WO2006085449A1 - Film de revêtement pour compensation optique, et élément optique - Google Patents

Film de revêtement pour compensation optique, et élément optique Download PDF

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Publication number
WO2006085449A1
WO2006085449A1 PCT/JP2006/301496 JP2006301496W WO2006085449A1 WO 2006085449 A1 WO2006085449 A1 WO 2006085449A1 JP 2006301496 W JP2006301496 W JP 2006301496W WO 2006085449 A1 WO2006085449 A1 WO 2006085449A1
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WIPO (PCT)
Prior art keywords
carbon atoms
optical compensation
coating film
cellulose
group
Prior art date
Application number
PCT/JP2006/301496
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English (en)
Japanese (ja)
Inventor
Michinori Tsukamoto
Yasuhiro Sekiguchi
Tomoki Hiiro
Sadao Fujii
Original Assignee
Kaneka Corporation
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Filing date
Publication date
Priority claimed from JP2005036958A external-priority patent/JP2006221116A/ja
Priority claimed from JP2005039873A external-priority patent/JP2006227222A/ja
Priority claimed from JP2005141980A external-priority patent/JP2006317813A/ja
Priority claimed from JP2006009344A external-priority patent/JP4772515B2/ja
Application filed by Kaneka Corporation filed Critical Kaneka Corporation
Publication of WO2006085449A1 publication Critical patent/WO2006085449A1/fr

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Classifications

    • 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
    • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/139—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent
    • G02F1/1393—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on orientation effects in which the liquid crystal remains transparent the birefringence of the liquid crystal being electrically controlled, e.g. ECB-, DAP-, HAN-, PI-LC cells
    • G02F1/1395—Optically compensated birefringence [OCB]- cells or PI- cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis

Definitions

  • the present invention relates to an optical compensation coating film for performing optical compensation of retardation by a liquid crystal cell or the like, an optical compensation coating film-forming coating solution suitable for forming the coating film, and the optical compensation
  • the present invention relates to a method for forming a coating film.
  • the present invention relates to a retardation adjusting agent, an optical compensation coating film containing the retardation adjusting agent, and a coating liquid for forming the optical compensation coating film.
  • the present invention relates to an optical element manufactured using them and a method for manufacturing the optical element.
  • the present invention relates to an optical compensation film (retardation film), a polarizing plate provided with the optical compensation film, and a liquid crystal display device.
  • a phase difference film for optical compensation is used in order to increase the viewing angle by compensating for the phase difference due to birefringence of a liquid crystal cell, a polarizing plate, and other liquid crystal display device constituent films.
  • a retardation film for example, a polymer such as polycarbonate, polyester, polystyrene, polyamide, polyimide, and polyethersulfone is subjected to a solution casting method, a uniaxial stretching method after a solution casting, and a drying after solution casting. And a biaxial stretching method, extrusion method, uniaxial stretching method of extruded product, biaxial stretching method of extruded product, calendar method, etc.
  • Such a retardation film is a film having a positive intrinsic birefringence value such as polycarbonate, polystyrene, etc. according to the applied liquid crystal cell, polarizing plate, other liquid crystal display device constituting film, etc.
  • a positive intrinsic birefringence value such as polycarbonate, polystyrene, etc.
  • One to several films with material strength having a negative intrinsic birefringence value such as the above are used separately. In order to use these films, first, a complicated film forming process is required for film formation, and it is also necessary to attach these films to liquid crystal display device components.
  • a retardation layer has been proposed by forming a thin film by coating (for example, see Patent Document 3).
  • those having optical properties of n> n ⁇ n in other words, (( n + n) / 2-nzxvxyz
  • Patent Document 1 JP-A-3-33719
  • Patent Document 2 Japanese Patent Laid-Open No. 11-248939
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2001-290023
  • Patent Document 4 JP-A-7-13022
  • An object of the present invention is to provide an optical compensation coating film at low cost without requiring a complicated film forming step. Furthermore, it provides an optical compensation coating film having the characteristics of [(n + n) / 2 ⁇ n] X d 0 at low cost, and has the characteristics without the need for film sticking or the like. It is to provide an optical element.
  • the present inventors have intensively studied and formed a cellulose N-substituted carbamate or any one of aromatic vinyl polymers.
  • the present inventors have found that the above-mentioned problems can be solved by an optical compensation coating film characterized by the above, and have reached the present invention.
  • the present invention relates to a coating film for optical compensation characterized by comprising a polymer of either cellulose N-substituted carbamate or aromatic bulle polymer.
  • the present invention relates to a coating film for optical compensation characterized by satisfying the relationship 1 ⁇ 0.
  • the cellulose N-substituted carbamate in the cellulose N-substituted carbamate, at least one of hydroxyl groups of cellulose is N-substituted carbamate, and at least one of hydrogen atoms bonded to a nitrogen atom of the cellulose strength carbamate is It is substituted with a group selected from the following general formulas (1) to (3), and the plurality of N-substituents are the same or different and are the following general formulas (1) to (3)
  • the present invention relates to a coating film for optical compensation, which is a compound.
  • R 4 and R 5 are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or carbon.
  • R 6 , R 7 , R 8 , R 9 , R 1Q , R U , R 12 are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms.
  • R 13 , R ′′, R 15 , R ln , R ′′, R 18 , R 19 are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.
  • the embodiment contains at least one selected from the group consisting of aromatic vinyl polymers such as poly (1-burnaphthalene), poly (2-burnaphthalene) and poly (4-birubiphthal). It is related with the coating film for optical compensation characterized by these.
  • Preferred embodiment is characterized in that it is formed containing a phase difference adjusting agent.
  • the present invention relates to a coating film for optical compensation.
  • the embodiment contains a phase difference adjusting agent for cellulose N-substituted carmate comprising at least one selected from force rubamic acid ester, N-substituted force rubamic acid ester, urea, and N-substituted urea force.
  • the present invention relates to an optical compensation coating film.
  • Preferred embodiments include ethyl carnomate, phenyl carnomate, N-phenyl carbamate, N phenyl carbamate, N- (4-tolyl) carbamate, N— (4-Tolyl) strength rubamate, urea, N, N, —diphenyl urea, N, N, —di-p-trilylurea, N—phenol—N '-(p-tolyl)
  • the present invention relates to a coating film for optical compensation, comprising a retardation adjusting agent for cellulose N-substituted carnomate, which has at least one force selected from the group of urea.
  • the present invention relates to a coating solution for forming an optical compensation coating film formed by containing the following (A) and (B).
