WO2020149357A1 - Corps stratifié, plaque de polarisation elliptique et composition de cristaux liquides polymérisables - Google Patents

Corps stratifié, plaque de polarisation elliptique et composition de cristaux liquides polymérisables Download PDF

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WO2020149357A1
WO2020149357A1 PCT/JP2020/001240 JP2020001240W WO2020149357A1 WO 2020149357 A1 WO2020149357 A1 WO 2020149357A1 JP 2020001240 W JP2020001240 W JP 2020001240W WO 2020149357 A1 WO2020149357 A1 WO 2020149357A1
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liquid crystal
cured film
crystal cured
vertically aligned
film
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PCT/JP2020/001240
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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 to CN202080009405.5A priority Critical patent/CN113302529B/zh
Priority to KR1020217023582A priority patent/KR20210114427A/ko
Publication of WO2020149357A1 publication Critical patent/WO2020149357A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • B29D11/00644—Production of filters polarizing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding 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
    • 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
    • H10K59/50—OLEDs integrated with light modulating elements, e.g. with electrochromic elements, photochromic elements or liquid crystal elements
    • 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 laminated body including a vertically aligned liquid crystal cured film and a substrate, an elliptical polarizing plate including the laminated body, and an organic EL display device. It also relates to a polymerizable liquid crystal composition that can be used to form the laminate.
  • the elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated, and for example, in a device that displays an image in a planar state such as an organic EL image display device, light reflection at an electrode that constitutes the device. It is used to prevent A so-called ⁇ /4 plate is generally used as the retardation plate constituting the elliptically polarizing plate.
  • a retardation plate composed of a horizontally aligned liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound in a state in which the polymerizable liquid crystal compound is oriented in the horizontal direction with respect to the plane of the retardation 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 vertical alignment film for orienting a polymerizable liquid crystal compound in the vertical direction is generally required to manufacture a vertically aligned liquid crystal cured film. For this reason, it is necessary to form the vertical alignment film before the formation of the vertical alignment liquid crystal cured film, and at least two or more coatings are required to obtain a coating film from each of the alignment film forming composition and the liquid crystal cured film forming composition. There is a problem that a film forming step is required and the productivity is likely to decrease. On the other hand, in order to improve productivity, there is a demand for a method of forming a vertical alignment liquid crystal cured film without forming a vertical alignment film. If only the step of forming the alignment film is omitted, there is a problem that the alignment property of the vertically aligned liquid crystal cured film becomes insufficient.
  • the present invention is a novel solution to the above problem, that is, it can be formed without a vertical alignment film, and the polymerizable liquid crystal compound is the same as the vertical alignment liquid crystal cured film formed on the vertical alignment film. It is an object of the present invention to provide a laminate including a vertically aligned liquid crystal cured film that is precisely aligned in the vertical direction.
  • a laminate including a vertically aligned liquid crystal cured film and a substrate The vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition that is cured in a state in which a polymerizable liquid crystal compound is aligned in a direction perpendicular to the liquid crystal cured film plane,
  • the vertical alignment liquid crystal cured film satisfies at least one of the following formulas (1) and (2), and at least one of the following formulas (3), (4), (5) and (6).
  • F(A) represents the abundance ratio (atom %) of elemental fluorine in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate
  • F(B) represents the abundance ratio (atom %) of elemental fluorine in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film
  • F(C) represents the abundance ratio (atom %) of the elemental fluorine in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film opposite to the substrate to the liquid crystal cured film side.
  • Si(A) represents the abundance ratio (atom %) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film opposite to the substrate
  • Si(B) represents the abundance ratio (atom %) of the silicon element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film
  • Si(C) represents the abundance ratio (atom %) of the silicon element in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film opposite to the substrate side to the liquid crystal cured film side.
  • N(B) represents the abundance ratio (atom %) of the nitrogen element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film
  • N(C) represents the abundance ratio (atom %) of the nitrogen element in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film opposite to the base material to the liquid crystal cured film side.
  • P(B) represents the abundance ratio (atom %) of the phosphorus element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film
  • P(C) represents the abundance ratio (atom %) of the phosphorus element in the liquid crystal cured film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film opposite to the substrate, to the liquid crystal cured film side. .. ] [2]
  • RthC (550) represents a retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm.
  • RthC (550) represents a retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm.
  • RthC(450) represents a retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm
  • RthC(550) represents a retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm.
  • [16] The laminate according to any one of [1] to [15], further including a horizontally oriented retardation film.
  • the horizontally aligned retardation film is a horizontally aligned liquid crystal cured film obtained by curing at least one polymerizable liquid crystal compound in a state of being aligned horizontally with respect to the in-plane direction of the retardation film.
  • the laminated body of description [18] An elliptically polarizing plate including the laminate according to [16] or [17] and a polarizing film. [19] The elliptically polarizing plate according to the above [18], wherein the angle between the slow axis of the horizontally oriented retardation film constituting the laminate and the absorption axis of the polarizing film is 45 ⁇ 5°.
  • An organic EL display device including the elliptically polarizing plate according to [18] or [19].
  • Polymerization including a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, and at least one selected from the group consisting of an ionic compound containing a nonmetal atom and a nonionic silane compound. Liquid crystal composition.
  • the polymerizable liquid crystal composition according to the above [21] which contains a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, an ionic compound containing a non-metal atom and a nonionic silane compound.
  • B11 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 16 -, -NR 16 -CO-, -CO-, -.
  • 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
  • the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms
  • the hydrogen atom contained in the alkoxy group. May be substituted with a halogen atom.
  • —CH 2 — constituting the alkanediyl group may be replaced with —O— or —CO—.
  • a base material is peeled off from the laminate according to any one of the laminates according to any one of [1] to [15], and the laminate peeled off from the base material and a horizontally aligned retardation film.
  • a vertical alignment liquid crystal that can be formed without a vertical alignment film, and in which a polymerizable liquid crystal compound is aligned in the vertical direction with high precision, like the vertical alignment liquid crystal cured film formed on the vertical alignment film.
  • a laminated body including a cured film can be provided.
  • the laminate of the present invention includes a vertically aligned liquid crystal cured film and a base material.
  • FIG. 1 shows one embodiment of the laminate of the present invention, and shows the most basic layer structure of the laminate of the present invention.
  • the laminated body 11 shown in FIG. 1 is formed by laminating a base material 1 and a vertically aligned liquid crystal cured film 2.
  • the vertically aligned liquid crystal cured film 2 is directly formed on the substrate 1, and the substrate 1 and the vertically aligned liquid crystal cured film 2 are adjacent to each other.
  • the laminate of the present invention may be configured to further include other layers in addition to the substrate and the vertically aligned liquid crystal cured film.
  • the vertical alignment liquid crystal cured film is provided on the base material or on the base material with or without a layer having a vertical alignment control force (hereinafter, also referred to as “vertical alignment film”). It can be formed on a layer having no vertical alignment control force.
  • the vertical alignment liquid crystal cured film can be laminated on the base material without the vertical alignment film interposed, and in the laminate of the present invention, the base material and the vertical alignment liquid crystal cured film are adjacent to each other. It is preferable that
  • the vertically aligned liquid crystal cured film constituting the laminate of the present invention satisfies at least one of the following formulas (1) and (2), and also satisfies the following formulas (3), (4), (5) and (6). At least one of F(A)>F(C) (1) Si(A)>Si(C) (2) N(B)>N(C) (3) P(B)>P(C) (4) F(B)>F(C) (5) Si(B)>Si(C) (6)
  • F(A) represents the abundance ratio (atom %) of elemental fluorine in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film on the side opposite to the substrate
  • F(B) represents the abundance ratio (atom %) of elemental fluorine in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film
  • F(C) represents the abundance ratio (atom %) of the elemental fluorine in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film opposite to the substrate to the liquid crystal cured film side.
  • Si(A) represents the abundance ratio (atom %) of the silicon element in the liquid crystal cured film at the interface of the vertically aligned liquid crystal cured film opposite to the substrate
  • Si(B) represents the abundance ratio (atom %) of the silicon element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film
  • Si(C) represents the abundance ratio (atom %) of the silicon element in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film opposite to the substrate side to the liquid crystal cured film side.
  • N(B) represents the abundance ratio (atom %) of the nitrogen element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film
  • N(C) represents the abundance ratio (atom %) of the nitrogen element in the liquid crystal cured film at a point 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film opposite to the base material to the liquid crystal cured film side.
  • P(B) represents the abundance ratio (atom %) of the phosphorus element in the liquid crystal cured film at the interface on the substrate side of the vertically aligned liquid crystal cured film
  • P(C) represents the abundance ratio (atom %) of the phosphorus element in the liquid crystal cured film at a point of 100 nm in the thickness direction from the interface of the vertically aligned liquid crystal cured film opposite to the substrate, to the liquid crystal cured film side. ..
  • the above formulas (1) to (6) serve as indices showing uneven distribution of a specific element in the vertically aligned liquid crystal cured film.
  • F, Si, N and P in the formulas (1) to (6) represent fluorine element, silicon element, nitrogen element and phosphorus element, respectively.
  • (A) is an interface of the vertically aligned liquid crystal cured film opposite to the substrate (hereinafter, also referred to as “non-substrate side interface”), and (B) is a vertically aligned liquid crystal cured film.
  • Point hereinafter, also referred to as “middle point”
  • fluorine element, silicon element, nitrogen element and phosphorus element are unevenly distributed in a specific positional relationship in the vertically aligned liquid crystal cured film.
  • Such uneven distribution of the specific element means that the additives functioning as the leveling agent and the vertical alignment promoter are unevenly distributed in the vertical alignment liquid crystal cured film in a specific positional relationship.
  • the surface energy of the cured film can be controlled and the electrostatic repulsive force with respect to the polymerizable liquid crystal compound can be expressed.
  • an alignment regulating force that aligns the polymerizable liquid crystal compound in the direction perpendicular to the film plane of the liquid crystal cured film is developed, and the polymerizable liquid crystal compound is aligned in the direction perpendicular to the film plane without the vertical alignment film. It is considered that a vertically aligned liquid crystal cured film having an orientation can be formed.
  • the unevenly distributed positions are tens of nm (maximum at maximum) from both the non-substrate side and the substrate side of the liquid crystal cured film.
  • nm maximum at maximum
  • the above formula (1) means that the abundance ratio (atom %) of the fluorine element at the non-base material side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom %) of the fluorine element at the midpoint, This indicates that elemental fluorine is unevenly distributed on the non-base material side interface.
  • the above formula (2) means that the abundance ratio (atom %) of the silicon element at the non-base material side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom %) of the silicon element at the midpoint, It means that the silicon element is unevenly distributed on the non-base material side interface.
  • the uneven distribution of the fluorine element and/or the silicon element at the non-base material side interface of the vertically aligned liquid crystal cured film may be due to, for example, that the liquid crystal cured film contains fluorine element and/or silicon element as a constituent component on the non-base material side interface side. It can be realized by including a component that easily segregates (for example, a surfactant or the like).
