WO2004081622A1 - 光学フィルムおよび液晶表示素子 - Google Patents
光学フィルムおよび液晶表示素子 Download PDFInfo
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- WO2004081622A1 WO2004081622A1 PCT/JP2004/003124 JP2004003124W WO2004081622A1 WO 2004081622 A1 WO2004081622 A1 WO 2004081622A1 JP 2004003124 W JP2004003124 W JP 2004003124W WO 2004081622 A1 WO2004081622 A1 WO 2004081622A1
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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
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/19—Hydroxy compounds containing aromatic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—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
- G02F1/133528—Polarisers
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- 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
- G02F1/133528—Polarisers
- G02F1/133541—Circular polarisers
Definitions
- the present invention provides an optical film which can easily fix liquid crystal alignment, has small birefringence wavelength dispersion, and is suitable for application to optical elements such as a retardation film, and a circular polarizing plate, an elliptically polarizing plate and the like using the same.
- optical elements such as a retardation film, and a circular polarizing plate, an elliptically polarizing plate and the like using the same.
- the retardation film is used in a liquid crystal display device such as an STN (Super twisted nematic) type or a TFT (Thin film transistor) type, and is used for color compensation and improvement of a viewing angle.
- a retardation film for color compensation a stretched film of polycarbonate, polyvinyl alcohol, polysulfone, polyether sulfone, amorphous polyolefin, etc.
- a liquid crystal film using a nematic liquid crystal is used.
- a liquid crystal film using a hybrid alignment of a nematic liquid crystal and a discotic liquid crystal is used.
- liquid crystal films have a high degree of orientation and a very large birefringence ⁇ n compared to polymer materials such as polycarbonate used for stretched films, so that the retardation of the same retardation ( ⁇ d)
- the thickness can be made extremely thin.
- the thickness can be as high as 40 to 100 ⁇ , but in a liquid crystal film, the effective thickness of the part that performs optical functions is only a few ⁇ m.
- liquid crystal display devices are often mounted on small devices such as mobile phones, and the demand for thinner retardation films is very large.Therefore, the superiority of liquid crystal films in terms of thinness is significant. .
- the materials used for these retardation films have wavelength dispersion (wavelength dependence) in birefringence. That is, as a general tendency, the birefringence ⁇ n of the retardation film depends on the wavelength; I, as represented by the following equation (1).
- ⁇ ( ⁇ ) ⁇ + ⁇ / ( ⁇ 2 - ⁇ 0 2 ) (1)
- a and B are constants, ⁇ .
- ⁇ Generally indicates an absorption edge wavelength in an ultraviolet region.
- the curve becomes a monotonically decreasing curve that diverges, and the measurement wavelength increases as the wavelength decreases and decreases as the wavelength increases.
- many mesogens that exhibit liquid crystallinity have a long conjugate structure with a benzene ring, naphthalene ring or ester group and have an absorption edge wavelength on the long wavelength side.
- the wavelength dispersion usually tends to increase as the birefringence increases.
- liquid crystal films have been mainly used as retardation films for color compensation in STN-type liquid crystal displays.
- STN-type LCDs have a faster response time than TFT-type It has the disadvantage of being slow. Since the response speed of STN-LCD is inversely proportional to the square of the cell thickness, it is necessary to reduce the cell thickness in order to increase the speed. At this time, since the retardation of the driving cell must be kept constant, it is necessary to use a liquid crystal having a large birefringence as the low molecular liquid crystal for the driving cell.
- the wavelength dispersion of the retardation film must also be It needs to be bigger. Therefore, the liquid crystal film that can control the wavelength dispersion greatly is suitable for the retardation film for the fast response type STN-LCD as described above.
- reflective color TFT-LCDs and transflective color TFT-LCDs are required from the viewpoints of outdoor visibility and low power consumption. Are also being used.
- These reflective and transflective TFT-LCDs often use a circularly polarized light mode, and the retardation film is a quarter-wave plate that can convert linearly polarized light into circularly polarized light and circularly polarized light into linearly polarized light. Is used.