  • the coating film for forming an optical compensation coating film is characterized by comprising (A) and (B), and further comprising (C) a retardation adjusting agent. Concerning the working fluid.
  • the present invention relates to a coating solution for forming a coating film for optical compensation, which is a phase difference adjusting agent for use in optical compensation.
  • Preferred embodiments include: (C) Retardation adjusting agent strength rubyl ethamine, force rubamate phenyl, N-phenol carbamic acid, N-phenol carbamic acid, N- ( 4-tolyl) -force rubamate, N— (4-tolyl) -force rubamate, urea, N, N, -diphenylurea, N, N, —di-p-tolylurea, N—phenol-N
  • the present invention relates to a coating solution for forming an optical compensation coating film, which is a retardation adjusting agent for cellulose N-substituted carbamate, comprising at least one selected from the group of, (p-tri) urea.
  • the present invention provides a rubamic acid ester, N-substituted rubamic acid ester, urea, N
  • the present invention relates to a retardation adjusting agent for cellulose N-substituted carbamate, characterized by comprising at least one selected from substituted urea.
  • Preferred embodiments include ethyl carnomate, phenyl carnomate, N-phenyl carbamate, N phenol carbamate, N- (4-tolyl) carbamate, N- Of (4-tolyl) force rubamate, urea, N, N, —diphenyl urea, N, N, —di-p-tolylurea, N—phenol—N ′-(ptolyl) urea
  • the present invention relates to a phase difference adjusting agent for cellulose N-substituted carnomate characterized by having at least one force selected from the group.
  • the present invention relates to a method for forming an optical compensation coating film, wherein the coating liquid is coated on a substrate to form a coated substrate, and then the coated substrate is dried.
  • the above-mentioned coated substrate is first dried at a temperature in the range of a lower limit of 0 ° C and an upper limit of 40 ° C, and then the coated substrate is further reduced to a lower limit of 80 ° C and an upper limit of 300
  • the present invention relates to a method for forming a coating film for optical compensation, characterized by secondary drying at ° C.
  • the present invention is characterized in that after the coating liquid is applied to a substrate to form a coated substrate, the coating film is annealed by exposure to the vapor of component (B) and further dried.
  • the present invention relates to a method for forming an optical compensation coating film.
  • the present invention relates to a method for manufacturing an optical element characterized by using the above-described forming method.
  • the present invention relates to an optical element manufactured using the above manufacturing method.
  • the present invention relates to an optical compensation film manufactured using the above-described forming method.
  • the present invention relates to a polarizing plate characterized in that the above optical compensation film is mounted as a polarizer protective film on at least one surface of a polarizer.
  • the present invention relates to a liquid crystal display device provided with the above optical compensation film.
  • the present invention relates to a liquid crystal display device provided with the above polarizing plate.
  • the optical compensation coating film of the present invention When the optical compensation coating film of the present invention is used, a complicated film forming process or film pasting is performed. In particular, an optical element having an optical compensation layer of [(n + 11) 72-11] (1 ⁇ 0 can be produced. Using the method of forming a film, the value represented by (n + n) / 2-n is negative, and a coating film for optical compensation having a larger absolute value can be formed. Since the device can be manufactured, it is extremely useful industrially.
  • the present invention is a coating film for optical compensation characterized by comprising a polymer of cellulose N-substituted carbamate or an aromatic vinyl polymer.
  • cellulose N-substituted carbamate of the present invention at least one hydroxyl group of cellulose is N-substituted carbamate, and at least one hydrogen atom bonded to a nitrogen atom of the cellulose carbamate is represented by the following general formula. It is a compound that is substituted with a group selected from (1) to (3), and a plurality of N-substituents are the same or different and have the following general formulas (1) to (3)
  • An optical compensation coating film characterized by
  • R 5 is the same or different and is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • R 6 , R 7 , R 8 , R 9 , R 1Q , R U , R 12 are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms.
  • R 13 , R ′′, R 15 , R ln , R ′′, R 18 and R 19 are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 21 carbon atoms, a halogen atom, and a nitro group.
  • the cellulose N-substituted carbamate in the present invention (hereinafter sometimes referred to as component (A)) is, for example, cellulose obtained from various wood pulp, cotton linter, cotton lint, etc. It can be produced by a known method of reacting an isocyanate compound in the presence of a base catalyst such as triethylamine.
  • the base catalyst can also be used as a solvent.
  • amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide can be suitably used.
  • an inorganic salt such as lithium chloride can be added to improve the solubility of cellulose in a solvent.
  • isocyanate compounds include the following general formulas (4) to (4) The compound represented by (6) is mentioned.
  • R ° and R z R z R z are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.
  • Alkyl halide group, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, and acyloxy group having 1 to 21 carbon atoms Represents a halogen atom or a nitro group.
  • R 25 , R 2 °, R 29 , R 3 °, 1 are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl halide having 1 to 20 carbon atoms. Group, a C1-C21 acyloxy group, a halogen atom, and a nitro group.
  • R 32 , R 33 , R 34 , R 35 , R 37 and R 38 are the same or different and are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 1 to 21 carbon atoms. Represents an acyloxy group, a halogen atom or a nitro group.
  • R 2 °, R 21 , R 22 , R 23 , R 24 may be the same or different and each is a hydrogen atom or an alkyl having 1 to 16 carbon atoms.
  • alkoxy group having 1 to 16 carbon atoms halogenated alkyl group having 1 to 16 carbon atoms, aryl group having 6 to 16 carbon atoms, aryloxy group having 6 to 16 carbon atoms, aralkyl group having 7 to 16 carbon atoms, carbon
  • An isocyanate compound represented by the general formula (4) which is an aralkyloxy group having 7 to 16 carbon atoms, an acyloxy group having 1 to 17 carbon atoms, a halogen atom, or a nitro group, is reacted, and at least one hydroxyl group of the cellulose is N-substituted carbamate cellulose N-substituted carbamate is preferably used.
  • R 25 , R 26 , R 27 , R 28 , R 29 , R 3 °, R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 are the same or different,
  • cellulose N-substituted carbamate in which isocyanate compounds represented by the general formulas (5) and (6) are reacted and at least one of hydroxyl groups of the cellulose is N-substituted carbamate.
  • R 2 °, R 21 , R 22 , R 23 , R 24 are the same or different and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen having 1 to 12 carbon atoms.
  • Alkyl group aryl group having 6 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, aralkyl group having 7 to 12 carbon atoms, aralkyloxy group having 7 to 12 carbon atoms, acyloxy group having 1 to 13 carbon atoms, halogen It is more preferable to use a cellulose N-substituted carbamate in which an isocyanate compound represented by the general formula (4), which is an atom or a nitro group, is reacted and at least one hydroxyl group of the cellulose is N-substituted carbamate.