  • the surface energy at the non-base material side interface of the liquid crystal cured film becomes low.
  • the polymerizable liquid crystal compound is easily oriented in the vertical direction.
  • the vertically aligned liquid crystal cured film constituting the laminate of the present invention satisfies at least one of the above formulas (3), (4), (5) and (6).
  • the above formula (3) means that the abundance ratio (atom %) of the nitrogen element at the substrate-side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom %) of the nitrogen element at the midpoint. Indicates that the nitrogen element is unevenly distributed on the material side interface.
  • the above formula (4) means that the abundance ratio (atom %) of the phosphorus element at the substrate-side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom %) of the phosphorus element at the midpoint. This indicates that the phosphorus element is unevenly distributed on the material-side interface.
  • the above formula (5) means that the abundance ratio (atom %) of the elemental fluorine at the substrate side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom %) of the elemental fluorine at the midpoint. This indicates that elemental fluorine is unevenly distributed on the material-side interface.
  • the above formula (6) means that the abundance ratio (atom %) of the silicon element at the substrate side interface of the vertically aligned liquid crystal cured film is higher than the abundance ratio (atom %) of the silicon element at the midpoint. This indicates that the silicon element is unevenly distributed on the material-side interface.
  • the uneven distribution of nitrogen element, phosphorus element, fluorine element and/or silicon element at the substrate side interface of the vertically aligned liquid crystal cured film is, for example, that the liquid crystal cured film constitutes nitrogen element, phosphorus element, fluorine element and/or silicon element. It can be realized by including a component that is included as a component and is easily segregated on the interface side on the substrate side (for example, an ionic compound or the like). Although the mechanism of exerting the vertical alignment control force due to the uneven distribution of these components is not clear, the polarities of the ionic compound having a charge and the polymerizable liquid crystal compound having no charge are usually largely different from each other.
  • the liquid crystal cured film When the cured liquid crystal film satisfies at least one of the formulas (3), (4), (5) and (6), the liquid crystal cured film is allowed to remain statically between the substrate side interface and the polymerizable liquid crystal compound. An electric repulsion effect can be produced, and the polymerizable liquid crystal compound is easily aligned in the vertical direction.
  • a vertical alignment liquid crystal cured film having a vertical alignment regulating force for the polymerizable liquid crystal compound is obtained. Therefore, the element unevenly distributed on the base material side interface side may be any of nitrogen element, phosphorus element, fluorine element or silicon element.
  • the vertically aligned liquid crystal cured film is represented by the formula (3) and the formula: It is preferable that at least one of (4) is satisfied and at least one of formula (5) and formula (6) is satisfied, and formulas (3), (4), (5) and (6) are satisfied. It is more preferable to satisfy at least 3 of the above, more preferably at least one of the formulas (3) and (4), and further preferable to satisfy the formulas (5) and (6).
  • the vertically aligned liquid crystal cured film constituting the laminate of the present invention satisfies at least one of formulas (1) and (2), and formulas (3), (4), (5) and (6). Satisfying at least one of By satisfying at least one of the formulas (1) and (2) and satisfying at least one of the formulas (3) to (6), the surface energy at the non-base material side interface of the liquid crystal cured film is satisfied. And the electrostatic repulsion effect at the interface of the liquid crystal cured film on the substrate side can exert a vertical alignment control force on the polymerizable liquid crystal compound from both interfaces of the liquid crystal cured film.
  • the polymerizable liquid crystal compound can be aligned in the direction perpendicular to the film plane of the liquid crystal cured film with higher accuracy without the vertical alignment film.
  • the vertically aligned liquid crystal cured film can have the following aspects. a) satisfying at least one of formulas (1) and (2), satisfying at least one of formulas (3) and (4), and at least one of formulas (5) and (6) Meet one. b) At least one of the expressions (1) and (2) is satisfied, and at least three of the expressions (3) to (6) are satisfied. c) at least one of the formulas (1) and (2) is satisfied, and at least one of the formulas (3) and (4) is satisfied, and the formulas (5) and (6) are simultaneously satisfied. Fulfill.
  • the aspect (b) is preferable because the polymerizable liquid crystal compound is easily aligned in the vertical direction, and the aspect (c) is more preferable because the polymerizable liquid crystal compound is easily aligned vertically with higher accuracy. ..
  • the difference [F(A)-F(C)] with the abundance ratio (atom %) is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably 0.5 or more.
  • the upper limit of the difference between F(A) and F(C) is not particularly limited and is usually 50 or less, preferably 30 or less.
  • the difference [Si(A)-Si(C)] with the abundance ratio (atom %) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10.
  • the upper limit of the difference between Si(A) and Si(C) is not particularly limited and is usually 50 or less, preferably 30 or less.
  • the existence ratio (atom %) of the nitrogen element at the base material side interface represented by N(B) and the nitrogen element at the intermediate point represented by N(C) is preferably 0.001 or more, more preferably 0.01 or more, and further preferably 0.05 or more.
  • the difference between N(B) and N(C) is at least the above lower limit, a sufficient amount of nitrogen element is unevenly distributed on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is vertically oriented. It becomes easy to orient accurately.
  • the upper limit of the difference between N(B) and N(C) is not particularly limited and is usually 30 or less, preferably 10 or less.
  • the phosphorus element existence ratio (atom %) at the substrate-side interface represented by P(B) and the phosphorus element at the intermediate point represented by P(C) is preferably 0.001 or more, more preferably 0.01 or more, still more preferably 0.05 or more.
  • the difference between P(B) and P(C) is not less than the above lower limit, a sufficient amount of phosphorus element is unevenly distributed on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is vertically oriented. It becomes easy to orient accurately.
  • the upper limit of the difference between P(B) and P(C) is not particularly limited and is usually 30 or less, preferably 10 or less.
  • the abundance ratio (atom %) of the elemental fluorine at the base material side interface represented by F(B) and the elemental fluorine content at the intermediate point represented by F(C) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10.
  • the difference between F(B) and F(C) is not less than the above lower limit, a sufficient amount of fluorine element is unevenly distributed on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is vertically oriented. It becomes easy to orient accurately.
  • the upper limit of the difference between F(B) and F(C) is not particularly limited and is usually 50 or less, preferably 30 or less.
  • the presence ratio (atom %) of the silicon element at the base material side interface represented by Si(B) and the silicon element at the intermediate point represented by Si(C) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10.
  • the difference between Si(B) and Si(C) is at least the above lower limit, a sufficient amount of silicon element is unevenly distributed on the substrate interface side of the vertically aligned liquid crystal cured film, and the polymerizable liquid crystal compound is vertically oriented. It becomes easy to orient accurately.
  • the upper limit of the difference between Si(B) and Si(C) is not particularly limited and is usually 50 or less, preferably 30 or less.
  • the existence ratio of the element in the non base material side interface is not particularly limited, and may be the same or higher than each other.
  • the above formulas (1) to (6) in the vertically aligned liquid crystal cured film are each a fluorine element and/or a silicon element depending on the polymerizable liquid crystal compound used to form the vertically aligned liquid crystal cured film.
  • a component which is included as a constituent component and is easily segregated on the interface side on the non-base material side or a component which contains nitrogen element, phosphorus element, fluorine element and/or silicon element as a constituent component and which is easily segregated on the interface side on the base material side.
  • the composition of the composition for forming a vertically aligned liquid crystal cured film can be controlled by adjusting the types, their blending amounts and combinations, the composition of the composition for forming a vertically aligned liquid crystal cured film, the manufacturing conditions for the vertically aligned liquid crystal cured film, the type of the substrate to be coated, the surface treatment conditions, etc. it can.
  • the formula (1) and/or (2) can be obtained.
  • a vertically aligned liquid crystal cured film that satisfies the requirement can be obtained.
  • the ratio of each element in the vertically aligned liquid crystal cured film can be measured by an X-ray photoelectron spectroscopy (XPS) method. For example, after the constituent elements of the interface on the non-base material side of the vertically aligned liquid crystal cured film are analyzed by XPS, etching is performed from the non-base material side interface to obtain 100 nm in the thickness direction of the liquid crystal cured film from the non-base material side interface.
  • XPS X-ray photoelectron spectroscopy
  • the constituent elements in the liquid crystal cured film at the point of are analyzed by XPS, then the base material is peeled from the vertically aligned liquid crystal cured film used in the analysis, and the constitution of the surface from which the base material is peeled (base material side interface) Elements can be analyzed by XPS. More detailed conditions such as XPS measurement conditions and etching conditions for analyzing the constituent elements at the intermediate points can be appropriately determined according to the measurement device, the sample to be measured, and the like. The conditions described in the examples can be adopted.
  • the vertically aligned liquid crystal cured film that constitutes the laminate of the present invention is a cured product of the polymerizable liquid crystal composition that is cured in a state where the polymerizable liquid crystal compound is aligned in the direction perpendicular to the plane of the liquid crystal cured film.
  • the polymerizable liquid crystal composition for forming the vertically aligned liquid crystal cured film is such that, in addition to the polymerizable liquid crystal compound, the liquid crystal cured film obtained is represented by Formulas (1) to (6). It is configured to include a component for causing uneven distribution of a specific element.
  • the vertically aligned liquid crystal cured film constituting the laminate contains a fluorine element and/or a silicon element as a constituent component and a component that easily segregates on the interface side on the non-base material side.
  • a fluorine element and/or a silicon element as a constituent component and a component that easily segregates on the interface side on the non-base material side.
  • the manufacturing process of the laminated body is simplified, and the laminated body can be manufactured with high productivity.
  • the component that contains elemental fluorine and/or elemental silicon and is prone to segregate on the interface side on the non-base material side include a leveling agent, a nonionic silane compound, and an ionic compound.
  • the vertically aligned liquid crystal cured film preferably contains a leveling agent.
  • the leveling agent has a function of adjusting fluidity of the polymerizable liquid crystal composition and flattening a coating film obtained by applying the composition, and a typical leveling agent includes a surfactant and the like. ..
  • elemental fluorine and/or elemental silicon is likely to be unevenly distributed on the non-base material side interface of the liquid crystal cured film, and while exerting the function as a conventional leveling agent, it exerts a high vertical alignment control force on the polymerizable liquid crystal compound.
  • the vertically aligned liquid crystal cured film is formed from a leveling agent containing a silicon element (hereinafter, also referred to as “silicone leveling agent”) and a leveling agent containing a fluorine element (hereinafter, also referred to as “fluorine leveling agent”). It is more preferred to include at least one leveling agent selected.
  • the vertically aligned liquid crystal cured film easily satisfies the formula (1) by containing the leveling agent containing the fluorine element, and easily satisfies the formula (2) by containing the leveling agent containing the silicon element.
  • these leveling agents only one kind may be used, or two or more kinds may be used in combination.
  • a commercially available product may be used as the leveling agent.
