US20120225274A1 - Film and uses thereof - Google Patents

Film and uses thereof Download PDF

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Publication number
US20120225274A1
US20120225274A1 US13/509,015 US201013509015A US2012225274A1 US 20120225274 A1 US20120225274 A1 US 20120225274A1 US 201013509015 A US201013509015 A US 201013509015A US 2012225274 A1 US2012225274 A1 US 2012225274A1
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United States
Prior art keywords
bis
film
compound
compounds
mercaptomethylthio
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US13/509,015
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English (en)
Inventor
Hisako Ishikawa
Toshinori Matsuda
Yosuke Ono
Kazuo Yagi
Akifumi Kagayama
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Assigned to MITSUI CHEMICALS, INC. reassignment MITSUI CHEMICALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YAGI, KAZUO, ISHIKAWA, HISAKO, MATSUDA, TOSHINORI, KAGAYAMA, AKIFUMI, ONO, YOSUKE
Publication of US20120225274A1 publication Critical patent/US20120225274A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • 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
    • B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
    • B29D11/00788—Producing optical films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/04—Prisms
    • G02B5/045—Prism arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
    • G02B5/0825—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only
    • G02B5/0841—Multilayer mirrors, i.e. having two or more reflecting layers the reflecting layers comprising dielectric materials only comprising organic materials, e.g. polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • 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
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the present invention relates to a film and uses of the film.
  • Patent Document 1 discloses an optical material composed of a thiourethane resin. Furthermore, Patent Document 2 discloses an optical material composed of polythiourethane produced by the use of a prescribed catalyst. According to the documents, these resins have a high refractive index and high transparency, and can be suitably used for optical lenses among optical materials.
  • the documents do not disclose physical properties when a thiourethane resin is formed into a film at a thickness of equal to or less than 1 mm, and a method of controlling transmission of light as a whole by the use in contact with other materials in a thin film form. Furthermore, when these resins are made into a thin film, there are difficulties in coating from the viewpoint of reactivity of a raw material, and a method of obtaining a stable film or thin film is not reviewed either.
  • Patent Document 3 discloses an optical material having a structure in which a polythiourethane skeleton is introduced into a polythiocarbonate skeleton. According to the document, the resulting film from the optical material is excellent in optical properties such as high refractive index, high Abbe's number and the like, and further excellent in mechanical properties such as tensile properties, high elasticity and the like.
  • the document discloses a case in which a film is formed from the aforementioned optical material by a casting (solution casting) method of a resin solution.
  • Patent Document 1 Japanese Laid-open Patent Publication No. 1990-270859
  • Patent Document 2 International Publication (WO) No. 2007/97116
  • Patent Document 3 Japanese Laid-open Patent Publication No. 2005-336476
  • the resin as disclosed in the above document 3 involves many steps in synthesis, so that there are problems in maintenance of a quality and the cost when the resin is made into a film. Furthermore, a method of forming a film from the resin described in the above document 3 also requires extra effort and the cost for removing the solvent at the time of production thereof due to cast (solution casting) with a solution after completion of polymerization, there are difficulties in controlling the degree of polymerization and thickness, and there are many rooms for improvement in a balance among refractive index, birefringence and light transmittance of the formed film.
  • a film comprising a resin having a thiourethane bond, wherein the molar ratio (S/N) of sulfur to nitrogen contained in said resin is equal to or more than 0.8 and less than 3.
  • Alight emitting device wherein the optical film according to (8) is formed inside or outside thereof.
  • the film of the present invention also includes a sheet-like film, and further includes the case that a thin film obtained by coating and curing on a substrate is used with the substrate.
  • the film of the present invention is excellent in a balance among high refractive index, low birefringence and light transmittance, and further excellent in a balance of mechanical characteristics toughness, hardness, dimensional stability and the like, so that effects of deformation and the like during processing are very small, while the film is further excellent in solvent resistance as well, so that the film can be used as various optical films.
  • the film of the present invention is composed of a resin having a thiourethane bond.
  • the resin constituting the film of the present invention has the number of sulfur atoms which is relatively smaller than the number of thiourethane bonds, that is, polymerization reaction bonds, and consequently the polymerization process is made in a relatively simple manner.