  • an isocyanate compound represented by the general formula (4) which is an atom or a nitro group
  • R 25 , R 26 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 are the same or different and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms.
  • isocyanate compounds represented by the general formulas (4) to (6) include phenyl isocyanate, o tolyl isocyanate, m-tolyl isocyanate, p tolyl isocyanate, 2 ethyl phenyl isocyanate, 3 Ethyl phenyl isocyanate, 4 Ethyl phenyl isocyanate, 2 Propyl phenol isocyanate, 3 Propyl phenyl isocyanate, 4 Propyl phenyl isocyanate, 2 Butyl phenyl isocyanate, 3 Butyl phenyl isocyanate, 4 Butyl phenyl isocyanate, 4 Butyl phenyl isocyanate, 4 Butyl phenyl isocyanate, 4 Butyl phenyl isocyanate, 4 Butyl phenyl isocyanate Dimethylphenol isocyanate, 2,5-Dimethylphenol isocyanate, 2,6 Dimethylphenol iso
  • Cellulose has three hydroxyl groups per glucose residue, which is a structural unit. Therefore, when these hydroxyl groups are substituted, the degree of substitution per glucose residue (hereinafter referred to as DS) is a maximum of 3.
  • the lower limit of DS is preferably 0.1, more preferably 0.5, more preferably 1, and the upper limit is preferably 3, more preferably 2.95, and even more preferably 2.9. .
  • DS is lower than 0.1, it tends to be difficult to dissolve in a solvent.
  • two or more cellulose N-substituted carbamates having different DSs may be used in combination, or may be used alone.
  • the lower limit of the number average molecular weight of component (A) is preferably 5000, more preferably 8000, more preferably ⁇ 10,000, and the upper limit is preferably ⁇ 500,000, more preferably ⁇ 300000, Preferably it is 200,000. If the number average molecular weight is less than 5,000, the coating film strength tends to decrease, and if the number average molecular weight is more than 500,000, it tends to be difficult to dissolve in a solvent (sometimes referred to as component (B)).
  • the number average molecular weight is determined by gel permeation chromatography. It is a value measured by the graphic (GPC) method.
  • cellulose N-substituted carnomates having different number average molecular weights
  • Any aromatic vinyl polymer of the present invention (hereinafter sometimes referred to as component (A)) may be used as long as it contains an aromatic bulule unit.
  • 2,4 dibutyl styrene poly (2,5 dibutyl styrene), poly (3,4 dibutinoles styrene), poly (3,5 dibutyl styrene) and other poly (alkyl styrene); poly (2-methoxystyrene), poly (3-methoxystyrene), poly (4-methoxystyrene), poly (2,4 dimethoxystyrene), poly (2,5 dimethoxystyrene), poly (3,4 dimethoxystyrene), poly (3,5 dimethoxystyrene) ), Poly (2 ethoxy styrene), poly (3 ethoxy styrene), poly (4 ethoxy styrene), poly (2, 4 ethoxy styrene), poly (2, 5 diethoxy styrene), poly (3,4-jet) Toxistyrene), poly (3,5-e
  • a copolymer of two or more of these; a copolymer of one or two or more of these with another polymer can also be used.
  • styrene mono ( ⁇ -methyl styrene) copolymer styrene mono (2-methyl styrene) copolymer, styrene mono (3-methyl styrene) copolymer, styrene mono (4-methyl styrene) copolymer, styrene Mono (2-methoxystyrene) copolymer, styrene mono (3-methoxystyrene) copolymer, styrene- (4-methoxystyrene) copolymer, styrene- (2 chlorostyrene) copolymer, styrene mono (3 Chlorostyrene) copolymer, styrene- (4-chlorost
  • the polymer can be produced by polymerizing a single monomer or two or more monomers in the presence of a radical polymerization initiator, a cation polymerization initiator, or a cationic polymerization initiator.
  • aromatic bur polymer poly (1 urnaphthalene), poly (2 It is preferable from the viewpoint of heat resistance and availability that it contains at least one selected from di (l-naphthalene) and poly (4-birubiphenol).
  • the lower limit of the weight average molecular weight of the aromatic vinyl polymer is preferably 10,000, more preferably 20000, still more preferably 30000, and the upper limit is preferably 1000000, more preferably ⁇ or 800,000, and even more preferably. Mas ⁇ until 600000. If the weight average molecular weight force is less than S 10000, the coating film strength tends to decrease, and if the weight average molecular weight is more than 1000000, it tends to be difficult to dissolve in the solvent.
  • the weight average molecular weight is a value measured by gel permeation chromatography (GPC). In the present invention, two or more polymers having different weight average molecular weights may be used in combination, or may be used alone!
  • the coating liquid contains (i) a polymer selected from the above-mentioned cellulose, a substituted carnomate, and an aromatic vinyl polymer, and (ii) a solvent in which the component (ii) is soluble and soluble.
  • the solvent of component ( ⁇ ) is not particularly limited as long as component ( ⁇ ) is soluble.
  • Specific examples include benzene, toluene, ⁇ -xylene, m-xylene, p Hydrocarbon solvents such as xylene, ethylbenzene, isopropylbenzene, and jetylbenzene isomer mixtures; methanol, ethanol, 1 propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1 propanol, furfuryl Alcohol solvents such as alcohol and benzyl alcohol; ether solvents such as ethyl ether, isopropyl ether, 1,3 dioxolane, 1,4 dioxane, tetrahydropyran, tetrahydrofuran, 1,2-dimethoxyethane; acetone, 2 butanone, Ketone solvents such as 4-methyl-2-pentanone and cyclohexanone; Len,
  • the amount of the solvent is preferably a lower limit that the ratio of the component (A) to the total weight of the component (A) and the component (B) is 1% by weight as the lower limit and 70% by weight as the upper limit. More preferably, the lower limit is 3% by weight, and the upper limit is 50% by weight.
  • the proportion of component (A) is less than 1% by weight, the coating film thickness tends to be thin, and the required film thickness tends to be difficult to obtain.
  • it exceeds 70% by weight the viscosity of the coating liquid is high. Therefore, workability tends to be inferior.
  • the thickness retardation of the coating film for optical compensation is the force expressed by [(n + n) / 2-n] X d.
  • (n + n) Z2 There are a method of adjusting the value represented by n and a method of adjusting d (film thickness).
  • the method of adjusting the film thickness is simple, but as mentioned earlier, increasing the film thickness and increasing the thickness phase difference only increases the bulk of the liquid crystal display device components after the coating film is formed. There arises a problem that the material cost of the film increases.