  • the silicone-based leveling agent and the fluorine-based leveling agent specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all above, Toray Dow Corning )), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all from Momentive Performance Materials Japan GK), Fluorinert (registered trademark) FC-72, FC-40, FC-43, FC-3283 (all Sumitomo 3M ( Co., Ltd.), Megafac (registered trademark) R-08, R-08
  • the content thereof is preferably 0.001 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film. Or more, more preferably 0.01 parts by mass or more, further preferably 0.03 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1.5 parts by mass or less. Is.
  • the content of the leveling agent is within the above range, the vertical alignment property of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coatability of the polymerizable liquid crystal composition.
  • the content of the leveling agent means the total content of all leveling agents contained in the vertically aligned liquid crystal cured film.
  • the vertically aligned liquid crystal cured film preferably contains a nonionic silane compound.
  • the nonionic silane compound generally tends to segregate on the non-base material side interface of the vertically aligned liquid crystal cured film, and by including this, a liquid crystal cured film satisfying the formula (2) can be obtained.
  • the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains a nonionic silane compound
  • the nonionic silane compound lowers the surface tension of the polymerizable liquid crystal composition, and the non-substrate side of the liquid crystal cured film Since the surface energy of the interface can be lowered, the vertical alignment regulating force for the polymerizable liquid crystal compound can be increased.
  • the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.
  • the inclusion of the nonionic silane compound in addition to the leveling agent described above causes the vertical alignment control force due to the above-mentioned effects to be more remarkably exhibited.
  • a nonionic silane compound is a nonionic compound containing silicon element.
  • the nonionic silane compound include silicon polymers such as polysilane, silicone resins such as silicone oil and silicone resin, and organic-inorganic silane compounds such as silicone oligomer, silsessiloxane and alkoxysilane (more specifically, Silane coupling agents, etc.) and the like.
  • the above-mentioned leveling agent containing a silicon element corresponds to a nonionic silane compound in terms of its molecular structure, but in the present invention, the leveling agent containing a silicon element (silicone-based leveling agent) has a remarkable leveling property.
  • the silicone-based leveling agent generally has a large molecular weight and preferably has a weight average molecular weight of 1000 or more in order to exhibit the leveling property.
  • the nonionic silane compound may be of a silicone monomer type or a silicone oligomer (polymer) type.
  • silicone oligomer is shown in the form of (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Copolymers containing mercaptopropyl groups such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetra Copolymers containing mercaptomethyl groups such as ethoxys
  • the silane coupling agent is selected from the group consisting of vinyl group, epoxy group, styryl group, methacrylic group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, isocyanate group, carboxyl group, and hydroxyl group at the terminal.
  • a compound containing an elemental silicon having at least one functional group as defined above and at least one alkoxysilyl group or silanol group.
  • 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 its molecule, the vertical alignment property of the polymerizable liquid crystal compound is more likely to be improved, and the vertical alignment promotion effect is remarkably obtained.
  • the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxyl group and a hydroxy group.
  • the polar group may optionally have a substituent or a protective group 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 Methoxysilane, 3-
  • silane coupling agents examples include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402 and 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. Are listed.
  • the content thereof is generally 100 in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film.
  • the amount is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass. It is not more than 3 parts by mass, more preferably not more than 3 parts by mass.
  • the vertically aligned liquid crystal cured film forming the laminate of the present invention preferably contains a nitrogen element, a phosphorus element, a fluorine element and/or a silicon element as constituent components, and contains a component which is easily segregated on the interface side of the substrate side. ..
  • a liquid crystal cured film satisfying the formulas (3), (4), (5) and/or (6) can be obtained.
  • the component that tends to segregate on the interface side on the base material side include ionic compounds containing nitrogen element, phosphorus element, elemental fluorine and/or elemental silicon.
  • a nitrogen element, a phosphorus element, or a fluorine element may be present at the interface on the substrate side of the liquid crystal cured film due to such a component.
  • an electrostatic repulsion effect is exerted on the polymerizable liquid crystal compound at the interface of the liquid crystal cured film where the element is present on the substrate side.
  • the polymerizable liquid crystal compound tries to arrange so that the contact area becomes small with respect to the interface of the liquid crystal cured film on the substrate side. Can be expressed.
  • the vertically aligned liquid crystal cured film preferably contains an ionic compound composed of a non-metal atom.
  • the ionic compound composed of a non-metal atom tends to be unevenly distributed at the interface on the substrate side in the vertically aligned liquid crystal cured film, and particularly when the polarity of the substrate film is high, for example, when a triacetyl cellulose film is used or When the material is subjected to corona treatment, plasma treatment, excimer light irradiation treatment, etc., it tends to become more unevenly distributed.
  • the vertically aligned liquid crystal cured film contains the above-mentioned leveling agent, in particular, a leveling agent containing a silicon element or a leveling agent containing a fluorine element, or an ionic compound containing a non-metallic atom together with a non-ionic silane compound, thereby providing a vertically aligned liquid crystal.
  • a leveling agent containing a silicon element or a leveling agent containing a fluorine element or an ionic compound containing a non-metallic atom together with a non-ionic silane compound, thereby providing a vertically aligned liquid crystal. Since the vertical alignment regulating force for the polymerizable liquid crystal compound acts from both sides of the non-base material side interface and the base material side interface of the cured film, the polymerizable liquid crystal compound is easily aligned in the vertical direction, and the alignment accuracy can be further improved. it can.
  • Examples of the ionic compound composed of a non-metal atom include an onium salt (more specifically, a quaternary ammonium salt having a nitrogen atom having a positive charge, a tertiary sulfonium salt, and a phosphorus atom having a positive charge). Quaternary phosphonium salts and the like).
  • the vertically aligned liquid crystal cured film easily satisfies the formula (3) when it contains an ammonium salt, and easily satisfies the formula (4) when it contains a phosphonium salt.
  • quaternary onium 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, quaternary phosphonium salts or quaternary salts.
  • Ammonium salts are more preferred.
  • the onium salt may have two or more quaternary onium salt moieties in the molecule, and may be an oligomer or polymer.
  • the molecular weight of the ionic compound composed of non-metal atoms is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, it is easy to improve the vertical alignment of the polymerizable liquid crystal compound while maintaining the coatability of the polymerizable composition.
  • the molecular weight of the ionic compound composed of non-metal atoms is more preferably 5,000 or less, still more preferably 3,000 or less.
  • Examples of the cation component of the ionic compound composed of non-metal atoms include inorganic cations and organic cations. Among them, organic cations are preferable because they are unlikely to cause alignment defects in the polymerizable liquid crystal compound. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, sulfonium cations and phosphonium cations.
  • Ionic compounds composed of non-metal atoms generally have a counter anion.
  • the anion component serving as the counter ion of the cation component include an inorganic anion and an organic anion. Among them, organic anions are preferable because they do not easily cause alignment defects of the polymerizable liquid crystal compound.
  • Formula (5) can be easily satisfied by using an anion containing a fluorine element in the molecular structure as a counter anion. The cation and the anion do not necessarily have to 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 anions [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 C
  • ionic compound composed of a non-metal atom can be appropriately selected from the combination of the above cation component and 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 composed of a non-metal atom is preferably a phosphonium salt having an alkyl group, an ammonium salt having an alkyl group, or the like, and as a counter anion thereof, a fluorine atom such as a fluorosulfonyl group or a trifluoroalkylsulfonyl group is contained.
  • a counter anion having a sulfonyl group and the like are preferable.
  • the alkyl group in the phosphonium salt having an alkyl group and the ammonium salt having an alkyl group may have a substituent such as a hydroxy group or an alkoxysilyl group.
  • a substituent such as a hydroxy group or an alkoxysilyl group.
  • an ionic compound consisting of a phosphonium salt or an ammonium salt having a positive charge on the nitrogen atom is preferable, and an anion containing a fluorine element in the molecular structure is used as a counter anion. More preferred are ionic compounds consisting of phosphonium salts or ammonium salts.
  • the ionic compound composed of a non-metal atom preferably has a silicon element and/or a fluorine element in the molecular structure of the cation site.
  • the ionic compound composed of a non-metal atom has a silicon element and/or a fluorine element in the molecular structure of the cation site, the ionic compound easily segregates on the surface of the vertically aligned liquid crystal cured film.
  • a salt composed of an ammonium cation or a phosphonium cation having a (C1-C4)alkoxysilylalkyl group and bis(trifluoromethanesulfonyl)imide is preferable, and the following ions
  • the compounds (I) to (III) and the like are more preferable.
  • a method of treating the substrate surface with a surfactant having an alkyl group with a somewhat long chain length to improve the liquid crystal alignment for example, "Liquid Crystal Handbook", Chapter 2, Liquid Crystal Alignment and Physical Properties). (Published by Maruzen Co., Ltd.) can be applied to further improve the vertical alignment of the polymerizable liquid crystal compound. That is, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved by treating the surface of the base material with an ionic compound having an alkyl group having a long chain length to some extent.
  • the ionic compound containing a non-metal atom satisfies the following formula (9). 5 ⁇ M ⁇ 16 (9)
  • a positive charge to be considered as a base point for a substituent having two or more atoms having a positive charge is defined as “the number of covalent bonds from the atom having a positive charge to the end of the molecular chain” in the definition of M above.
  • the ionic compound composed of a non-metal atom is an oligomer or polymer having two or more repeating units, the constitutional unit is considered as one molecule, and the above M is calculated.
  • the number of covalent bonds up to the atom with a positive charge via the ring structure or the end of the substituent bonded to the ring structure is defined as "the number of covalent bonds from the atom having a positive charge to the end of the molecular chain" in the definition of M above.
  • the content of the ionic compound in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film is usually the same as that of the polymerizable liquid crystal composition contained in the polymerizable liquid crystal composition. It is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, relative to 100 parts by mass of the liquid crystal compound. It is preferably 4 parts by mass or less, more preferably 3 parts by mass or less.
  • the vertically aligned liquid crystal cured film contains both a nonionic silane compound and an ionic compound consisting of a non-metal atom, electrostatic interaction derived from the ionic compound and surface tension reduction derived from the nonionic silane compound The effect makes it easier to promote vertical alignment of the polymerizable liquid crystal compound. This makes it possible to form a liquid crystal cured film in which the polymerizable liquid crystal compound is vertically aligned more accurately. Therefore, in a preferred embodiment of the present invention, the vertically aligned liquid crystal cured film contains a nonionic silane compound and an ionic compound containing a nonmetal atom.
  • the vertical alignment liquid crystal cured film contains a leveling agent, a nonionic silane compound, and an ionic compound composed of a nonmetal atom, whereby the alignment accuracy of the polymerizable liquid crystal compound can be further improved. Therefore, in another preferred embodiment of the present invention, the vertically aligned liquid crystal cured film contains a leveling agent, a nonionic silane compound, and an ionic compound composed of a nonmetal atom.
