches and dirt A protective film.
  • a display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light-emitting source.
  • a liquid crystal display device As the display device, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, a field emission display device (FED), a surface field emission display device) (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (eg, grating light valve (GLV) display device, display device having digital micromirror device (DMD))
  • the liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, and a projection liquid crystal display device.
  • These display devices include a table for displaying a two-dimensional image.
  • the device may be a three-dimensional display device that displays a three-dimensional image, and in particular, the elliptically polarizing plate of the present invention is notable for its effect, so that it is an organic electroluminescence (EL) display device.
  • the laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device, and the display device can be thinned by using the laminate or the elliptically polarizing plate of the present invention. Therefore, it is possible to obtain a display device that is easy to perform, has excellent optical characteristics, and can exhibit good image display characteristics.
  • Example 1 Preparation of composition for forming horizontal alignment film 5 parts by mass (weight average molecular weight: 30000) of photoalignment material having the following structure and 95 parts by mass of cyclopentanone (solvent) were mixed as components, and the resulting mixture was obtained. Was stirred at 80 ° C. for 1 hour to obtain a composition for forming a horizontal alignment film.
  • polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) having the following molecular structures were respectively prepared.
  • the polymerizable liquid crystal compound (X1) was produced according to the method described in JP 2010-31223 A.
  • the polymerizable liquid crystal compound (X2) was produced according to the method described in JP-A-2009-173893.
  • LC242 Paliocolor LC242 (registered trademark of BASF)
  • a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is applied on the horizontal alignment film, heated at 120 ° C. for 60 seconds, and then a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). Is used to form a horizontally aligned liquid crystal cured film by irradiating ultraviolet rays from the surface coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film (integrated light quantity at a wavelength of 365 nm: 500 mJ / cm 2 ) in a nitrogen atmosphere.
  • stacked the base material, the horizontal alignment film, and the horizontal alignment liquid crystal cured film adjacently in this order was obtained.
  • the film thickness of the obtained horizontally aligned liquid crystal cured film was measured by an ellipsometer and found to be 1.1 ⁇ m.
  • Is irradiated (accumulated light quantity at a wavelength of 365 nm in a nitrogen atmosphere: 500 mJ / cm 2 ) to form a vertical alignment liquid crystal cured film, and a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film are formed.
  • a laminated body laminated adjacently in this order was obtained.
  • the thickness of the obtained vertically aligned liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation) and found to be 0.6 ⁇ m.
  • the total film thickness T1 from the surface opposite to the vertical alignment liquid crystal cured film of the horizontal alignment liquid crystal cured film in this laminate to the surface opposite to the horizontal alignment liquid crystal cured film of the vertical alignment liquid crystal cured film is 1.7 ⁇ m. Met.
  • the front retardation value of the laminate including the aligned liquid crystal cured film and the horizontal aligned liquid crystal cured film, and the phase difference value when tilted by 40 ° about the fast axis center were measured. Also, the front phase difference value of the laminate composed of glass, pressure-sensitive adhesive, horizontal alignment liquid crystal cured film, horizontal alignment film, and substrate by the same method, and the phase difference value when tilted by 40 ° about the fast axis center It was measured. Subsequently, the average refractive index at each wavelength of each of the above-described vertically aligned liquid crystal cured film and horizontally aligned liquid crystal cured film was measured using an ellipsometer M-220 manufactured by JASCO Corporation.
  • the film thickness was measured using an Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics. From the above-mentioned front phase difference value, phase difference value when tilted by 40 ° about the fast axis center, average refractive index, and film thickness value, the technical data of Oji Measuring Instruments (http://www.oji-keisoku.co .Jp / products / kobra / reference.html) to calculate a three-dimensional refractive index.
  • the optical properties of the laminated body including the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film are calculated according to the following formula, and the vertical alignment is performed from the difference between the values.
  • RthC ( ⁇ ) ((nxC ( ⁇ ) + nyC ( ⁇ )) / 2 ⁇ nzC ( ⁇ )) ⁇ dC
  • RthC ( ⁇ ) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at the wavelength ⁇ nm.