  • the molar ratio (S/N) of sulfur to nitrogen contained in the resin is equal to or more than 0.8 and less than 3, preferably equal to or more than 0.8 and equal to or less than 2.8, and further preferably equal to or more than 0.9 and equal to or less than 2.2.
  • the film of the present invention is excellent in a balance of optical properties such as high refractive index, low birefringence, light transmittance and the like, and further excellent in mechanical characteristics such as toughness and solvent resistance as well.
  • the film has the properties as described below.
  • the refractive index in a sodium D line is equal to or more than 1.6 and preferably equal to or more than 1.64.
  • the in-plane birefringence ⁇ n xy of a film having a film thickness of 1 to 200 ⁇ m at a wavelength 590 nm is equal to or less 1.0 ⁇ 10 ⁇ 2 , preferably equal to or less than 1.0 ⁇ 10 ⁇ 3 , more preferably equal to or less than 2.0 ⁇ 10 ⁇ 5 , and further preferably equal to or less than 1.1 ⁇ 10 ⁇ 5 .
  • the birefringence ⁇ n x , in the thickness direction is equal to or less than 1.0 ⁇ 10 ⁇ 3 and further preferably equal to or less than 8.0 ⁇ 10 ⁇ 4 .
  • the average light transmittance to the light having a wavelength 400 to 800 nm is equal to or more than 80%, preferably equal to or more than 85%, and further preferably equal to or more than 88%.
  • the front birefringence ⁇ n xy is defined by nx-ny, while the in-plane retardation Re is defined by ⁇ n xy ⁇ d (wherein n x represents the refractive index in the in-plane delayed-phase direction of the resin film; n y represents the refractive index in the in-plane advanced-phase direction of the resin film (unit: nm)).
  • n x represents the refractive index in the in-plane delayed-phase direction of the resin film
  • n y represents the refractive index in the in-plane advanced-phase direction of the resin film
  • n z represents the refractive index in the film thickness direction
  • d is a film thickness (unit: nm)
  • the film of the present invention is excellent in a balance among high refractive index, low birefringence and light transmittance, so that the film can be suitably used for optical applications. Furthermore, the film of the present invention is excellent in strong toughness, and also excellent in solvent resistance because the film is composed of a thermosetting resin. Incidentally, the above numerical range may be used in any combination.
  • the breaking elongation is from 3 to 6%. Furthermore, the tensile modulus measured by a test for tensile strength is equal to or more than 3 GPa. Since the film is excellent in these mechanical characteristics, for the products obtained by using the film of the present invention, the yield rate thereof is improved and at the same time product reliability is improved. Thus, the film can be further suitably used for various optical films.
  • the film of the present invention has a thickness of from 0.1 to 1,000 ⁇ m, and a film having a thickness of 1 to 1,000 ⁇ m can also be used. From the viewpoint of low birefringence, the thickness is preferably from 0.1 to 200 ⁇ m. In case of a self-support film used by peeling off from the base material after coating, polymerizing and curing a thin film on a base material, or used by peeling off from the mold after cast polymerization, the thickness is particularly preferably from 10 to 200 ⁇ m.
  • the film can be used as a transparent base material of a liquid crystal display, a solar cell, an organic electroluminescence device and the like.
  • the water vapor transmittance rate of the film of the present invention is measured under the conditions of a temperature of 60 degrees centigrade, a humidity of 90% RH and a film thickness of 100 ⁇ m in accordance with JIS Z0208, the value is equal to or less than 10 g/m 2 ⁇ 24 hr.
  • a sulfur atom-containing resin having a thiourethane bond used in the present invention is obtained by polymerizing the following polymerizable composition.
  • the polymerizable composition is mainly composed of one or more kinds of isocyanates selected from the group consisting of an isocyanate compound and an isothiocyanate compound, and one or more kinds of active hydrogen compounds having a mercapto group.
  • a hydroxy compound may further be added.