  • the vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is oriented in a direction perpendicular to the film plane of the liquid crystal cured film. It is a liquid crystal cured film that is cured in a state of being aligned in the direction.
  • 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.
  • the polymerizable liquid crystal compound is not particularly limited, and for example, a conventionally known polymerizable liquid crystal compound in the field of retardation film can be used.
  • Polymerizable group means a group that can participate in a polymerization reaction by an active radical or acid generated from a polymerization initiator.
  • examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group and an oxetanyl group.
  • 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 further preferable.
  • the liquid crystallinity of the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferable in that precise film thickness control is possible.
  • the phase ordered structure in the thermotropic liquid crystal may be nematic liquid crystal or smectic liquid crystal.
  • the polymerizable liquid crystal compounds can be used alone or in combination of two or more kinds.
  • the polymerizable liquid crystal compound generally includes a polymerizable liquid crystal compound exhibiting a positive wavelength dispersibility and a polymerizable liquid crystal compound exhibiting a reverse wavelength dispersibility, and it is possible to use only one type of the polymerizable liquid crystal compound. Alternatively, both types of polymerizable liquid crystal compounds may be mixed and used.
  • a display device incorporating the obtained laminate preferably contains a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion from the viewpoint of increasing the effect of suppressing the oblique reflection hue during black display.
  • the polymerizable liquid crystal compound only one kind may be used, or two or more kinds may be used in combination.
  • the polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is preferably a compound having the following characteristics (A) to (D).
  • B It has ⁇ electrons in the major axis direction (a) of the polymerizable liquid crystal compound.
  • D A polymerizable liquid crystal compound defined by the following formula (i), where N( ⁇ a) is the total of ⁇ electrons existing in the major axis direction (a) and N(Aa) is the total of molecular weights present in the major axis direction.
  • ⁇ electron density in the major axis direction (a) of: D( ⁇ a) N( ⁇ a)/N(Aa) (i) And a total of ⁇ electrons existing in the cross direction (b) is N( ⁇ b), and a total of molecular weights existing in the cross direction (b) is N(Ab), and the polymerizable liquid crystal compound is defined by the following formula (ii).
  • the polymerizable liquid crystal compound having ⁇ electrons in the major axis and in the direction intersecting with the major axis has, for example, a T-shaped structure.
  • the major axis direction (a) and the ⁇ electron number N are defined as follows.
  • the major axis direction (a) is, for example, a rod-shaped major axis direction in the case of a compound having a rod-shaped structure.
  • the number of ⁇ electrons N ( ⁇ a) existing in the major axis direction (a) does not include ⁇ electrons that disappear due to the polymerization reaction.
  • the number of ⁇ electrons existing in the major axis direction (a) is the total number of ⁇ electrons on the major axis and ⁇ electrons conjugated with this, and exists in the major axis direction (a), for example.
  • the number of ⁇ electrons existing in a ring that satisfies Huckel's rule is included.
  • 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.
  • a liquid crystal phase (nematic phase, smectic phase) is developed by this mesogenic structure.
  • a nematic phase or a smectic phase by applying a polymerizable liquid crystal compound satisfying the above (A) to (D) onto a film (layer) forming a liquid crystal cured film and heating the film above a phase transition temperature.
  • the polymerizable liquid crystal compounds are usually aligned such that the major axis directions thereof are parallel to each other, and the major axis direction is the alignment direction of the nematic phase.
  • a polymer film composed of a polymer polymerized in a state of being aligned 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 maximum absorption wavelength of ultraviolet rays absorbed by ⁇ electrons in the crossing 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 crossing direction (b) is higher than the ⁇ electron density in the major axis direction (a).
  • the absorption of the linearly polarized ultraviolet light having a wavelength of ⁇ bmax is larger than that of the linearly polarized ultraviolet light having a vibration plane in the major axis direction (a) (the wavelength is ⁇ bmax).
  • the ratio (the ratio of the absorbance in the crossing direction (b) of the linearly polarized ultraviolet light/the absorbance in the major 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. Is.
  • the polymerizable liquid crystal compound having the above-mentioned properties generally exhibits reverse wavelength dispersion.
  • Examples of the polymerizable liquid crystal compound include compounds represented by the following formula (X).
  • Ar represents a divalent group having an aromatic group which may have a substituent.
  • aromatic group refers to an aromatic group having a number of ⁇ electrons of [4n+2] according to Huckel's rule, and is exemplified by (Ar-1) to (Ar-23) described later. You may have two or more such Ar groups through the bivalent coupling group.
  • n represents an integer.
  • the aromatic group 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. When there is one aromatic group, the divalent group Ar may be a divalent aromatic group which may have a substituent. When 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 or a divalent bonding group such as —CO—O— or —O—. May be.
  • G 1 and G 2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group.
  • the hydrogen atom contained in the divalent aromatic group or the 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 which may be substituted with an alkoxy group, a cyano group or a nitro group of the formulas 1 to 4 and which constitutes the divalent aromatic group or divalent alicyclic hydrocarbon group is an oxygen atom or 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.
  • k and l each independently represent an integer of 0 to 3 and satisfy the relationship of 1 ⁇ k+l.
  • B 1 and B 2 , and G 1 and G 2 may be the same as or different from each other.
  • E 1 and E 2 each independently represent an alkanediyl group having 1 to 17 carbon atoms, and an alkanediyl group having 4 to 12 carbon atoms is more preferable.
  • P 1 and P 2 independently of each other 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.
  • a 1,4-cyclohexanediyl group which may be 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.
  • At least one of a plurality of G 1 and G 2 present is preferably a divalent alicyclic hydrocarbon group, and at least one of G 1 and G 2 bonded to L 1 or L 2 is 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.
  • R a1 to R a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms
  • R c and R d represent 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 more preferably 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 —, or —R a13.
  • R a9 to R a16 each independently represent 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 an epoxy group, a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group and an oxiranyl group. , And an oxetanyl group. Among them, 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 heterocycle 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.
  • the aromatic heterocycle includes a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring and a pyrazole ring.
  • a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferable, and a benzothiazole group is more preferable.
  • Ar contains 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, further preferably 14 or more, and particularly It is preferably 16 or more. Further, it is preferably 30 or less, more preferably 26 or less, and further preferably 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 group having 1 to 12 carbon atoms.
  • Z 0 , Z 1 and Z 2 may include a polymerizable group.
  • Q 1 and Q 2 each independently represent —CR 2′ R 3′ —, —S—, —NH—, —NR 2′ —, —CO— or —O—, and R 2′ and R 3 ' 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 represent an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.
  • W 1 and W 2 each independently represent 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 for Y 1 , Y 2 and Y 3 include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl group, naphthyl group, anthryl group, phenanthryl group and biphenyl group, and phenyl group. , A naphthyl group is preferable, and a phenyl group is more preferable.
  • the aromatic heterocyclic group includes a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, a benzothiazolyl group and the like, a nitrogen atom, an oxygen atom, a sulfur atom and the like, which has at least one hetero atom and has 4 to 20 carbon atoms.
  • Examples of the aromatic heterocyclic group include furyl group, thienyl group, pyridinyl group, thiazolyl group and benzothiazolyl group.
  • 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 means a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly.
  • the polycyclic aromatic heterocyclic group means a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.
  • Z 0 , Z 1 and Z 2 are preferably each independently 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
  • Z 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 further 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 include a polymerizable group.
  • Q 1 and Q 2 are preferably —NH—, —S—, —NR 2′ — and —O—, and R 2′ is preferably a hydrogen atom.
  • R 2′ is preferably a hydrogen atom.
  • —S—, —O—, and —NH— are particularly preferable.
  • formulas (Ar-1) to (Ar-23), formula (Ar-6) and formula (Ar-7) 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 which Ar may have, and examples thereof include a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring and an 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-mentioned optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z 0 .
  • examples thereof include a benzofuran ring, a benzothiazole ring, a benzoxazole ring and the like.
  • a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm may be used as the polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film.
  • a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm generally tends to exhibit positive wavelength dispersibility.
  • a polymerizable liquid crystal compound for example, a compound containing a structure represented by the following formula (Y), which generally tends to exhibit positive wavelength dispersibility (hereinafter, also referred to as “polymerizable liquid crystal compound (Y)”) ) Is mentioned.
  • the absorbance of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer, and the absorbance can be measured with reference to the method described in Examples, for example.
  • the solvent is a solvent capable of dissolving the polymerizable liquid crystal compound, and examples thereof include tetrahydrofuran and chloroform.
  • P11-B11-E11-B12-A11-B13- (Y) [In the formula (Y), P11 represents a polymerizable group.
  • A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group.
  • B11 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR 16 -, -NR 16 -CO-, -CO-, -.
  • 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
  • the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms
  • the hydrogen atom contained in the alkoxy group. May be substituted with a halogen atom.
  • —CH 2 — constituting the alkanediyl group may be replaced with —O— or —CO—.
  • the aromatic hydrocarbon group and alicyclic hydrocarbon group represented by A11 preferably have 3 to 18 carbon atoms, more preferably 5 to 12 carbon atoms, and particularly 5 or 6 carbon atoms. preferable.
  • the hydrogen atom contained in the divalent alicyclic hydrocarbon group represented by A11 and the 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, It may be substituted with a cyano group or a nitro group, and the 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.
  • A11 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.
  • a linear alkanediyl group having 1 to 12 carbon atoms is preferable.
  • —CH 2 — constituting the alkanediyl group may be replaced with —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 —O
  • B11 is preferably -O-, -S-, -CO-O-, or -O-CO-, and more preferably -CO-O-.
  • the polymerizable group represented by P11 is preferably a radically polymerizable group or a cationically polymerizable group from the viewpoint of high polymerization reactivity, particularly photopolymerization reactivity, and is easy to handle and easy to produce the liquid crystal compound itself. Therefore, the polymerizable group is preferably a group represented by the following formula (P-11) to formula (P-15). [In the formulas (P-11) to (P-15), R 17 to R 21 each independently represent 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.
  • the group represented by P11-B11- is more preferably an acryloyloxy group or a methacryloyloxy group.
  • Examples of the polymerizable liquid crystal compound (Y) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V) or 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-A11-B13-
  • F11 is hydrogen atom, alkyl group having 1 to 13 carbon atoms, alkoxy group having 1 to 13 carbon atoms, cyano group, nitro group, trifluoromethyl group, dimethylamino group, hydroxy group, methylol group, formyl group, sulfo group (—SO 3 H), a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms or a halogen atom, and —CH 2 — constituting the alkyl group and the alkoxy group may be replaced with —O— Good.
  • polymerizable liquid crystal compound (Y) examples include “3.8.6 network (completely crosslinked)” in the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000). , "6.5.1 Liquid crystal material, b. Polymerizable nematic liquid crystal material", the compound having a polymerizable group, JP 2010-31223A, JP 2010-270108A, JP Examples thereof include polymerizable liquid crystals described in JP 2011-6360 A and JP 2011-207765 A.