  • the retardation adjusting agent of the present invention is particularly suitable for such a thickness retardation. It's no surprise that you can adjust it.
  • the retardation adjusting agent for cellulose N-substituted carbamate of the present invention is preferably composed of at least one selected from strength rubamate ester, N-substitution strength rubamate ester, urea, and N-substituted urea. ! /
  • the retardation adjusting agent for cellulose N-substituted carbamate of the present invention is cellulose N-
  • the thickness phase difference of the substituted carbamate can be adjusted in the negative direction.
  • the strong rubamic acid ester can be obtained by, for example, a known method of reacting ammonia with a chloroformate
  • the N-substituted rubamic acid ester can be obtained by, for example, forming a primary amine or a secondary amine with a chloroformate. It can be produced by a known method of reacting.
  • the urea can be obtained, for example, by an industrial production method in which ammonia and carbon dioxide are reacted under high temperature and high pressure.
  • the N-substituted urea is obtained by reacting, for example, an isocyanate compound with a primary amine or a secondary amine. It can be produced by a known method.
  • the strength rubamic acid ester of the present invention contains a strength rubamoyloxy group (NH—CO—O—).
  • Any compound having 1 to 8 powerful rubamoyloxy groups that can be used is preferred.
  • a compound containing 1 is more preferred.
  • a compound represented by the following general formula (7) is preferred.
  • R 39 represents an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. ;).
  • R 39 is an alkyl group having 1 to 16 carbon atoms, a halogenated alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, or an alkyl group having 7 to 16 carbon atoms.
  • R 39 is more preferably an aralkyl group.
  • R 39 is an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. Particularly preferred is a group.
  • the N-substituted rubamic acid ester of the present invention contains an N-substituted rubamoyloxy group (R-NH-CO-O-, R is an alkyl group, a halogenated alkyl group, an aryl group, an aralkyl group). Any of them can be used. N—Substitution power A compound containing 1 to 8 rubamoyloxy groups is preferred. A compound containing 1 is more preferred. Viewpoint of availability of raw materials Compounds represented by the following general formula (8) are preferred. Yes.
  • R 4Q and R 41 are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents ⁇ 20 aralkyl groups).
  • R 4Q and R 41 are the same or different and each represents an alkyl group having 1 to 16 carbon atoms, a halogenated alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • R 4Q and R 41 are more preferably an aralkyl group having 7 to 16 carbon atoms, the same or different, and an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, Particularly preferred are aryl groups having 6 to 12 carbon atoms and aralkyl groups having 7 to 12 carbon atoms.
  • N-substituted urea of the present invention can be used as long as it contains a ureylene group (one NH—CO—NH—).
  • a compound represented by the following general formula (9) is also preferable from the viewpoint of availability of raw materials.
  • R 42 and R 43 are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, Represents a 7-20 aralkyl group having carbon atoms).
  • R 42 and R 43 are the same or different and each represents an alkyl group having 1 to 16 carbon atoms, a halogenated alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms.
  • R 42 and R 43 are more preferably an aralkyl group having 7 to 16 carbon atoms, the same or different, and an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, Carbon number 6-12 Particularly preferably an aryl group, an aralkyl group having 7 to 12 carbon atoms.
  • carnomate ester examples include, for example, methyl carnomate, ethyl rubamate, cyclopentyl rubamate, cyclohexyl rubamate, trichloromethyl rubamate, ferro-carbamate fe- , Naphthyl chloride, naphthyl chloride, benzyl carbamate, ethylene glycol dicarbamate, propylene glycol dicarbamate, hydroquinone dicarbamate, pyrocatechol dicarbamate, pyrogallol tricarbamate and the like.
  • N-substituted rubamic acid ester examples include, for example, methyl N-methylcarbamate, ethyl N-methylcarbamate, cyclopentyl N-methylcarbamate, cyclohexyl N-methylcarbamate, and trichloro N-methylcarbamate.
  • ⁇ -substituted urea examples include ⁇ , N'-dimethylurea, ⁇ , N'-diethylurea, ⁇ , ⁇ , -dichloromethylurea, ⁇ , ⁇ , -diphenolurea. , ⁇ , ⁇ , -dibenzylurea, ⁇ ethyl- ⁇ , monomethylurea, ⁇ -methyl- ⁇ , one-phenolurea, ⁇ -benzyl ⁇ , -phenolurea, ⁇ , ⁇ , —di- ⁇ -tolyl Urea, ⁇ ferrule ⁇ ,-( ⁇ -tolyl) urea, and the like.
  • These retardation agents for cellulose ⁇ -substituted carbamates may be used alone or in combination of two or more.
  • the retardation adjusting agent for cellulose ⁇ substituted carnomates is carnomate ethyl, carnomate phenol, ⁇ -carcarnomate ethyl, ⁇ -phenol.
  • the total weight of the polymer as component (i) and the phase difference adjusting agent as component (C) is 100% by weight. %, It is preferable to use the lower limit of 0.1% by weight and the upper limit of 70% by weight. The lower limit of 0.2% by weight and the upper limit of 65% by weight are preferred. More preferably, the lower limit is 0.3% by weight, and the upper limit is 60% by weight.
  • the ratio of the phase difference adjusting agent is less than 0.1% by weight, the effect of adjusting the thickness phase difference tends to be small, and when it is larger than 70% by weight, it tends to bleed from the coating film for optical compensation. is there.
  • the resin that can be added for the purpose of modifying the properties of the coating film of the present invention.
  • the resin that can be added include polycarbonate resin, talyl resin, polyester resin, polystyrene resin, polyolefin resin, polyamide resin, polyimide resin, polyvinyl alcohol resin, polybuta resin.
  • examples include settal resin, polyether sulfone resin, polyarylate resin, epoxy resin, silicone resin, phenol resin, urethane resin, and the like. ⁇ can be added.
  • Additives include antioxidants (eg, Malawi phenols such as IRGANOX 1010, IRGANOX 1135, IRGANOX 1330, etc.
  • processing stabilizers eg, HP-136, IRGANOX manufactured by Ciba 'Specialty' Chemicals
  • processing stabilizers eg, HP-136, IRGANOX manufactured by Ciba 'Specialty' Chemicals
  • E201 IRGAFOS 168, etc.
  • light stabilizers for example, hindered amines such as Sanol LS-765, Sanol LS-770 from Sankyo Lifetech
  • UV absorbers for example, TINUVIN P, TINUVIN made by Chinoku 'Specialty' Chemicals) 213, benzotriazoles such as TINUVIN 326)
  • adhesion improvers eg, silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane
  • silanol condensation catalysts eg, rivers
  • aluminum tris ethyl acetate acetate
  • aluminum chelate M etc.