  • concrete examples of the isocyanate compound which is preferably used as a raw material of the resin having a thiourethane bond include monofunctional isocyanate compounds such as methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, myristyl isocyanate, octadecyl isocyanate, 3-pentyl isocyanate, 2-ethylhexyl isocyanate, 2,3-dimethylcyclohexyl isocyanate, 2-methoxyphenyl isocyanate, 4-methyl iso
  • halogen substituted compounds such as chlorine substituted compounds, bromine substituted compounds and the like, alkyl substituted compounds, alkoxy substituted compounds, nitro substituted compounds, prepolymer type modified products modified with polyhydric alcohols, carbodiimide modified products, urea modified products, biuret modified products, dimerization or trimerization reaction products, and the like may be employed.
  • isocyanate compounds maybe used singly, or two or more kinds thereof may be used in combination.
  • an isothiocyanate compound which is used as a raw material of the resin having a thiourethane bond is selected from an isothiocyanate compound and an isothiocyanate compound having an isocyanate group.
  • halogen substituted compounds such as chlorine substituted compounds, bromine substituted compounds and the like, alkyl substituted compounds, alkoxy substituted compounds, nitro substituted compounds, prepolymer type modified products modified with polyhydric alcohols, carbodiimide modified products, urea modified products, biuret modified products, dimerization or trimerization reaction products, and the like may be employed.
  • isothiocyanate compounds may be used singly, or two or more kinds thereof may be used in combination.
  • Examples of the isothiocyanate compound having an isocyanate group which is used as a raw material in the present invention include aliphatic or alicyclic compounds such as 1-isocyanato-3-isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, 1-isocyanato-6-isothiocyanatohexane, isocyanatocarbonyl isothiocyanate, 1-isocyanato-4-isothiocyanatocyclohexane and the like; aromatic compounds such as 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene and the like; heterocyclic compounds such as 2-isocyanato-4,5-diisothiocyanato-1,3,5-triazine and the like; and isothiocyanate groups such as 4-isocyanato-4′-isothiocyanatodipheny
  • halogen substituted compounds such as chlorine substituted compounds, bromine substituted compounds and the like, alkyl substituted compounds, alkoxy substituted compounds, nitro substituted compounds, prepolymer type modified products modified with polyhydric alcohols, carbodiimide modified products, urea modified products, biuret modified products, dimerization or trimerization reaction products, and the like may be employed.
  • a resin having a thiourethane bond has an aromatic group, a heterocyclic group or an alicyclic group in the structure. Namely, it is preferable to use a compound having an aromatic group, a heterocyclic group or an alicyclic group as isocyanates.
  • isocyanates may be used singly, or two or more kinds thereof may be used in combination.
  • isocyanates more preferably used are phenylene diisocyanate, m-xylylene diisocyanate, 2,5-bis (isocyanatomethyl) -bicyclo[2.2.1] heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, tolylene diisocyanate and 4,4-diphenylmethane diisocyanate, while particularly preferably used are phenylene diisocyanate, m-xylylene diisocyanate, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 2,5-bis (isocyanatomethyl) -
  • a resin having a thiourethane bond has an aromatic group, a heterocyclic group or an alicyclic group in the structure. Namely, it is preferable to use a compound having an aromatic group, a heterocyclic group or an alicyclic group as isocyanates.
  • An active hydrogen compound having a mercapto group which is used as a raw material of the resin having a thiourethane bond is selected from a mercapto compound and a mercapto compound having a hydroxy group.
  • Examples of the mercapto compound used in the present invention include aliphatic polythiol compounds such as methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, 1,2-dimercaptopropylmethyl ether
  • halogen substituted compounds such as chlorine substituted compounds, bromine substituted compounds and the like may be employed.
  • mercapto compounds may be used singly, or two or more kinds thereof may be used in combination.
  • Examples of the mercapto compound having one or more sulfide bonds in one molecule include aliphatic polythiol compounds such as bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropylthio)ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(2-mercaptoethylthi
  • the present invention is not limited to these exemplified compounds.
  • their halogen substituted compounds such as chlorine substituted compounds, bromine substituted compounds and the like may be employed.
  • These mercapto compounds having a sulfide bond may be used singly, or two or more kinds thereof may be used in combination.