  • 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 Represented by formula (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 represent an integer of 2 to 12.
  • 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 further preferably 90 to 95 parts by mass.
  • 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 solid content of the polymerizable liquid crystal composition means all components except the volatile components such as the organic solvent from the polymerizable liquid crystal composition.
  • the total content of all polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition is preferably within the above range.
  • the polymerizable liquid crystal composition used for forming the vertically aligned liquid crystal cured film further contains additives such as a solvent, a polymerization initiator, an antioxidant and a photosensitizer in addition to the vertical alignment accelerator and the polymerizable liquid crystal compound. You can leave.
  • additives such as a solvent, a polymerization initiator, an antioxidant and a photosensitizer in addition to the vertical alignment accelerator and the polymerizable liquid crystal compound. You can leave.
  • additives such as a solvent, a polymerization initiator, an antioxidant and a photosensitizer in addition to the vertical alignment accelerator and the polymerizable liquid crystal compound. You can leave.
  • additives such as a solvent, a polymerization initiator, an antioxidant and a photosensitizer in addition to the vertical alignment accelerator and the polymerizable liquid crystal compound. You can leave.
  • 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 dissolved in a solvent and then applied onto a substrate or the like, and therefore it is preferable to include 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 water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, propylene glycol monomethyl ether, and the like.
  • 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 and methyl isobutyl ketone Ketone solvent; Aliphatic hydrocarbon solvent such as pentane, hexane and heptane; Alicyclic hydrocarbon solvent such as ethylcyclohexane; Aromatic hydrocarbon solvent such as toluene and xylene; Nitrile solvent such as acetonitrile; Tetrahydrofuran and dimethoxyethane etc.
  • ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, ⁇ -butyrolactone, propylene
  • Ether solvents chlorine-containing solvents such as chloroform and chlorobenzene
  • amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone.
  • NMP N-methyl-2-pyrrolidone
  • 1,3-dimethyl-2-imidazolidinone 1,3-dimethyl-2-imidazolidinone.
  • solvents can be used alone or in combination of two or more.
  • 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, based on 100 parts by weight of the polymerizable liquid crystal composition. Therefore, 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 easily. The solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.
  • a polymerization initiator is a compound capable of initiating a polymerization reaction such as a polymerizable liquid crystal compound by generating a reactive species by contribution of heat or light.
  • the reactive species include radicals, cations, and anions.
  • photopolymerization initiators that generate radicals upon irradiation with light are preferable from the viewpoint of easy reaction control.
  • photopolymerization initiator examples include benzoin compounds, benzophenone compounds, benzyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone 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 (above, BASF Japan Ltd.).
  • the photopolymerization initiator can fully utilize the energy emitted from the light source and is excellent in productivity. Therefore, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and most preferably ⁇ -acetophenone-based.
  • a polymerization initiator and an oxime-based photopolymerization initiator are preferable.
  • Examples of the ⁇ -acetophenone compound include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1.
  • Examples of commercially available ⁇ -acetophenone compounds include Irgacure 369, 379EG, 907 (all manufactured by BASF Japan Ltd.) and Sequol BEE (manufactured by Seiko Chemical Co., Ltd.).
  • Oxime-based photopolymerization initiators generate radicals such as phenyl radicals and methyl radicals when irradiated with light. Polymerization of the polymerizable liquid crystal compound suitably proceeds with this radical, but among them, an oxime-based photopolymerization initiator that generates a methyl radical is preferable because the initiation efficiency of the polymerization reaction is high. Further, from the viewpoint of more efficiently proceeding the polymerization reaction, it is preferable to use a photopolymerization initiator capable of efficiently utilizing ultraviolet rays having a wavelength of 350 nm or more.
  • the photopolymerization initiator that can efficiently use ultraviolet rays having a wavelength of 350 nm or more, a triazine compound or a carbazole compound having an oxime structure is preferable, and a carbazole compound having an oxime ester structure is more preferable from the viewpoint of sensitivity.
  • the oxime photopolymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methyl Examples thereof include benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime).
  • oxime ester-based photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Ltd.), Adeka Optimer N-1919, and Adeka Arcules NCI-831. (Above, manufactured by ADEKA Co., Ltd.) and the like.
  • the content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Is. Within the above range, the reaction of the polymerizable group sufficiently proceeds, and it is difficult to disturb the alignment of the polymerizable liquid crystal compound.
  • 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 the 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. %, preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass.
  • the antioxidants can be used alone or in combination of two or more.
  • the photosensitizer include xanthones such as xanthone and thioxanthone; anthracenes having a substituent such as anthracene and alkyl ether; phenothiazine; rubrene.
  • the photosensitizer can be used alone or in combination of two or more kinds.
  • the content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and 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.
  • the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film has a component that functions as a leveling agent or a vertical alignment accelerator, a polymerizable liquid crystal compound, and a solvent other than these components and other components such as a photopolymerization initiator. It can be obtained by stirring at temperature.
  • the vertically aligned liquid crystal cured film is preferably oriented with a high degree of order in the vertical direction of the liquid crystal cured film.
  • the polymerizable liquid crystal compound is aligned with a high degree of order, so that when a laminate including the vertically aligned liquid crystal cured film is incorporated into an organic EL display device, it is oblique when displaying black. It tends to be excellent in the effect of suppressing the change in reflection hue.
  • the vertical alignment liquid crystal cured film may satisfy the following formula (7) as an index showing the high alignment state of the polymerizable liquid crystal compound in the vertical alignment liquid crystal cured film and indicating the degree of the orthorhombic optical compensation effect during black display.
  • 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.
  • the retardation value RthC(550) in the film thickness direction of the vertically aligned liquid crystal cured film is more preferably ⁇ 130 nm or more, further preferably ⁇ 100 nm or more, and particularly It is preferably ⁇ 90 nm or more, more preferably ⁇ 40 nm or less, further preferably ⁇ 50 nm or less.
  • the vertically aligned liquid crystal cured film satisfies the following formula (8).
  • RthC( ⁇ ) represents a retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of ⁇ 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 further preferably Is 0.7 or more, more preferably 0.75 or more, and further 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( ⁇ ) is the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of ⁇ nm.
  • nxC( ⁇ ) nyC( ⁇ )
  • nxC( ⁇ ) is an arbitrary value in the film plane.
  • Direction refractive index, and dC indicates the thickness of the vertically aligned liquid crystal cured film) Therefore, in order to obtain the 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 alignment state of the polymerizable liquid crystal compound described above.
  • Examples of the base material forming the laminate of the present invention include a glass base material and a film base material, and a resin film base material 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 ester; polyacrylic acid ester; triacetyl cellulose, Cellulose esters such as diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalates; polycarbonates; polysulfones; polyether sulfones; polyether ketones; plastics such as polyphenylene sulfides and polyphenylene oxides.
  • Such a resin can be used as a substrate by forming a film by a known means such as a solvent casting method or a melt extrusion method.
  • the surface of the base material may be subjected to surface treatment such as release treatment such as silicone treatment, corona treatment, plasma treatment and the like.
  • 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” Cellulose ester base materials and the like.
  • a commercially available cyclic olefin-based resins include cyclic olefin-based resins manufactured by Ticona (Germany) such as “Topas (registered trademark)"; cyclic olefins manufactured by JSR Corporation such as "Arton (registered trademark)".
  • cyclic olefin resins manufactured by Nippon Zeon Co., Ltd. such as "ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; Mitsui such as "Apel” (registered trademark)
  • a cyclic olefin resin manufactured by Kagaku Co., Ltd. may be mentioned.
  • a commercially available cyclic olefin resin base material can also be used. Examples of commercially available cyclic olefin resin base materials include cyclic olefin resin base materials manufactured by Sekisui Chemical Co., Ltd.
  • the substrate may be one that can be finally peeled from the laminate of the present invention.
  • the thickness of the substrate is usually from 5 to 300 ⁇ m, and preferably from 10 to 150 ⁇ m, from the viewpoints of thinning the laminate, ease of peeling the substrate, handleability of the substrate, and the like.
  • the layered product of the present invention may include layers other than the substrate and the vertically aligned liquid crystal cured film as long as the effects of the present invention are not affected.
  • examples of such other layer include, for example, a horizontal alignment retardation film (horizontal alignment liquid crystal cured film), a horizontal alignment film, and a cured resin for the purpose of increasing or reinforcing the mechanical strength of the liquid crystal cured film.
  • a vertically aligned liquid crystal satisfying at least one of formulas (1) and (2) and satisfying at least one of formulas (3), (4), (5) and (6).
  • a vertically aligned liquid crystal cured film in which the polymerizable liquid crystal compound is aligned in the vertical direction with high accuracy can be obtained without the vertical alignment film. Therefore, the present invention satisfies at least one of the above formulas (1) and (2) and at least one of the formulas (3), (4), (5) and (6).
  • a polymerizable liquid crystal composition capable of forming a vertically aligned liquid crystal cured film is also targeted.
  • a polymerizable liquid crystal composition As such a polymerizable liquid crystal composition, a polymerizable liquid crystal compound, a leveling agent, and a polymerizable liquid crystal composition containing at least one selected from the group consisting of an ionic compound containing a nonmetal atom and a nonionic silane compound. And a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, a leveling agent, an ionic compound containing a non-metal atom and a non-ionic silane compound is preferable.
  • the polymerizable liquid crystal compound may be either a reverse wavelength dispersible polymerizable liquid crystal compound or a positive wavelength dispersible polymerizable liquid crystal compound.
  • the polymerizable liquid crystal compound, the leveling agent, the ionic compound composed of a non-metal atom and the non-ionic silane compound are those exemplified above as those which can be contained in the vertically aligned liquid crystal cured film constituting the laminate of the present invention.
  • the same can be used.
  • the polymerizable liquid crystal composition may further include additives such as a solvent, a polymerization initiator, an antioxidant and a photosensitizer.
  • additives such as those exemplified above as those that can be contained in the vertically aligned liquid crystal cured film constituting the laminate of the present invention can be used.
  • the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, and an ionic compound and a nonionic compound composed of a nonmetal atom.
  • the polymerizable liquid crystal composition of the present invention is a polymerizable liquid crystal compound having an absorbance of 0.10 or less at a wavelength of 350 nm, a leveling agent, an ionic compound containing a non-metal atom, and a non-ionic compound.
  • the polymerizable liquid crystal compound having an absorbance at a wavelength of 350 nm of 0.10 or less in each of the above aspects is preferably a polymerizable liquid crystal compound having a structure represented by the above formula (Y).
  • the laminate of the present invention for example, A step of applying a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film containing a polymerizable liquid crystal compound onto a substrate to obtain a coating film, Drying the coating film to form a dried coating film, and It can be manufactured by a method including a step of irradiating a dry coating film with active energy rays to form a vertically aligned liquid crystal cured film.