  • Luminium chelates for example, esters such as di-2-ethylhexyl phthalate and diisobutyl adipate
  • surfactants for example, fluorine compounds such as Fluorad FC-430 and Fluorad FC-4430 manufactured by Sumitomo 3EM
  • antistatic agents for example, IRG ASTAT P18, IRGASTAT P22, etc. manufactured by Ciba Specialty Chemicals
  • the coating liquid of the present invention can be obtained, for example, by mixing the above-mentioned components at a temperature not lower than the melting point of the solvent and not higher than the boiling point, or after being mixed or stirred.
  • the substrate it is preferable to be transparent in view of the power with which various types of substrates can be used, particularly the application power.
  • specific compounds used for the substrate include polycarbonate polymers produced by polycondensation of bisphenol A and salty carbon; polymethyl acrylate, polymethyl methacrylate, etc. Poly Acrylic acid ester; Condensation of dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid and the like, and ring opening of latatones with ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, neopentyl darlicol, etc.
  • Polyester polymers obtained by polymerization styrene polymers such as polystyrene and poly (-methylstyrene); copolymers of acrylic acid esters and styrene; hydrogenated products of polyethylene, polynorbornene and polyisoprene, Polyolefin-based polymers such as hydrogenated polybutadienes; Cellulose-based resins such as triacetyl cellulose; Polyamides such as nylon 6 and nylon 66; Polyimides; Polyamide imides; Polybulal alcohol; Butyl chloride; Polyethersulfone; Examples thereof include xylose resin; silicone resin; compounds described in International Publication No. 01Z37007 pamphlet.
  • these polymers can be used as a solution casting method, a uniaxial stretching method of a dried product after solution casting, a biaxial stretching method of a dried product after solution casting, an extrusion method, a uniaxial stretching method of extrusion, and a biaxial stretching method of an extruded product.
  • These substrates can also be used as substrates for forming an optical compensation coating film.
  • the coating film for optical compensation can be suitably prepared on a substrate by applying the coating liquid of the present invention on one or both sides of the substrate to form a coated substrate, and then drying the coated substrate.
  • the coating methods include gravure roll coating method, Mayer bar coating method, doctor blade coating method, linole roll coating method, dip coating method, air knife coating method, calendar coating method, squeeze coating method, kiss coating method, bar coating method. Slot die coating method, spin coating method and the like.
  • drying method for example, a method of leaving the coated substrate in air or an inert gas such as nitrogen (air drying), a method of heating and drying in a hot air oven, an infrared heating furnace, or the like, a vacuum dryer, or the like Can be carried out by a method of drying under reduced pressure, etc., or a combination thereof.
  • air drying air drying
  • a method of heating and drying in a hot air oven, an infrared heating furnace, or the like, a vacuum dryer, or the like can be carried out by a method of drying under reduced pressure, etc., or a combination thereof.
  • the drying temperature condition constant temperature, multi-step temperature increase! /, Or deviation can be used.
  • the lower limit is 30 ° C
  • the upper limit is 300 ° C.
  • the lower limit is 0 ° C and the upper limit is 280 ° C.
  • the preferred lower limit is 10 ° C and the upper limit is 260 ° C.
  • the drying temperature is lower than -30 ° C
  • the drying time tends to be longer.
  • the drying temperature is higher than 300 ° C, the coating film or the substrate tends to be thermally deteriorated.
  • primary drying and secondary drying are particularly preferable from the economical viewpoint that it is preferable to increase the temperature in multiple stages in order to effectively dry.
  • the lower limit is 5 ° C
  • the lower limit is 0 ° C
  • the upper limit is 40 ° C
  • the upper limit is 35 ° C.
  • the lower limit is 10 ° C
  • the upper limit is 30 ° C. preferable.
  • Primary drying is (n + n)
  • the lower limit of 80 ° C and the upper limit of 300 ° C are preferable lower limit of 90 ° C, and the upper limit of 280 ° C is more preferable lower limit of 100 ° C and upper limit of 260 ° C. preferable.
  • Secondary drying is necessary to establish the coating film internal structure necessary to increase the absolute value of the value represented by (n + n) / 2-n.
  • the secondary drying temperature is lower than 80 ° C, the internal structure of the coating film tends to be insufficiently established, and when it is higher than 300 ° C, the coating film and the substrate tend to be thermally deteriorated.
  • the absolute value of (n + n) Z2 ⁇ n is sufficiently large, the established internal structure of the coating film is observed with a transmission electron microscope (TEM) or the like. can do.
  • TEM transmission electron microscope
  • the present invention provides a coating for optical compensation by applying a coating solution to a substrate to form a coated substrate, then exposing the coating film to the vapor of component (B), and further drying. This is the method of forming a film.
  • Annealing is preferably performed for improving the leveling property of the coating film, stress relaxation, and the like, and is effective, for example, for reducing in-plane retardation and reducing in-plane retardation fluctuation.
  • the annealing is preferably performed in the vapor of the component (B) by standing still horizontally with the coating film of the coated substrate facing upward.
  • the temperature during annealing can be set in various ways.
  • Lower limit 30 ° C, upper limit (boiling point of component (B)) is preferred Lower limit 15 ° C, upper limit (component (B) boiling point (° C) -5 ° C] is more preferred lower limit 0 ° C, and upper limit [(B) component boiling point (° C) -10 ° C] is more preferred. If the temperature during annealing is lower than 30 ° C, the annealing time tends to be longer, and if the temperature during annealing is higher than the boiling point (° C) of component (B), the coating film tends to flow out from the substrate. Tend to be. Various pressures can be set during annealing, and atmospheric pressure, increased pressure, or reduced pressure can be used, but atmospheric pressure is preferable in terms of workability.
  • the optical element here is composed of a substrate and an optical compensation coating film coated on the substrate. Also included is an element used for optical use after the substrate force is once peeled off from the coating film for optical compensation.
  • the optical element is coated with the coating liquid of the present invention on one or both surfaces of the substrate using the coating method described in the method for forming a coating film for optical compensation, and then dried or optically compensated. After coating using the coating method described in the method for forming a coating film for coating, it can be suitably produced by annealing and drying.
  • Drying can be suitably performed by using the drying method and the drying temperature described in the method for forming the optical compensation coating film.
  • the coating film for optical compensation of the present invention has a maximum refractive index n in the plane, n is the minimum refractive index, n is the refractive index in the thickness direction, and d is the film thickness.