  • examples of the mercapto compound having a hydroxy group include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerine di(mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-l-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate), pentaerythritol pentakis(3-mercaptopropionate), hydroxymethyl-tris(mercaptoe),
  • the present invention is not limited to these exemplified compounds.
  • their halogen substituted compounds such as chlorine substituted compounds, bromine substituted compounds and the like may be employed.
  • These mercapto compounds having a hydroxy group may be used singly, or two or more kinds thereof may be used in combination.
  • active hydrogen compounds may be used singly, or two or more kinds thereof may be used in combination.
  • active hydrogen compound preferably used are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane and 2-(2,2-bis(mercaptodimethylthi
  • the active hydrogen compounds contain at least one kind of compound having three or more mercapto groups which is selected from the above compounds, and it is more preferable that all compounds have three or more mercapto groups.
  • the refractive index of the thus obtained resin is improved, the birefringence is also reduced because optical anisotropy is hardly caused, and mechanical properties such as impact resistance and the like are improved.
  • the resin having a thiourethane bond is mainly composed of one or more kinds of isocyanates selected from the group consisting of an isocyanate compound and an isothiocyanate compound, and one or more kinds of active hydrogen compounds having a mercapto group.
  • a resin modifier such as a hydroxy compound, an amine compound, an epoxy compound, an episulfide compound, an organic acid and its anhydride, an olefin compound containing a (meth)acrylate compound or the like may be added.
  • the resin modifier is a compound which adjusts or improves physical properties such as refractive index, Abbe's number, heat resistance, specific gravity and the like, and mechanical strength such as impact resistance of a polythiourethane resin.
  • hydroxy compound which may be added as the resin modifier examples include diethylene glycol, triethylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,7-heptanediol, 1,8-octanediol, thiodiethanol, dithiodiethanol, thiodipropanol, dithiodipropanol, their oligomers, and the like.
  • the present invention is not limited to these exemplified compounds. These alcohol compounds may be used singly, or two or more kinds thereof
  • Examples of the amine compound which may be added as the resin modifier include monofunctional primary amine compounds such as ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine, aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline, benzylamine, phenethylamine, 2,3-, or 4-methylbenzylamine, o-, m-, or p-methylaniline, o-, m-, or
  • Examples of the epoxy resin which may be added as the resin modifier include a phenol type epoxy compound obtained by the condensation reaction of a polyhydric phenol compound such as bisphenol A glycidyl ether with an epihalohydrin compound, an alcohol type epoxy compound obtained by condensation of a polyhydric alcohol compound such as hydrogenated bisphenol A glycidyl ether with an epihalohydrin compound, a glycidyl ester type epoxy compound obtained by condensation of a multivalent organic acid compound such as 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate or 1,2-hexahydrophthalic acid diglycidyl ester with an epihalohydrin compound, an amine type epoxy compound obtained by condensation of a primary or secondary diamine compound with an epihalohydrin compound, and an aliphatic multivalent epoxy compound such as vinylcyclohexene diepoxide, and the like.
  • the present invention is not limited to these exemplified compounds.
  • Examples of the episulfide compound which may be added as the resin modifier include chain aliphatic 2,3-epithiopropylthio compounds such as bis(2,3-epithiopropylthio)sulfide, bis(2,3-epithiopropylthio)disulfide, bis(2,3-epithiopropylthio)methane, 1,2-bis(2,3-epithiopropylthio)ethane, 1,5-bis(2,3-epithiopropylthio)-3-thiapentane and the like; 2,3-epithiopropylthio compounds having an alicyclic or heterocyclic ring such as 1,3-bis(2,3-epithiopropylthio)cyclohexane, 2,5-bis(2,3-epithiopropylthiomethyl)-1,4-dithiane and the like; and aromatic 2,3-epithiopropylthi
  • These episulfide compounds maybe used singly, or two or more kinds thereof may be used in combination.
  • Examples of the organic acid and its anhydride which may be added as the resin modifier include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnorbornene anhydride, methylnorbornene anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride and the like.
  • the present invention is not limited to these exemplified compounds. These organic acids and anhydrides thereof may be used singly, or two or more kinds thereof may be used in combination.