  • the formation of the coating film of the polymerizable liquid crystal composition is performed, for example, for forming a vertically aligned liquid crystal cured film on a base material or another layer such as a cured resin layer having no vertical alignment control force provided on the base material. It can be carried out by applying the polymerizable liquid crystal composition.
  • 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, and a printing method such as a flexo method. And other known methods.
  • the solvent is removed by drying or the like to form a dry coating film.
  • the drying method include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method.
  • the solvent can be dried and removed from the coating film, and the polymerizable liquid crystal compound can be aligned in the direction perpendicular to the plane of the coating film.
  • 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 of the base material forming the coating film, etc., but in order to cause the polymerizable liquid crystal compound to undergo a phase transition to a liquid crystal phase state, It is usually necessary to have a temperature above the phase transition temperature.
  • the liquid crystal phase transition temperature (smectic phase transition temperature of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition is It can be heated to a temperature above the temperature or nematic phase transition temperature).
  • the liquid crystal phase transition temperature can be measured using, for example, a polarization microscope equipped with a temperature adjustment stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. Further, when two or more polymerizable liquid crystal compounds are used in combination, the above-mentioned phase transition temperature is the 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. Means a temperature measured in the same manner as in the case of using one kind of polymerizable liquid crystal compound using a mixture of the polymerizable liquid crystal compounds. It is generally known that 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 depending on the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent and the boiling point and amount thereof, etc., but is usually 15 seconds to 10 minutes, preferably 0.5 to 10 minutes. 5 minutes.
  • the removal of the solvent from the coating film may be carried out at the same time as heating the liquid crystal phase transition temperature of the polymerizable liquid crystal compound or higher, or may be carried out separately, but it is preferably carried out simultaneously from the viewpoint of improving productivity.
  • the solvent in the coating film Before heating to above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, the solvent in the coating film is moderately added under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize.
  • a preliminary drying step for removing may be provided. Examples of the drying method in the preliminary drying step include a natural drying method, a ventilation drying method, a heating drying method and a reduced pressure drying method.
  • the drying temperature (heating temperature) in the drying step is the kind of the polymerizable liquid crystal compound used, the solvent. It can be appropriately determined according to the type, the boiling point and the amount thereof.
  • the vertically aligned liquid crystal cured film is formed by polymerizing the polymerizable liquid crystal compound while maintaining the vertically aligned state of the polymerizable liquid crystal compound.
  • the polymerization method include a thermal polymerization method and a photopolymerization method, and the photopolymerization method is preferable from the viewpoint of easy control of the polymerization reaction.
  • ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction, and that widely used in the art as a photopolymerization device can be used, and by ultraviolet light, photopolymerization is possible. It is preferable to select the types of the polymerizable liquid crystal compound and the polymerization initiator contained in the polymerizable liquid crystal composition. Further, during the polymerization, the polymerization temperature can be controlled by irradiating with light while cooling the dried coating film by an appropriate cooling means.
  • a vertically aligned liquid crystal cured film can be appropriately formed even if a substrate having relatively low heat resistance is used. It is also possible to accelerate the polymerization reaction by raising the polymerization temperature in a range where defects due to heat during light irradiation (deformation due to heat of the substrate, etc.) do not occur. It is also possible to obtain a patterned cured film by performing masking or development during photopolymerization.
  • 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 with light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and further preferably 0.1 seconds to 1 minute. is there.
  • the integrated light amount thereof is 10 to 3,000 mJ/cm 2 , preferably 50 to 2,000 mJ/cm 2 , and more preferably 100 to 1,000 mJ/cm 2. It is 2 .
  • the thickness of the vertically aligned liquid crystal cured film can be appropriately selected according to the applied display device, and is preferably 0.3 ⁇ m or more and 5.0 ⁇ m or less, more preferably 3.0 ⁇ m or less, and further preferably 2.0 ⁇ m or less. is there.
  • the horizontally aligned retardation film that can form the laminate of the invention means a retardation film that is aligned in the horizontal direction with respect to the in-plane direction of the vertically aligned liquid crystal cured film, and includes, for example, a stretched film and a polymerizable liquid crystal compound.
  • a cured product of a polymerizable liquid crystal composition containing, wherein the polymerizable liquid crystal compound is cured in a state of being aligned in the horizontal direction with respect to the plane of the retardation film hereinafter, referred to as “horizontal alignment liquid crystal cured film”). Also referred to as).
  • the horizontally oriented retardation film preferably satisfies the following formula (11).
  • the horizontally oriented retardation film When the horizontally oriented retardation film satisfies the formula (11), the horizontally oriented retardation film has a so-called reverse wavelength dispersion in which the in-plane retardation value at the short wavelength is smaller than the in-plane retardation value at the long wavelength. Shows sex.
  • ReA(450)/ReA(550) is preferably 0.70 or more, and more preferably Is 0.78 or more, preferably 0.95 or less, and more preferably 0.92 or less.
  • the horizontally oriented retardation film satisfies the following formula (12). 120 nm ⁇ ReA (550) ⁇ 170 nm (12) [In Formula (12), ReA( ⁇ ) has the same meaning as above]
  • the in-plane retardation ReA (550) of the horizontally oriented retardation film is within the range of formula (12)
  • a laminate (elliptical polarizing plate) including the horizontally oriented retardation film is applied to an organic EL display device.
  • a more preferable range of the in-plane retardation value is 130 nm ⁇ ReA(550) ⁇ 150 nm.
  • the horizontally aligned retardation film is a horizontally aligned liquid crystal cured film because the desired retardation of the retardation film can be easily controlled and thinned.
  • a polymerizable liquid crystal compound conventionally known in the field of retardation film can be used.
  • the compounds represented by the formulas (X) and/or (Y) exemplified as the polymerizable liquid crystal compound that can be used for forming the vertically aligned liquid crystal cured film can be used.
  • a polymerizable liquid crystal compound exhibiting properties is preferable, and for example, the compound represented by the above formula (X) can be preferably used.
  • the polymerizable liquid crystal compounds may be used alone or in combination of two or more kinds.
  • 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 based on 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, further preferably 90 to 95 parts by mass.
  • the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the resulting liquid crystal cured film.
  • the polymerizable liquid crystal composition used for forming the horizontally aligned liquid crystal cured film further contains an additive such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound. You may stay. Examples of these components are the same as those exemplified above as components that can be used in the vertically aligned liquid crystal cured film, and only one type may be used, or two or more types may be used in combination. ..
  • the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film can be obtained by stirring a polymerizable liquid crystal compound and a component other than the polymerizable liquid crystal compound such as a solvent or a photopolymerization initiator at a predetermined temperature. ..
  • Horizontal alignment liquid crystal cured film for example, A step of applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a substrate or a horizontally aligned film to obtain a coating film, Drying the coating film to form a dried coating film, and It can be produced by a method including a step of irradiating a dry coating film with an active energy ray 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 the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film on a substrate or a horizontal alignment film as described below. ..
  • the base material that can be used here the same base materials as those exemplified above as the base material that can be used for producing the vertically aligned liquid crystal cured film can be used.
  • the solvent is removed by drying or the like to form a dry coating film.
  • the drying method include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method. From the viewpoint of productivity, heat drying is preferable, and the heating temperature in that case is preferably the temperature at which the solvent can be removed and the phase transition temperature of the polymerizable liquid crystal compound or higher.
  • the procedure and conditions in this step are the same as those that can be adopted in the method for producing a vertically aligned liquid crystal cured film.
  • the resulting dried coating film is irradiated with active energy rays (more specifically, ultraviolet rays or the like), and the polymerizable liquid crystal compound is maintained while maintaining the state in which the polymerizable liquid crystal compound is aligned in the horizontal direction with respect to the coating film plane.
  • active energy rays more specifically, ultraviolet rays or the like
  • a horizontally aligned liquid crystal cured film is formed by polymerizing. Examples of the polymerization method include the same methods as those that can be used in the method for producing a vertically aligned liquid crystal cured film.
  • the thickness of the horizontally aligned liquid crystal cured film can be appropriately selected according to the applied display device, and is preferably 0.2 to 5 ⁇ m, more preferably 0.2 to 4 ⁇ m, and further preferably 0.2 to 3 ⁇ m. ..
  • a horizontal alignment film is formed on a vertical alignment liquid crystal cured film that constitutes the laminate of the present invention, and a horizontal alignment liquid crystal cured film-forming polymerizable liquid crystal composition is applied thereon to obtain a horizontal alignment liquid crystal cured film.
  • a horizontally aligned liquid crystal cured film is formed on a base material or a horizontal alignment film provided on the base material and then bonded to a vertically aligned liquid crystal cured film via an adhesive layer or the like.
  • the alignment film can be appropriately selected from materials having a horizontal alignment regulating force for aligning the polymerizable liquid crystal compound in the horizontal direction with respect to the coating film plane.
  • the alignment regulating force can be arbitrarily adjusted depending on the type of the alignment layer, the surface state, the rubbing conditions, etc., and when it is formed from a photoalignable polymer, it can be adjusted arbitrarily by the polarized light irradiation conditions, etc. It is possible.
  • the alignment film has solvent resistance such that it is not dissolved by coating the polymerizable liquid crystal composition and the like, and has heat resistance in the heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound described later.
  • the alignment film include an alignment film containing an alignment polymer, a photo-alignment film and a glob alignment film having an uneven pattern and a plurality of grooves on the surface, a stretched film stretched in the alignment direction, and the like. From the viewpoint of quality, a photo-alignment film is preferable.
  • the oriented polymer examples include polyamides and gelatins having an amide bond in the molecule, polyimides having an imide bond in the molecule and polyamic acid which is a hydrolyzate thereof, polyvinyl alcohol, alkyl modified polyvinyl alcohol, polyacrylamide, polyacrylamide. Examples include oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic acid esters. Of these, polyvinyl alcohol is preferable.
  • the oriented polymer may be used alone or in combination of two or more kinds.
  • the alignment film containing the alignment polymer is usually obtained by applying a composition in which the alignment polymer is dissolved in a solvent (hereinafter, sometimes referred to as “alignment polymer composition”) to a substrate to remove the solvent, or It is obtained by applying the oriented polymer composition to a substrate, removing the solvent, and rubbing (rubbing method).
  • a solvent hereinafter, sometimes referred to as “alignment polymer composition”
  • the solvent include the same solvents as those exemplified above as the solvent that can be used for the polymerizable liquid crystal composition.
  • the concentration of the oriented polymer in the oriented polymer composition may be in the range where the oriented polymer material can be completely dissolved in the solvent, but is preferably 0.1 to 20% in terms of solid content in the solution, and 0 It is more preferably about 1 to 10%.
  • 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 Sanever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) and Optomer (registered trademark, manufactured by JSR Corporation).
  • the same methods as those exemplified as the method of applying the polymerizable liquid crystal composition to the substrate can be mentioned.
  • 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 reduced pressure drying method.