  • n is the minimum refractive index
  • n is the refractive index in the thickness direction
  • d is the film thickness.
  • the above-mentioned properties are obtained by a coating film for optical compensation formed by containing any one of cellulose N-substituted carbamates satisfying the relationship of X d and 0 or an aromatic bur polymer.
  • the thickness of the optical compensation coating film is d (nm)
  • the in-plane retardation is expressed by (nn) X d
  • the thickness retardation is [(n + n) / 2 ⁇ n] X d.
  • the expressed in-plane phase difference is preferably lower limit Onm and upper limit 200 nm force, preferably lower limit Onm and upper limit 300 nm, more preferably lower limit Onm and upper limit lOOnm, when measured with 590 nm light.
  • the thickness retardation is 590 nm, and the lower limit—1000 ⁇ m, the upper limit—lnm is the lower limit of 800 nm, and the upper limit—lOnm is the lower limit—60 Onm, an upper limit of 20 nm is more preferable. If the thickness retardation is smaller than lOOOnm, it tends to be difficult to compensate for the retardation due to birefringence of liquid crystal cells.
  • a coating film for optical compensation satisfying the relationship of [(n + n) / 2-n] Xd ⁇ 100 used in another application can be obtained by containing a cellulose derivative.
  • Cellulose derivatives can be produced, for example, by chemically modifying cellulose obtained from various wood pulps, cotton linters, cotton lint and the like as raw materials.
  • carboxylic acid ester derivatives such as cellulose formate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, cellulose trifluoroacetate; cellulose sulfate, cellulose nitrate, cellulose phosphate, etc.
  • ether derivatives are preferred from the standpoint of physical properties such as low hydrolyzability and low hygroscopicity. More preferably, it is an ether derivative in which at least one hydroxyl group of cellulose is substituted with an alkoxy group having 1 to 20 carbon atoms, and more preferably, at least one of hydroxyl groups of cellulose is substituted with an alkoxy group having 1 to 10 carbon atoms. It is an ether derivative.
  • Preferable examples of the preferred! / ⁇ ⁇ cellulose derivatives are methylcellulose, ethyl cellulose, propinoresenorelose, butinoresenorelose, pentinoresenorelose, hexinoresenorelose, heptinoresenorelose, tasty cutinore Senorelose, Cyclopentino Resenellose, Succeed Hexino Resenorelose, Methinore Ethino Resenorelose, Methinorepropino Resenorelose, Methinore Butino Resenorelose, Methino Resentino Resenorelose, Methino Resenorelose , Methinoles, petitenoresenorelose, methinoreoctinoresenorelose, methinorecyclopentinoresenolesose, methinorecyclohexenoresenorelose, ethinorepropinoresenorelose, ethinorebutinores
  • the above ether-based derivative of cellulose can be produced, for example, by converting it to alkaline cellulose with sodium hydroxide or the like, and then adding and heating and stirring an alkyl halide such as chlorinated alkyl. At this time, when two or more alkyl halides are used, an ether derivative substituted with two or more alkoxy groups can be obtained.
  • Cellulose has three hydroxyl groups per glucose residue as its structural unit, and the degree of substitution per glucose residue (hereinafter sometimes referred to as DS) is 3 at maximum.
  • the lower limit is preferably 0.1, more preferably 0.5, even more preferably 1, and the upper limit is preferably 3, more preferably 2.95, and even more preferably 2.9. If the degree of substitution is lower than 0.1, it tends to be difficult to dissolve in a solvent.
  • two or more cellulose derivatives having different degrees of substitution may be used in combination, or may be used alone!
  • the lower limit of the number average molecular weight of the cellulose derivative is preferably 5000, more preferably 8000, still more preferably 10000, and the upper limit is preferably 300000, more preferably 250000, and even more preferably 200000. If the number average molecular weight is less than 5,000, the coating film strength tends to decrease, and if the number average molecular weight is more than 300,000, it tends to be difficult to dissolve in a solvent.
  • the number average molecular weight is a value measured by gel permeation chromatography (GPC). In the present invention, two or more cellulose derivatives having different number average molecular weights may be used in combination, or may be used alone.
  • cellulose derivatives exemplified as the cellulose derivative may be used alone, or two or more kinds may be used in combination.
  • the optical compensation film (retardation film) of the present invention will be described.
  • the optical compensation film a film formed from those exemplified as the substrate for the optical element is used, and the optical compensation layer is formed by using the method for forming the optical compensation coating film. It can be suitably manufactured.
  • a protective film is attached to both surfaces of a polarizer using an adhesive such as a polyester-based adhesive, a polyacrylic adhesive, an epoxy-based adhesive, a cyanacrylic adhesive, or a polyurethane-based adhesive.
  • an adhesive such as a polyester-based adhesive, a polyacrylic adhesive, an epoxy-based adhesive, a cyanacrylic adhesive, or a polyurethane-based adhesive.
  • polarizers include iodine and Z or Z Is a polarizer produced by adsorbing and orienting a dichroic dye, a polybulualcohol-based film is dehydrated to form a polyene, and a polarizer and polysalt hybrid film produced by orienting are dehydrochlorinated.
  • Examples include those prepared by forming and orienting polyene.
  • Examples of the hydrophilic polymer film used for the polarizer include a polybulal alcohol film, a partially formalized polybulal alcohol film, and a saponified film of an ethylene acetate butyl copolymer.
  • Examples of the protective film include those exemplified as the substrate for the optical element, those formed into a film, and the optical compensation film (retardation film) of the present invention.
  • the substrates for the optical element When the film is pasted on both sides of the polarizer, the optical compensation coating film of the present invention is formed on at least one side of the polarizing plate using the method for forming an optical compensation coating film after preparing the polarizing plate.
  • the optical compensation film (retardation film) of the present invention can be used as a protective film, it can be used on both sides of a polarizer, or the optical compensation film (retardation film) of the present invention is used on one side and the opposite. It is also possible to use a film made of the optical element substrate on the surface. Also, after producing a polarizing plate using the optical compensation film (retardation film) of the present invention on one side and a film formed on the opposite side of the substrate for the optical element, a new polarizing plate is prepared on one side or both sides.
  • the optical compensation coating film of the present invention can also be provided.
  • liquid crystal display device of the present invention As a liquid crystal display device, for example,
  • Light source Z light guide plate Z light diffusing film Z lens film Z brightness enhancement film Z polarizing plate Z liquid crystal cell display device configured in the order of Z polarizing plate, the incident light side of the liquid crystal cell and the Z or outgoing light side
  • the liquid crystal of the present invention is mounted by mounting the optical compensation film (retardation film) of the present invention on the polarizing plate of the incident light side and the Z or outgoing light side of the Z or liquid crystal cell. It can be a display device.