  • Examples of the olefin compound which may be added as the resin modifier include (meth)acrylate compounds such as benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, n
  • the proportion of isocyanates used as a raw material, the active hydrogen compound and the hydroxy compound as the resin modifier in terms of the molar ratio of functional groups (NCO+NCS)/(SH+OH) is usually in the range of 0.5 to 3.0, preferably in the range of 0.6 to 2.0, and further preferably in the range of 0.8 to 1.3.
  • a variety of substances may be added in the same manner as in a known molding method depending on the purposes.
  • the substance include a catalyst such as dibutyltin dichloride, dimethyltin dichloride or the like, an ultraviolet absorber such as a benzotriazole ultraviolet absorber or the like, an external or internal mold release agent, a light stabilizer, a chain extender, a cross-linking agent, an anti-oxidant, an anti-coloring agent, an anti-oxidant, a reaction initiator such as a radical reaction initiator or the like, a chain extender, a cross-linking agent, an anti-coloring agent, an oil-soluble dye, a filler, an adhesion improving agent and the like.
  • a catalyst such as dibutyltin dichloride, dimethyltin dichloride or the like
  • an ultraviolet absorber such as a benzotriazole ultraviolet absorber or the like
  • an external or internal mold release agent such as a light stabilizer, a chain extender, a
  • an inorganic compound having a sulfur atom or a selenium atom easily causes remarkable deterioration of color or turbidity, so that the content of these inorganic compounds in the polymerizable composition is preferably equal to or less than 1 weight %.
  • the order of addition of the catalyst, the mold release agent and other additives will vary depending on their solubility into the monomers. However, they may be added to isocyanates and dissolved therein in advance, added to the active hydrogen compounds and dissolved therein in advance, or added to a mixture of isocyanates and the active hydrogen compounds and dissolved therein.
  • the catalyst, the mold release agent and other additives may be dissolved in a part of the monomers in use to prepare a master solution, and then the master solution may be added to the monomer mixture.
  • the order of addition is not restricted to these exemplified methods, and is properly selected on the basis of operability, safety, expediency and the like.
  • the catalyst may be added as it is, or the catalyst maybe dissolved in a part of the monomers in use to prepare a master solution, and then the master solution may be added to the monomer mixture.
  • the temperature at this time is usually equal to or less than 25 degrees centigrade. From the viewpoint of pot life of the composition, it is sometimes preferable to employ a lower temperature than 25 degrees centigrade.
  • the solubility of the reaction catalyst, the mold release agent and the additives into the monomers is insufficient, it is also possible to heat them in advance and then to dissolve them in the isocyanates or the active hydrogen compounds that are the monomers, or a monomer mixture.
  • the film of the present invention can be produced by a usual method, and can be obtained by the use of the aforementioned polymerizable composition according to a casting (thin film coating—polymerization curing) method, a spin coating—polymerization curing method, a cast molding polymerization method or the like.
  • the casting method or the spin coating—polymerization curing method refers to a method involving extruding a viscosity-adjusted polymerizable composition which is a mixture of a compound having an isocyanate group and a compound having a thiol group, which is capable of forming a thiourethane, from a cast coating equipment and casting it on a base material, or rotating a base material with the composition placed thereon at a high speed to form a thin film, and then polymerizing and curing it to obtain a film containing partially a thiourethane bond.
  • the viscosity at the time of casting (coating) of the mixture is properly selected by the coating method and uses thereof.
  • the cast molding polymerization method refers to a method involving injecting a polymerizable composition which is a mixture of a compound having an isocyanate group and a compound having a thiol group containing partially a thiourethane bond and further capable of forming thiourethane between surfaces of a mold having a space of equal to or less than 200 ⁇ m composed of a pair of inorganic glasses, metals or resin plates with four sealed sides, and polymerizing it to obtain a film.
  • the viscosity at the time of injecting the mixture is properly selected by the injection method, curing process and the like.
  • the resulting film may be subjected to annealing.
  • the polymerizable composition may be mixed with fine particles of a metal oxide, a filler or the like to form a film.