  • nxC ( ⁇ ) is the in-plane main refractive index of the vertically aligned liquid crystal cured film at the wavelength ⁇ nm
  • nyC ( ⁇ ) is the refractive index in the direction orthogonal to nxC ( ⁇ ) at the wavelength ⁇ nm
  • nzC ( ⁇ ) indicates the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at the wavelength ⁇ nm.
  • nxC ( ⁇ ) nyC ( ⁇ )
  • nxC ( ⁇ ) is the refractive index in an arbitrary direction within the film plane.
  • DC represents the thickness of the vertically aligned liquid crystal cured film.
  • the adhesion test of the laminate was performed as follows with reference to the adhesion test (cross-cut method) of JIS K5600-5-6. First, the vertically aligned liquid crystal cured film side of the laminate and a glass of 5 ⁇ 5 cm ⁇ 0.7 mm thickness were bonded via a pressure sensitive adhesive (25 ⁇ m) manufactured by Lintec, and only the substrate was peeled from the laminate. . 100 mm of cuts of 1 mm ⁇ were made on the laminate side of the obtained sample with a cutter.
  • Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) is pasted on the obtained notch of 100 squares, peeled off the cellophane tape, and then confirmed the number of squares peeled between the layers in the laminate. The adhesion was judged. The results are shown in Table 1. Evaluation criteria: ⁇ : After peeling of the tape, the mass peeled between the layers in the laminate is less than 30 squares. (Triangle
  • Example 2 Except that the preparation of the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film and the formation of the horizontal alignment liquid crystal cured film were changed as follows, the substrate, the horizontal alignment film, and the horizontal alignment liquid crystal curing were the same as in Example 1. A laminate in which a film and a vertically aligned liquid crystal cured film were laminated adjacently in this order was prepared, and the adhesion and orientation of the laminate were evaluated. Table 1 shows the results.
  • NMP N-methyl-2-pyrrolidone
  • a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is applied onto the horizontal alignment film, heated at 120 ° C. for 60 seconds, and then a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). ) To irradiate ultraviolet rays from the surface coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film (accumulated light amount at a wavelength of 365 nm: 500 mJ / cm 2 in a nitrogen atmosphere) to form a horizontally aligned liquid crystal cured film.
  • Example 3 The substrate, the horizontal alignment film, and the horizontal alignment liquid crystal curing were the same as in Example 2 except that the preparation of the polymerizable liquid crystal composition for forming the vertical alignment liquid crystal cured film and the formation of the vertical alignment liquid crystal cured film were changed as follows. A laminate in which a film and a vertically aligned liquid crystal cured film were laminated adjacently in this order was prepared, and the adhesion and orientation of the laminate were evaluated. Table 1 shows the results.
  • polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film
  • Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture.
  • the ionic compound A (molecular weight: 645) prepared with reference to 0.25 parts by mass of the leveling agent “F-556” (manufactured by DIC) and Japanese Patent Application No. 2016-514802 with respect to 100 parts by mass of the obtained mixture.
  • silane coupling agent “KBE-9103” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Irgacure (registered trademark) 369 (Irg369) manufactured by BASF Japan Ltd.
  • NMP N-methyl-2-pyrrolidone
  • the vertical aligned liquid crystal cured film was formed by adjusting the integrated light quantity at 500 mJ / cm 2 .
  • the thickness of the obtained vertically aligned liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation) and found to be 1.2 ⁇ m.
  • Example 4 Except for changing the formation of the horizontal alignment liquid crystal cured film as follows, the substrate, the cured resin layer, the horizontal alignment film, the horizontal alignment liquid crystal cured film, and the vertical alignment liquid crystal cured film are adjacent in this order in the same manner as in Example 3. Thus, a laminated body was produced, and the adhesion and orientation of the laminated body were evaluated. Table 1 shows the results.
  • the COP film (ZF14-50) manufactured by Nippon Zeon Co., Ltd. was subjected to corona treatment, and then the cured resin layer forming composition was applied with a bar coater and dried at 50 ° C. for 1 minute.