  • Rubbing treatment can be performed as necessary to give the alignment control force to the alignment film (rubbing method).
  • a rubbing cloth is wrapped around a rubbing roll which is rotated, and the orientational polymer composition is applied to the substrate and annealed to form the substrate surface. Examples include a method of bringing a film of an oriented polymer into contact. If masking is performed during the rubbing treatment, a plurality of regions (patterns) having different alignment directions can be formed in the alignment film.
  • the photo-alignment film is usually prepared by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as “composition for forming photo-alignment film”) to a substrate and polarizing the film after removing the solvent. (Preferably polarized UV).
  • composition for forming photo-alignment film a composition containing a polymer or monomer having a photoreactive group and a solvent
  • polarized UV Preferably polarized UV.
  • the photo-alignment film is also 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.
  • Photoreactive group refers to a group that produces liquid crystal alignment ability when irradiated with light. Specific examples thereof include a group involved in a photoreaction which is a source of liquid crystal alignment ability such as an orientation induction or isomerization reaction of molecules generated by light irradiation, a dimerization reaction, a photocrosslinking reaction or a photodecomposition reaction. Of these, a group involved in a dimerization reaction or a photocrosslinking reaction is preferable in terms of excellent orientation.
  • a photoreactive group involved in the photodimerization reaction is preferable, the irradiation amount of polarized light required for photoalignment is relatively small, and in that a photoalignment film excellent in thermal stability and stability over time is easily obtained, Cinnamoyl and chalcone groups are preferred.
  • the polymer having a photoreactive group a polymer having a cinnamoyl group such that the end portion of the polymer side chain has a cinnamic acid structure is particularly preferable.
  • the photo-alignment inducing layer can be formed on the substrate by applying the composition for forming a photo-alignment film onto the substrate.
  • the solvent contained in the composition include the same solvents as those exemplified above as the solvent that can be used in the polymerizable liquid crystal composition, and are appropriately selected depending on the solubility of the photoreactive group-containing polymer or monomer. can do.
  • the content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted depending on the kind of the polymer or the monomer and the thickness of the desired photo-alignment film. It is preferably at least 0.2% by mass, and more preferably in the range of 0.3 to 10% by mass.
  • the composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer as long as the characteristics of the photo-alignment film are not significantly impaired.
  • the same method as the method of applying the oriented polymer composition to the base material can be mentioned.
  • 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 reduced pressure drying method.
  • polarized light is radiated from the substrate side and the polarized light is transmitted.
  • the irradiation may be performed.
  • the polarized light is substantially parallel light.
  • the wavelength of the polarized light to be irradiated is preferably in the wavelength range in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet) having a wavelength range of 250 to 400 nm is particularly preferable.
  • Examples of the light source used for the irradiation of polarized light include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF.
  • High-pressure mercury lamps, ultra-high-pressure mercury lamps and metal halide lamps are more preferable.
  • a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide lamp are preferable because they have high emission intensity of ultraviolet rays having a wavelength of 313 nm.
  • Polarized UV can be irradiated by irradiating the light from the light source through an appropriate polarizer.
  • a polarizer a polarizing filter, a polarizing prism such as Glan-Thompson or Glan-Taylor, or a wire grid type polarizer can be used.
  • masking can be performed to form a plurality of regions (patterns) having different liquid crystal alignment directions.
  • the groove alignment film is a film having an uneven 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 globbings arranged at equal intervals, liquid crystal molecules are aligned in the direction along the groove.
  • a method for obtaining a glube alignment film after exposure through an exposure mask having a patterned slit on the surface of a photosensitive polyimide film, a method of forming an uneven pattern by developing and rinsing, a plate having a groove on the surface
  • a method for forming a layer of UV curable resin before curing on a sheet-shaped master, transferring the formed resin layer to a substrate, and then curing, and a film of the UV curable resin before curing formed on the substrate Examples include a method in which a roll-shaped master having a plurality of grooves is pressed to form irregularities and then cured.
  • the vertically aligned liquid crystal cured film and the horizontally aligned retardation film can be laminated, for example, via an adhesive layer or an adhesive layer.
  • the adhesive or the adhesive those conventionally known in the art can be used.
  • the horizontally aligned liquid crystal is aligned on the vertically aligned liquid crystal cured film.
  • a retardation film horizontal alignment liquid crystal cured film
  • 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 having adsorbed a dye having absorption anisotropy and a film including a film coated with a dye having absorption anisotropy as a polarizer. Examples of the dye having absorption anisotropy include dichroic dyes.
  • a film containing a stretched film adsorbing a dye having absorption anisotropy as a polarizer is usually a step of uniaxially stretching a polyvinyl alcohol-based resin film, by dyeing the polyvinyl alcohol-based 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-based resin film on which a dichroic pigment is adsorbed with a boric acid aqueous solution, and a step of washing with water after the treatment with the boric acid aqueous solution. It is produced by sandwiching one surface with a transparent protective film via an adhesive.
  • Polyvinyl alcohol resin is obtained by saponifying polyvinyl acetate resin.
  • polyvinyl acetate-based resin in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith is used.
  • the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.
  • the saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol %, preferably 98 mol% or more.
  • the polyvinyl alcohol-based 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-based resin is usually about 1,000 to 10,000, preferably 1,500 to 5,000.
  • a film produced from such a polyvinyl alcohol resin is used as a raw film for a polarizing film.
  • the method for forming a film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method.
  • the film thickness of the polyvinyl alcohol-based original film can be set to, 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 the boric acid treatment or during the boric acid treatment. It is also possible to carry out uniaxial stretching in these plural stages.
  • the uniaxial stretching it may be uniaxially stretched between rolls having different peripheral speeds, or may be uniaxially stretched using a heat roll.
  • the uniaxial stretching may be dry stretching in which stretching is performed in the atmosphere, or wet stretching in which a polyvinyl alcohol-based resin film is swollen using a solvent.
  • the draw ratio is usually about 3 to 8 times.
  • the dyeing of the polyvinyl alcohol-based resin film with the dichroic dye is performed by, for example, immersing the polyvinyl alcohol-based 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 dye examples include C.I. I.
  • the polyvinyl alcohol-based resin film is preferably immersed in water before dyeing.
  • the method of immersing the polyvinyl alcohol resin film in an aqueous solution containing iodine and potassium iodide and dyeing is usually adopted.
  • the content of iodine 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 1800 seconds.
  • a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing 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, and 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 aid.
  • the temperature of the dichroic dye aqueous 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 the dichroic dye can usually be performed by a method of immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution.
  • the content of boric acid 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, and the content of potassium iodide in that case 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 aqueous boric acid solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds.
  • the temperature of the 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 is usually washed with water.
  • the water washing treatment can be performed by, for example, a method of immersing the polyvinyl alcohol-based resin film treated with boric acid 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 polarizer After drying with water, a polarizer is obtained.
  • the drying treatment can be performed using, for example, a hot air dryer or a far infrared heater.
  • the temperature of 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 water content of the polarizer is reduced to a practical level.
  • the water content thereof is usually about 5 to 20% by mass, preferably 8 to 15% by mass.
  • the thermal stability of the polarizer may deteriorate.
  • the thickness of the polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying 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 coating 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 thereof. Examples of the protective film include the same resin films as those exemplified above as the substrate that can be used for producing the vertically aligned liquid crystal cured film.
  • the film coated with a dye having absorption anisotropy is thin, but if it is too thin, the strength will decrease and the processability will tend to be poor.
  • 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 the absorption anisotropy include films described in JP 2012-33249 A and the like.
  • a transparent protective film may be laminated on at least one surface of the thus obtained polarizer, for example, via an adhesive layer.
  • a transparent film similar to the resin film exemplified above as a substrate that can be used for producing a vertically aligned liquid crystal cured film can be used.
  • the elliptically polarizing plate of the present invention comprises the laminate of the present invention, or a laminate obtained by removing the base material from the laminate of the present invention, and a polarizing film, for example, the laminate of the present invention.
  • the elliptically polarizing plate of the present invention can be obtained by laminating a polarizing film with a polarizing film via an adhesive layer or the like. Further, the elliptically polarizing plate of the present invention can be obtained by laminating the polarizing film with the laminate obtained by removing the substrate from the laminate of the present invention.
  • a method for producing an elliptically polarizing plate by peeling a substrate from the laminate of the present invention and further laminating the laminate peeled from the substrate, a horizontally aligned retardation film, and a polarizing film is also applied. It is one of the inventions.
  • a laminate of the present invention including a horizontal alignment retardation film and a polarizing film are laminated, a slow axis (optical axis) and polarization of a horizontal alignment retardation film forming the laminate It is preferable to stack the films so that the angle formed by the absorption axis of the film is 45 ⁇ 5°.
  • the elliptically polarizing plate of the present invention may have a configuration such that a conventional general elliptically polarizing plate, or a polarizing film and a retardation film have.
  • a structure for example, it is used for the purpose of protecting the surface of an adhesive layer (sheet) for laminating an elliptically polarizing plate on a display element such as an organic EL, a polarizing film or a liquid crystal cured film from scratches and stains.
  • the protective film etc. which are used are mentioned.
  • 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, field emission display device (FED), surface field emission display device).
  • EL organic electroluminescence
  • EL inorganic electroluminescence
  • FED field emission display device
  • Liquid crystal display devices include any of transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection liquid crystal display devices. These display devices may be a display device that displays a two-dimensional image or may be a stereoscopic display device that displays a three-dimensional image.
  • the laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device.
  • EL organic electroluminescence
  • the laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device.
  • the elliptically polarizing plate it is possible to easily obtain a thin display device, obtain a display device having excellent optical characteristics and exhibiting good image display characteristics.
  • Example 1 Preparation of Polymerizable Liquid Crystal Compound A polymerizable liquid crystal compound (X1), a polymerizable liquid crystal compound (X2) and a polymerizable liquid crystal compound (X3) having the following molecular structures were prepared respectively.
  • the polymerizable liquid crystal compound (X1) was produced according to the method described in JP 2010-31223A. Further, the polymerizable liquid crystal compound (X2) was produced according to the method described in JP-A-2009-173893.
  • the polymerizable liquid crystal compound (X3) was prepared with reference to JP-A-2011-207765.
  • a solution was obtained by dissolving 1 mg of the polymerizable liquid crystal compound (X1) in 50 mL of tetrahydrofuran.
  • the solution obtained as a measurement sample was put into a measurement cell having an optical path length of 1 cm, the measurement sample was set in an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), and an absorption spectrum was measured.
  • UV-2450 ultraviolet-visible spectrophotometer
  • the maximum absorption wavelength ⁇ max in the wavelength range of 300 to 400 nm was 350 nm.