  • the film of the present invention is excellent in a balance among high refractive index, low birefringence and light transmittance, and further excellent in a balance of mechanical characteristics such as toughness, hardness, dimensional stability and the like, so that effects of deformation and the like during processing are very small, while the film is further excellent in solvent resistance as well, so that the film can be used as various optical films.
  • the optical film examples include a polarizing film, a polarizing element and a polarizing plate protective film constituting the polarizing film, a phase difference film, an alignment film, a viewing angle improving (compensation) film, a diffused plate (film), a prism sheet, a light-guiding plate, a luminance improving film, a near-infrared absorption film, a reflection film, an anti-reflection (AR) film, a low reflection (LR) film, an anti-glare (AG) film, a transparent conductive (ITO) film, a base material for transparent conductive films, an anisotropic conductive film (ACF), an electromagnetic wave shielding (EMI) film, a film for electrode substrates, a film for color filter substrates, a barrier film, a color filter layer, a black matrix layer and the like.
  • the optical film of the present invention may be formed inside or outside of various optical members of a liquid crystal display, an organic EL display, a plasma display, a solar cell and
  • the optical film of the present invention is particularly positioned on a surface of a light emitting surface or a light capturing surface, whereby light can be taken out or captured with good efficiency and the optical film is most suitably used for applications that require these actions.
  • one surface of the film is processed into a concavo-convex pattern and the other surface is attached to the light emitting surface of a light emitting device, whereby it is possible to provide a light emitting device having improved luminous efficiency by taking out light that is reflected inside a luminous body to the outside.
  • this film itself is used as a substrate and a light emitting element is directly formed on a surface of the film, whereby it is possible to provide a light emitting device having improved luminous efficiency by reducing reflection inside the element.
  • a light emitting device in which the optical film is formed inside or outside thereof, and further a lighting device using the light emitting device (a LED lamp, a back light of a display, and a flashlight of a camera or a cellular phone or the like) and an image display device using the light emitting device (a flat panel display or the like).
  • a lighting device using the light emitting device a LED lamp, a back light of a display, and a flashlight of a camera or a cellular phone or the like
  • an image display device using the light emitting device
  • the optical film of the present invention may be composed of one film having two or more functions of such an optical film, or may constitute a part or the whole of a film (a composite film) having two or more of such optical films.
  • These optical films formed on a base material such as glass, other resin films or the like are used without peeling off, whereby it is also possible to provide a laminated member, and a multi-layer structure.
  • a polythiol compound (B-2) containing 5,7-dimercaptomethyl-1,11-dimercapto-3,6-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6-trithiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6-trithiaundecane was synthesized in accordance with the method described in Example 1 of Japanese Laid-open Patent Publication No. 1995-252207.
  • a polythiol compound (B-3) containing 1, 1, 3, 3-tetrakis (mercaptomethylthio) propane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiane and 2-(2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiethane was synthesized in accordance with the method described in Production Example 2 of Japanese Laid-open Patent Publication No. 2004-2820.
  • a Kapton tape of 80 ⁇ m was affixed to four sides of a blue plate glass in a frame shape to build a wall, the monomer mixed solution was added dropwise to the inside of the wall, and a plate glass of the same size was further placed from the top. It was confirmed that the inside of the Kapton tape wall was filled with the monomer mixed solution, and then two plates of glasses with the solution sandwiched between them were fixed with a clip. The resulting material was subjected to a temperature elevation from 20 to 120 degrees centigrade slowly and cured over 20 hours. After cooling, a film was obtained by peeling it off from the glass.
  • the resulting film was colorless and transparent.
  • Stepan Company as an internal release agent were added to 36.4 g of m-xylylene diisocyanate in advance, and the contents were dissolved to give a monomer mixed solution.
  • 33.6 g of 4 -mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane was added thereto, and the contents were well mixed to give a monomer mixed solution.
  • the monomer mixed solution was degassed under reduced pressure for 1 hour, and then applied to a polyethylene naphthalate film (Teonex Q51, a product of Teijin Ltd.) using an applicator (a product of Coating Tester Industries Co., Ltd.) with a coating gap set at 70 ⁇ m.
  • the monomer mixed solution was uniformly wet spread on the base material.