  • a cured resin layer was formed by irradiating ultraviolet rays (integrated light amount at a wavelength of 365 nm: 400 mJ / cm 2 under a nitrogen atmosphere) using “UNICURE VB-15201BY-A” (manufactured by USHIO INC.). It was 2.0 micrometers when the film thickness of the obtained cured resin layer was measured with the contact-type film thickness meter.
  • a corona treatment was performed on the cured resin layer of the laminate comprising the base material and the cured resin layer produced by the above-described method, and the polymerizable liquid crystal composition for forming a horizontal alignment film was applied using a bar coater. .
  • a bar coater After drying at 80 ° C. for 1 minute, using a polarized UV irradiation apparatus (SPOT CURE SP-9; manufactured by USHIO INC.), Polarized UV exposure is performed at an integrated light amount of 100 mJ / cm 2 at a wavelength of 313 nm, and horizontal alignment is performed. A membrane was obtained. It was 200 nm when the film thickness of the obtained horizontal alignment film was measured with the ellipsometer.
  • a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is applied on the horizontal alignment film, heated at 120 ° C. for 60 seconds, and then a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.).
  • a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.).
  • the thickness of the obtained horizontally aligned liquid crystal cured film was measured with an ellipsometer and found to be 2.2 ⁇ m.
  • Example 5 A substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film were prepared in the same manner as in Example 3 except that the preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was changed as follows. A laminated body laminated adjacently in this order was produced, and the adhesion and orientation of the laminated body were evaluated. Table 1 shows the results.
  • polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film
  • Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture.
  • the ionic compound A (molecular weight: 645) prepared with reference to 0.25 parts by mass of the leveling agent “F-556” (manufactured by DIC) and Japanese Patent Application No. 2016-514802 with respect to 100 parts by mass of the obtained mixture.
  • Example 6 A substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film were prepared in the same manner as in Example 3 except that the preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was changed as follows. A laminated body laminated adjacently in this order was produced, and the adhesion and orientation of the laminated body were evaluated. Table 1 shows the results.
  • NMP N-methyl-2-pyrrolidone
  • Comparative Example 1 A substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film were prepared in the same manner as in Example 3 except that the preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was changed as follows. A laminated body laminated adjacently in this order was produced, and the adhesion and orientation of the laminated body were evaluated. Table 1 shows the results.
  • NMP N-methyl-2-pyrrolidone
  • a vertically aligned liquid crystal cured film can be produced without forming a vertically aligned film, and the liquid crystal alignment and adhesion can be improved at the same time (Examples 1 to 6).
  • a polymerizable liquid crystal composition containing no vertical alignment accelerator was used, a vertical alignment liquid crystal cured film could not be obtained without forming a vertical alignment film on the horizontal alignment liquid crystal cured film ( Comparative Example 1).

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Abstract

L'invention concerne un stratifié qui contient dans l'ordre un film durci à cristaux liquides orienté horizontalement et un film durci à cristaux liquides orienté verticalement. Ledit film durci à cristaux liquides orienté horizontalement consiste en un produit durci d'une composition de cristaux liquides polymérisable durcie dans un état tel qu'un composé cristallin liquide polymérisable est orienté horizontalement par rapport à la surface de ce film durci à cristaux liquides. Ledit film durci à cristaux liquides orienté verticalement consiste en un produit durci d'une composition de cristaux liquides polymérisable durcie dans un état tel qu'un composé cristallin liquide polymérisable est orienté verticalement par rapport à la surface de ce film durci à cristaux liquides. Ledit film durci à cristaux liquides orienté verticalement contient un promoteur d'orientation verticale. L'épaisseur totale de film d'une face dudit film durci à cristaux liquides orienté horizontalement côté opposé audit film durci à cristaux liquides orienté verticalement jusqu'à une face dudit film durci à cristaux liquides orienté verticalement côté opposé audit film durci à cristaux liquides orienté horizontalement, est inférieure ou égale à ５μｍ.
PCT/JP2019/004846 2018-02-14 2019-02-12 Stratifié, et procédé de fabrication de celui-ci WO2019159889A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114375418A (zh) * 2019-09-17 2022-04-19 住友化学株式会社 层叠体及包含该层叠体的椭圆偏振板

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