  • the absorbance of the polymerizable liquid crystal compound (X2) at a wavelength of 350 nm was measured according to the following method. First, 1 mg of the polymerizable liquid crystal compound (X1) was dissolved in 50 mL of tetrahydrofuran to obtain a solution. The solution obtained as a measurement sample was put into a measurement cell having an optical path length of 1 cm, the measurement sample was set in an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), and an absorption spectrum was measured. When the absorbance at a wavelength of 350 nm was measured from the obtained absorption spectrum, it was confirmed to be 0.05 or less.
  • UV-2450 ultraviolet-visible spectrophotometer
  • a 1 mg/50 mL tetrahydrofuran solution of the polymerizable liquid crystal compound (X3) was prepared.
  • the solution obtained as a measurement sample was put into a measurement cell having an optical path length of 1 cm, the measurement sample was set in an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), and an absorption spectrum was measured.
  • UV-2450 ultraviolet-visible spectrophotometer
  • the maximum absorption wavelength ⁇ max in the wavelength range of 300 to 400 nm was 354 nm.
  • 2016-514802 (molecular weight: 645) 2.0 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, and Irgacure OXE-03 (manufactured by BASF Japan Ltd.) 4 parts by mass as a photopolymerization initiator were added. .. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.
  • NMP N-methyl-2-pyrrolidone
  • a vertical alignment liquid crystal cured film was formed by irradiating ultraviolet rays from the surface coated with (in a nitrogen atmosphere, an integrated light amount at a wavelength of 365 nm: 500 mJ/cm 2 ).
  • the thickness of the obtained vertically aligned liquid crystal cured film was measured by an ellipsometer (M-220 manufactured by JASCO Corporation), and it was 1.2 ⁇ mm.
  • ⁇ Rth measurement of vertically aligned liquid crystal cured film Corona treatment is applied to the vertically aligned liquid crystal cured film surface of the laminate composed of the substrate and the vertically aligned liquid crystal cured film prepared by the above procedure, and the laminate is bonded to glass via a Lintec 25 ⁇ m pressure-sensitive adhesive, The material was peeled off.
  • the obtained glass, the adhesive, and the vertically aligned liquid crystal cured film were used to change the incident angle of light to the sample for measuring optical characteristics by using KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. The value and the phase difference value when tilted at 40° to the center of the fast axis were measured.
  • the average refractive index at each wavelength 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 K.K. From the above-mentioned front phase difference value, phase difference value when tilted by 40° about the axis of the fast axis, average refractive index, and film thickness value, Oji Scientific Instruments technical data (http://www.oji-keisoku.co) .Jp/products/kobra/reference.html), and the three-dimensional refractive index was calculated.
  • 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 the nxC( ⁇ ) in the plane at the wavelength ⁇ nm
  • nzC( ⁇ ) indicates the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of ⁇ nm.
  • nxC( ⁇ ) nyC( ⁇ )
  • nxC( ⁇ ) is the refractive index in any direction in the film plane.
  • dC represents the thickness of the vertically aligned liquid crystal cured film.
  • the vertical alignment liquid crystal cured film is obtained by extracting the elemental analysis information at the 100 nm point from the interface on the opposite side to the substrate.
  • the constituent elements in the liquid crystal cured film were confirmed at a point (intermediate point C) of 100 nm in the thickness direction from the interface on the opposite side of the substrate to the liquid crystal cured film side.
  • the vertically aligned liquid crystal cured film side was separately prepared with a pressure sensitive adhesive (25 ⁇ m) manufactured by Lintec Co., Ltd. (KC4UY manufactured by Konica Minolta).
  • Example 2 Except that the preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film and the formation of the vertically aligned liquid crystal cured film were changed as follows, and that the etching rate was changed to 100 sec ⁇ 35 times when the constituent elements were analyzed. In the same manner as in Example 1, a vertically aligned liquid crystal cured film was produced, constituent elements were confirmed, and optical characteristics and orientation were evaluated. The results are shown in Table 3 and Table 9.
  • a vertical alignment liquid crystal cured film was formed by irradiating ultraviolet rays from the surface coated with (in a nitrogen atmosphere, an integrated light amount at a wavelength of 365 nm: 500 mJ/cm 2 ).
  • the film thickness of the obtained vertically aligned liquid crystal cured film was measured by an ellipsometer (M-220 manufactured by JASCO Corporation) and found to be 0.6 ⁇ m.
  • Example 3 Example 1 was repeated except that the method for preparing the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and the etching rate was changed to 5 sec ⁇ 50 times when the constituent elements were analyzed. A vertically aligned liquid crystal cured film was manufactured by the above, the constituent elements were confirmed, and the optical characteristics and the orientation were evaluated. The results are shown in Tables 4 and 9.
  • 2016-514802 (molecular weight: 645) 2.0 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl) as a photopolymerization initiator ) 6 parts by mass of butan-1-one (“IRGACURE (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.
  • silane coupling agent "KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 4 Example 1 was repeated except that the method for preparing the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and the etching rate was changed to 5 sec ⁇ 50 times when the constituent elements were analyzed. A vertically aligned liquid crystal cured film was manufactured by the above, the constituent elements were confirmed, and the optical characteristics and the orientation were evaluated. The results are shown in Table 5 and Table 9.
  • 2016-514802 (molecular weight: 645) 3.0 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0 parts by mass, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl) as a photopolymerization initiator ) 6 parts by mass of butan-1-one (“IRGACURE (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.
  • silane coupling agent "KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 5 Example 1 was repeated except that the method for preparing the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and the etching rate was changed to 50 sec ⁇ 100 times when the constituent elements were analyzed. A vertically aligned liquid crystal cured film was manufactured by the above, the constituent elements were confirmed, and the optical characteristics and the orientation were evaluated. The results are shown in Table 6 and Table 9.
  • 2016-514802 (molecular weight: 645) 2.0 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl) as a photopolymerization initiator ) 6 parts by mass of butan-1-one (“IRGACURE (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.
  • silane coupling agent "KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.
  • Example 6 Example 1 was repeated except that the method for preparing the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, and the etching rate was changed to 5 sec ⁇ 50 times when the constituent elements were analyzed. A vertically aligned liquid crystal cured film was manufactured by the above, the constituent elements were confirmed, and the optical characteristics and the orientation were evaluated. The results are shown in Tables 7 and 9.
  • Comparative Example 1 Vertical alignment was performed in the same manner as in Example 1 except that the preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows and the etching rate was changed to 100 sec ⁇ 35 times when the constituent elements were analyzed. An oriented liquid crystal cured film was manufactured, constituent elements were confirmed, and optical characteristics and orientation were evaluated. The results are shown in Tables 8 and 9.
  • Base material 2 Vertically aligned liquid crystal cured film 11: Laminate (A): Non-base material side interface (B): Base material side interface (C): Intermediate point

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  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Theoretical Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ophthalmology & Optometry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Electroluminescent Light Sources (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention concerne un corps stratifié contenant un film durci de cristaux liquides orienté verticalement et un matériau de base, le film durci de cristaux liquides orienté verticalement étant un produit durci d'une composition de cristaux liquides polymérisable qui a été durcie tandis que le composé de cristaux liquides polymérisable était dans un état d'orientation dans une direction orthogonale par rapport au plan du film durci de cristaux liquides, et le film durci de cristaux liquides orienté verticalement satisfait au moins l'une parmi les formules (1) et (2), et satisfait également au moins l'une parmi les formules (3), (4), (5), et (6).　F(A) > F(C) (1) Si(A) > Si(C) (2) N(B) > N(C) (3) P(B) > P(C) (4) F(B) > F(C) (5) Si(B) > Si(C) (6) (Dans les formules (1) à (6) : F(A) représente le rapport (% atomique) de l'élément fluor présent dans le film durci de cristaux liquides au niveau de la limite, sur le côté opposé au matériau de base, du film durci de cristaux liquides orienté verticalement ; F(B) représente le rapport (% atomique) de l'élément de fluor présent dans le film durci de cristaux liquides à la limite, sur le côté de matériau de base, du film durci de cristaux liquides orienté verticalement ; F(C) représente le rapport (% atomique) de l'élément fluor présent dans le film durci de cristaux liquides sur un site correspondant à 100 nm de la limite, sur le côté opposé au matériau de base, du film durci de cristaux liquides orienté verticalement dans la direction de l'épaisseur sur le côté du film durci de cristaux liquides ; Si(A) représente le rapport (% atomique) de l'élément silicium présent dans le film durci de cristaux liquides à la limite, sur le côté opposé au matériau de base, du film durci de cristaux liquides orienté verticalement ; Si(B) représente le rapport (% atomique) de l'élément silicium présent dans le film durci de cristaux liquides à la limite, sur le côté de matériau de base, du film durci de cristaux liquides orienté verticalement ; Si(C) représente le rapport (% atomique) de l'élément silicium présent dans le film durci de cristaux liquides sur un site correspondant à 100 nm de la limite, sur le côté opposé au matériau de base, du film durci de cristaux liquides orienté dans la direction de l'épaisseur sur le côté du film durci de cristaux liquides ; N(B) représente le rapport (% atomique) de l'élément azote présent dans le film durci de cristaux liquides à la limite, sur le côté de matériau de base, du film durci de cristaux liquides orienté verticalement ; N(C) représente le rapport (% atomique) de l'élément azote présent dans le film durci de cristaux liquides sur un site correspondant à 100 nm de la limite, sur le côté opposé au matériau de base, du film durci de cristaux liquides orienté verticalement dans la direction de l'épaisseur sur le côté de film durci de cristaux liquides ; P(B) représente le rapport (% atomique) de l'élément phosphore présent dans le film durci de cristaux liquides à la limite, sur le côté de matériau de base, du film durci de cristaux liquides orienté verticalement ; et P(C) représente le rapport (% atomique) de l'élément phosphore présent dans le film durci de cristaux liquides sur un site correspondant à 100 nm de la limite, sur le côté opposé au matériau de base, du film durci de cristaux liquides orienté verticalement dans la direction de l'épaisseur sur le côté de film durci de cristaux liquides.)
PCT/JP2020/001240 2019-01-18 2020-01-16 Corps stratifié, plaque de polarisation elliptique et composition de cristaux liquides polymérisables WO2020149357A1 (fr)

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CN202080009405.5A CN113302529B (zh) 2019-01-18 2020-01-16 层叠体、椭圆偏光板及聚合性液晶组合物
KR1020217023582A KR20210114427A (ko) 2019-01-18 2020-01-16 적층체, 타원 편광판 및 중합성 액정 조성물

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JP2019007269A JP7302974B2 (ja) 2019-01-18 2019-01-18 積層体、楕円偏光板および重合性液晶組成物

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JP2008523443A (ja) * 2004-12-11 2008-07-03 エルジー・ケム・リミテッド 配向膜の要らないホメオトロピック配向液晶フィルム及びその製造方法
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JP7302974B2 (ja) 2023-07-04
KR20210114427A (ko) 2021-09-23
TW202037711A (zh) 2020-10-16
CN113302529B (zh) 2023-10-17
CN113302529A (zh) 2021-08-24

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