  • the resulting material was subjected to a temperature elevation from 20 to 120 degrees centigrade slowly and cured over 13 hours. After cooling, a film was obtained by peeling off the base material. The resulting film was colorless and transparent. Respective physical properties of the film were as follows:
  • a Kapton tape of 80 ⁇ m was affixed to four sides of a blue plate glass in a frame shape to build a wall, the monomer mixed solution was added dropwise to the inside of the wall, and a plate glass of the same size was further placed from the top. It was confirmed that the inside of the Kapton tape wall was filled with the monomer mixed solution, and then two plates of glasses with the solution sandwiched between them were fixed with a clip. The resulting material was subjected to a temperature elevation from 20 to 120 degrees centigrade slowly and cured over 13 hours. After cooling, a film was obtained by peeling it off from the glass. The resulting film was colorless and transparent.
  • a Kapton tape of 80 ⁇ m was affixed to four sides of a blue plate glass in a frame shape to build a wall, the monomer mixed solution was added dropwise to the inside of the wall, and a plate glass of the same size was further placed from the top. It was confirmed that the inside of the Kapton tape wall was filled with the monomer mixed solution, and then two plates of glasses with the solution sandwiched between them were fixed with a clip. The resulting material was subjected to a temperature elevation from 20 to 120 degrees centigrade slowly and cured over 13 hours. After cooling, a film was obtained by peeling it off from the glass. The resulting film was colorless and transparent.
  • a Kapton tape of 80 ⁇ m was affixed to four sides of a blue plate glass in a frame shape to build a wall, the monomer mixed solution was added dropwise to the inside of the wall, and a plate glass of the same size was further placed from the top. It was confirmed that the inside of the Kapton tape wall was filled with the monomer mixed solution, and then two plates of glasses with the solution sandwiched between them were fixed with a clip. The resulting material was subjected to a temperature elevation from 50 to 120 degrees centigrade slowly and cured over 22 hours. After cooling, a film was obtained by peeling it off from the glass. The resulting film was colorless and transparent.
  • a Kapton tape of 80 ⁇ m was affixed to four sides of a blue plate glass in a frame shape to build a wall, the monomer mixed solution was added dropwise to the inside of the wall, and a plate glass of the same size was further placed from the top. It was confirmed that the inside of the Kapton tape wall was filled with the monomer mixed solution, and then two plates of glasses with the solution sandwiched between them were fixed with a clip. The resulting material was subjected to a temperature elevation from 50 to 120 degrees centigrade slowly and cured over 24 hours. After cooling, a film was obtained by peeling it off from the glass. The resulting film was colorless and transparent.
  • a Kapton tape of 80 ⁇ m was affixed to four sides of a blue plate glass in a frame shape to build a wall, the monomer mixed solution was added dropwise to the inside of the wall, and a plate glass of the same size was further placed from the top. It was confirmed that the inside of the Kapton tape wall was filled with the monomer mixed solution, and then two plates of glasses with the solution sandwiched between them were fixed with a clip. The resulting material was subjected to a temperature elevation from 20 to 120 degrees centigrade slowly and cured over 22 hours. After cooling, a film was obtained by peeling it off from the glass. The resulting film was colorless and transparent.
  • Example 1 Example 3
  • Example 4 Example 5
  • Example 6 Monomer composition (g) A-1 (36.4) A-2 (6.1) A-2 (5.6) A-2 (41.3) A-3 (35.0) A-1 (44.5) B-1 (33.6) B-1 (6.3) B-2 (6.3) B-3 (58.7) A-4 (2.3) B-3 (55.5) B-3 (62.7) Film thickness ( ⁇ m) 80 80 80 100 90 90 S/N 1.67 1.67 1.75 2.00 2.00 2.67 Refractive index (D line) 1.66 1.68 1.68 1.71 1.73 1.69 Refractive index (e line) 1.67 1.69 1.69 1.72 1.74 1.70 Abbe's number ( ⁇ d) 31 25.4 24.6 25.5 24.5 31.1 Transmittance-1 (Total 89 89 89 89 88 88 light transmittance, haze meter) Transmittance-2 (550 nm) 89 89 88 88 88 88 In-plane retardation (Re) 0.8 0.6 0.5 0.4 0.7 (nm) Solvent
  • A-1 m-xylylene diisocyanate
  • A-2 2,4-tolylene diisocyanate
  • A-3 m-phenylene diisocyanate
  • A-4 hexamethylene diisocyanate
  • B-1 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane
  • B-2 Polythiol compound synthesized in Production Example 1
  • B-3 Polythiol compound synthesized in Production Example 2
  • a film was obtained in the same manner as in Example 1, except that the height of the Kapton tape wall was changed to 400 ⁇ m. The resulting film was colorless and transparent.