  • the liquid crystal cell method include a VA (Vertical Alignment) method, an IPS (In-Plane Switching) method, and an OCB (Optically Compensated Birefringence) method.
  • the thickness phase difference was determined by [(n + n) / 2-n] Xd.
  • the phase difference was measured with the slow axis as the tilt center axis, if the phase difference increased as the tilt angle increased!]
  • the following method was also used to determine the sign of the phase difference. Overlay the polycarbonate ⁇ 4 plate on the manufactured optical element, and attach it to the automatic birefringence meter KOBRA-WR so that the orientation angle force of the ⁇ 4 plate is 0 ⁇ 1 degree. 2
  • the phase difference was measured with 590nm light at 5 ° C.
  • phase difference of the optical element alone is also rising in the positive direction as the tilt angle is increased, and when it is lower than the phase difference of ⁇ ⁇ 4 plate alone.
  • the phase difference of the single optical element decreases in the negative direction as the tilt angle increases, and adds a positive or negative sign to the phase difference of the single optical element measured earlier to calculate the three-dimensional refractive index. did. From the obtained results, the in-plane phase difference was determined by ( ⁇ n) Xd. Also, the thickness phase difference is expressed as [(n + n) / 2-n
  • the degree of substitution DS of synthetic product (2) was 3 as a result of proton NMR analysis. DS is obtained by comparing the chemical shift area (3.4 to 5.5 ppm) of protons derived from the cellulose skeleton with the chemical shift area (6.7 to 7.8 ppm) of protons in the phenolic group. Were determined.
  • Synthetic product (1) 4.85 g of butyl acetate was added to 0.85 g and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane phase difference: Onm, thickness phase difference: lnm) using a bar coater, and then 120 ° An optical element was fabricated by drying in air for 1 minute at C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained as described above were measured, and the results are shown in Table 1.
  • Synthetic product (1) 4.85 g of ethyl acetate sorb acetate was added to 0.85 g and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, It was placed in a glass container filled with solvacetate vapor, sealed, and then annealed at 25 ° C for 24 hours. Thereafter, the coated substrate was taken out and dried in air at 120 ° C for 1 minute to produce an optical element. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, the physical properties of the optical element obtained as described above were measured, and the results are shown in Table 1.
  • Synthetic product (3) Black mouth form 9. Og was added to Og and dissolved at 25 ° C. Next, this coating solution was applied to a 150 / zm-thick glass substrate (average refractive index: 1.52, in-plane phase difference: Onm, thickness phase difference: lnm) using a bar coater. The optical device was fabricated by drying in air for 1 minute at ° C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, the physical properties of the optical element obtained above were measured, and the results are shown in Table 1.
  • the optical element produced in Experimental Example 3 was placed in a glass container filled with Kuroguchi-form vapor, sealed, and then annealed at 30 ° C for 7.5 hours. Then remove the optical element and Dry in air for 1 minute.
  • the coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate.
  • physical properties of the optical element obtained as described above were measured, and the results are shown in Table 1.
  • an in-plane birefringence (n ⁇ n) smaller than that in Experimental Example 3 was obtained. In other words, the in-plane retardation can be reduced by annealing.
  • Synthetic product (2) 0.5 g of butyl acetate 4. Og and ethylene glycol monomethyl etherate 0.5 g were added and dissolved at 23 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: 1 nm) using a bar coater. It was. Thereafter, this coated substrate was dried in air at 23 ° C. for 25 minutes to produce an optical element. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Then obtained by above The physical properties of the optical element were measured. The results are shown in Table 2.
  • Example 5 The same procedure as in Example 5 was performed, except that the coated substrate was dried in air at 23 ° C for 44 hours and further dried in air at 100 ° C for 1 minute to produce an optical element. It was. The physical properties of the obtained optical element were measured. The results are shown in Table 2. An optical element in which the absolute value of (n + n) / 2 ⁇ n is larger than that in Experimental Example 5, which was simply dried in air at 23 ° C. for 44 hours, was obtained.
  • a polyvinyl alcohol film was impregnated with iodine and stretched to produce a polarizer.
  • An 80 m thick cellulose acetate film was bonded to one side of this polarizer using a polyacrylic adhesive.
  • the optical compensation film produced in Experimental Example 13 was bonded to the opposite surface of the polarizer using a polyacrylic adhesive so that the coating film surface was on the outside, and a polarizing plate having an optical compensation layer was produced. .
  • a liquid crystal display device equipped with an IPS liquid crystal cell was prepared, and a display device was produced in which the optical compensation film produced in Experimental Example 13 was superimposed on the outgoing light side of the liquid crystal cell. As a result of observing the display screen, a good image was obtained in which the color display did not change when looking at the front force or the oblique direction force.
  • Styrene Maleic anhydride copolymer (Dylark D332 from Nova Chemical) 30. Og was added with 70.0 g of chloroform and dissolved at 25 ° C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater, and this coating was applied. The substrate was placed in a glass container filled with black mouth form vapor at atmospheric pressure, sealed, and then annealed at 25 ° C for 48 hours. Then, the coated substrate was taken out and air-dried at 25 ° C for 6 hours to produce an optical element.
  • the coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained above were measured, and the results are shown in Table 3. Here, an optical element of [(n + n) Z2-n] Xd ⁇ 0 was obtained.
  • Ethylcellulose (ETHOCEL STD-100, manufactured by Dow Chemical, number average molecular weight: 634 00, DS: 2.5) 20. Og Dissolved under C. Next, apply this coating solution to a 150 m thick glass substrate (average refractive index: 1.52, in-plane phase difference: Onm, thickness phase difference: Inm) using a bar coater, then 25 The optical element was fabricated by air drying in air for 6 hours at ° C. The coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained above were measured, and the results are shown in Table 4. Here, [(n + n) / 2-n] X d ⁇ l
  • Example 22 150 m thick glass substrate by reducing the applied pressure of the bar coater using the coating solution prepared in Example 22 (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: Inm)
  • the coated substrate was placed in a glass container filled with black mouth form vapor at atmospheric pressure, sealed, and then annealed at 25 ° C. for 72 hours. Thereafter, the coated substrate was taken out and air-dried in air at 25 ° C for 6 hours to produce an optical element.
  • the coating thickness after drying (d (nm)) was determined by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, physical properties of the optical element obtained above were measured, and the results are shown in Table 4.