  • a film was obtained in the same manner as in Example 1, except that the height of the Kapton tape wall was changed to 700 ⁇ m.
  • the resulting film was colorless and transparent.
  • a film was obtained in the same manner as in Example 5, except that the height of the Kapton tape wall was changed to 200 ⁇ m. The resulting film was colorless and transparent.
  • a film was obtained in the same manner as in Example 6, except that the height of the Kapton tape wall was changed to 200 ⁇ m. The resulting film was colorless and transparent.
  • the resulting material was subjected to a temperature elevation from 20 to 120 degrees centigrade slowly and cured over 13 hours. After curing was completed, the cured product was annealed at 120 degrees centigrade for 2 hours under a nitrogen atmosphere and placed under reduced pressure overnight. The thickness of the cured resin film was 50 ⁇ m. Thereafter, an ITO sputtered film was formed on the cured resin film.
  • a target of SnO 2 (10 wt %) in a mixed atmosphere of argon and oxygen, the substrate temperature was set at room temperature to form an ITO film having a thickness of 150 nm on the cured resin film (sputtering apparatus for forming thin film, a product of ULVAC, Inc.). Furthermore, ITO directly formed into a film on the borosilicate glass was also prepared.
  • the monomer mixed solution was degassed under reduced pressure for 1 hour, and then applied to the frosted surface of a Tempax one-side frosted glass plate (grit # 320: concavo-convex height of 1 to 4 ⁇ m) cleaned by means of a UV ozone cleaning equipment using an applicator with a coating gap set at 120 ⁇ m.
  • the monomer mixed solution was uniformly wet spread on the glass base material.
  • the resulting material was subjected to a temperature elevation from 20 to 120 degrees centigrade slowly and cured over 13 hours. After curing was completed, the cured product was annealed at 120 degrees centigrade for 2 hours under a nitrogen atmosphere and placed under reduced pressure overnight.
  • the thickness of the cured resin film was 120 ⁇ m.
  • an ITO sputtered film was formed on the cured resin film.
  • the substrate temperature was set at room temperature to form an ITO film having a thickness of 150 nm on the cured resin film (sputtering apparatus for forming thin film, a product of ULVAC, Inc.).
  • ITO directly formed into a film on the borosilicate glass was also prepared.
  • a film comprising a resin having a thiourethane bond, wherein the molar ratio (S/N) of sulfur to nitrogen contained in said resin is equal to or more than 0.8 and less than 3.
  • the film of the present invention also includes a sheet-like one.

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US20130230336A1 (en) * 2012-03-05 2013-09-05 Fuji Xerox Co., Ltd. Roll member, charging device, image forming apparatus, and process cartridge
US10308755B2 (en) 2014-04-18 2019-06-04 Bridgestone Corporation Sheet-forming body, adhesive sheet, and laminate
US20190338092A1 (en) * 2017-02-02 2019-11-07 Ares Materials Inc. Flexible color filter and method of manufacturing
US20230399942A1 (en) * 2022-06-08 2023-12-14 Saudi Arabian Oil Company Fluorescent dye oil tracer compositions
US11999855B2 (en) 2021-12-13 2024-06-04 Saudi Arabian Oil Company Fluorescent dye molecules having hydrophilicity and hydrophobicity for tracer applications

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US10329373B2 (en) * 2014-03-28 2019-06-25 Hoya Lens Thailand Ltd. Polyisocyanate monomer composition for optical members, and optical member and production method therefor
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KR20120073328A (ko) 2012-07-04
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US10106660B2 (en) 2018-10-23
CN102666676B (zh) 2015-11-25

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