  • the in-plane retardation also increased at the same time as the thickness retardation increased.
  • the in-plane retardation is Onm, that is, the same thickness retardation as in Experimental Example 23, that is, [(n + n) / 2-n] X d ⁇
  • Ethylcellulose (ETHOCEL STD-100, manufactured by Dow Chemical, number average molecular weight: 634 00, DS: 2.5) 20. Dissolved under C. Next, this coating solution was applied to a 150 m thick glass substrate (average refractive index: 1.52, in-plane retardation: Onm, thickness retardation: lnm) using a bar coater. The optical element was fabricated by air-drying in air for 6 hours at ° C. The coating thickness after drying (d (nm)) was obtained by measuring the thickness of the entire optical element and subtracting the thickness of the glass substrate. Next, the physical properties of the optical element obtained above were measured, and the results are shown in Table 4. Here, [(n + n) / 2-n] X d
  • an optical element was produced.
  • the in-plane retardation force S0 nm and the thickness retardation were 37 nm, and [(n + n) / 2 ⁇ n
  • an optical element was produced.
  • the in-plane retardation was 1 nm and the thickness retardation was 70 nm, and [(n + n) / 2-n
  • the obtained polymer was dissolved by adding 300 ml of acetone, and then dropped into 3 L of pure water to cause precipitation. After filtration and washing with water and vacuum drying at 60 ° C for 4 hours, the polymer was put into a Soxhlet extractor. After performing Soxhlet extraction with methanol 20 times and vacuum drying at 25 ° C for 4 hours, 6.8 g of cellulose N- (p-tolyl) carbamate (4) was obtained (hereinafter referred to as synthetic product (4) may be called.) 0 DS of synthetic (4) is the result of proton NMR analysis, it was 3.
  • the DS is obtained by comparing the chemical shift area (3.4 to 5.5 ppm) of protons derived from the cellulose skeleton with the chemical shift area (6.6 to 7.7 ppm) of protons in the p-tolyl group. Were determined.
  • the coating film for optical compensation of the present invention, the coating liquid for forming the coating film for optical compensation, the optical element produced using them, and the optical compensation film (retardation film) are VA system, It can be used to expand the viewing angle of liquid crystal display devices using liquid crystal cells such as IPS and OCB.
  • the IPS method is particularly preferable in order to sufficiently exhibit the performance of the optical properties of the coating film for optical compensation in the present invention.
  • the optical compensation coating film, the coating film forming coating liquid, the optical element and the optical compensation film (retardation film) produced using the coating film, video, camera, mobile phone, laptop computer It can be suitably used for liquid crystal display device production parts such as televisions, monitors, and instrument panels of automobiles.

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Abstract

La présente invention concerne un film de revêtement pour compensation optique à faible coût ne nécessitant pas de phase compliquée d’élaboration de film, et un élément optique ayant les mêmes propriétés que celles fournies par la phase d’application de film malgré le fait que l’on peut se dispenser de tâches fastidieuses d’application de film et autre. Elle concerne également un procédé d’élaboration d’un film de revêtement pour compensation optique. Dans le film de revêtement, la valeur obtenue par (nx + ny)/2 - nz est négative, et la valeur absolue est plus importante. Dans l’équation, nx représente l’indice de réfraction maximal dans le plan, ny représente l’indice de réfraction minimal dans le plan, nz représente l’indice de réfraction dans le sens de l’épaisseur, et d représente l’épaisseur de film. On peut obtenir un élément optique en utilisant le procédé d’élaboration de film de revêtement. Le film de revêtement pour compensation optique est caractérisé en ce qu’il comprend tout polymère de carbamate substitué N de cellulose ou bien un polymère de vinyle aromatique.
PCT/JP2006/301496 2005-02-14 2006-01-31 Film de revêtement pour compensation optique, et élément optique WO2006085449A1 (fr)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP2005-036958 2005-02-14
JP2005036958A JP2006221116A (ja) 2005-02-14 2005-02-14 光学補償用塗工膜、該塗工膜形成用塗工液、その塗工液を用いて製造した光学素子並びに光学素子の製造方法
JP2005039873A JP2006227222A (ja) 2005-02-16 2005-02-16 光学補償用塗工膜、該塗工膜形成用塗工液、その塗工液を用いて製造した光学素子並びに光学素子の製造方法
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JP2005-141980 2005-05-13
JP2005141980A JP2006317813A (ja) 2005-05-13 2005-05-13 位相差調整剤、光学補償用塗工膜、該塗工膜形成用塗工液、その塗工液を用いて製造した光学素子並びに光学素子の製造方法
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JP5035242B2 (ja) * 2006-07-13 2012-09-26 コニカミノルタアドバンストレイヤー株式会社 偏光板保護フィルムの製造方法、偏光板保護フィルム、偏光板、及び液晶表示装置
WO2016060144A1 (fr) * 2014-10-17 2016-04-21 コニカミノルタ株式会社 Composition polymère, film optique, plaque de polarisation circulaire et dispositif d'affichage

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JP2004290963A (ja) * 2003-03-07 2004-10-21 Nitto Denko Corp 塗布膜の乾燥方法、それによって形成される光学機能層を積層した構造を有する光学フィルム、その光学フィルムを有する偏光板、及び、その偏光板を備えた画像表示装置
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JP2001131291A (ja) * 1999-11-02 2001-05-15 Daicel Chem Ind Ltd 光干渉粒子およびその製造方法
JP2003238601A (ja) * 2002-02-14 2003-08-27 Toray Ind Inc セルロースカーバメートの製造方法
JP2004004474A (ja) * 2002-04-18 2004-01-08 Nitto Denko Corp 光学補償偏光板及び表示装置
JP2004290963A (ja) * 2003-03-07 2004-10-21 Nitto Denko Corp 塗布膜の乾燥方法、それによって形成される光学機能層を積層した構造を有する光学フィルム、その光学フィルムを有する偏光板、及び、その偏光板を備えた画像表示装置
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Publication number Priority date Publication date Assignee Title
JP5035242B2 (ja) * 2006-07-13 2012-09-26 コニカミノルタアドバンストレイヤー株式会社 偏光板保護フィルムの製造方法、偏光板保護フィルム、偏光板、及び液晶表示装置
WO2016060144A1 (fr) * 2014-10-17 2016-04-21 コニカミノルタ株式会社 Composition polymère, film optique, plaque de polarisation circulaire et dispositif d'affichage
JPWO2016060144A1 (ja) * 2014-10-17 2017-07-27 コニカミノルタ株式会社 高分子組成物、光学フィルム、円偏光板及び表示装置

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