- the quarter-wave plate in this application can convert linearly polarized light into circularly polarized light and circularly polarized light into linearly polarized light in the entire visible light region.
- the phase difference at the measurement wavelength ⁇ always be ⁇ 4.
- An object of the present invention is to provide an optical film made of polyester which can easily fix the alignment of liquid crystal, can realize small wavelength dispersion of birefringence, and is industrially inexpensive and can be easily manufactured.
- a further object of the present invention is to provide an optical film capable of accurately adjusting optical characteristics such as wavelength dispersion of birefringence to a desired value, fixing a desired alignment state, and having a uniform and large area.
- the first aspect of the present invention relates to an optical film comprising a polyester containing a structural unit represented by the following general formulas (a) and (b).
- W represents a divalent group selected from the group consisting of groups represented by the following formula (w), and the substituent Rb is a hydrogen atom, F, Cl, Br , CF 3 , a fluoro group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, q is 1 to 4, and the formula (b) represents two or more different It may be composed of structural units.
- a second aspect of the present invention relates to the optical film, wherein the polyester exhibits liquid crystallinity.
- a third aspect of the present invention is that, in addition to the structural units (a) and (b), the polyester has at least one of structural units represented by the following formulas (c), (d), and (e):
- the present invention relates to the optical film, comprising a polyester containing a structural unit.
- X represents a divalent group selected from the group consisting of groups represented by the following formula (x), and the substituent R c is a hydrogen atom, F, C 1, B r, CF 3 , an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, r is 1 to 4, and formula (c) is composed of two or more different structural units.
- Y represents a divalent group selected from the group consisting of groups represented by the following formula (y), and R d represents a hydrogen atom, F, Cl, Br, CF 3 , carbon number Represents an alkyl group having 1 to 5 or an alkoxy group having 1 to 5 carbon atoms, s is 1 to 4, m is 2 to 10, and formula (d) is a different two or more structural units. May be composed by the expression
- Z represents a divalent group selected from the group consisting of groups represented by the following formula (z), R e is a hydrogen atom, F, C 1, B r , CF 3, Shiano group , Carbon number :! Represents an alkyl group of 5 to 5 or an alkoxy group of 1 to 5 carbon atoms, t is 1 to 4, and formula ( e ) may be composed of two or more different structural units. )
- a fourth invention wherein the polyester structural unit (a) 1 to 4 5 mol%, (b);! ⁇ 4 5 mol 0/0, (c) 1 0 ⁇ 5 0 mole 0 / o, ( d) related to the optical film characterized in that it consists configured liquid crystal Poryesuteru from 0-44 mole% and (e) 0 to 44 mole 0/0.
- a fifth aspect of the present invention is that the polyester has a structural unit (a) of 1 to 50 mol% and (b):! 0 to 49 mol%, (c) 0 to 50 monol%, (d) 0 to 49 mol% and (e)
- the optical film comprising a liquid crystalline polyester composed of 1 to 49 mol%.
- the ratio of the birefringence value ( ⁇ n (450 nm)) for light having a measurement wavelength of 450 nm to the birefringence value ( ⁇ n (590 nm)) for light having a measurement wavelength of 590 nm is determined.
- a seventh aspect of the present invention relates to the optical film, wherein any one of a homogenous orientation, a homeotropic orientation, a hybrid orientation, a twisted nematic orientation and a cholesteric orientation is fixed.
- An eighth aspect of the present invention relates to a liquid crystal display device comprising at least one optical film according to any one of the first to seventh aspects of the present invention.
- a ninth aspect of the present invention relates to a circularly polarizing plate comprising the optical film of any one of the first to seventh aspects of the present invention.
- a tenth aspect of the present invention relates to an elliptically polarizing plate comprising the optical film of any one of the first to seventh aspects of the present invention.
- the eleventh aspect of the present invention relates to a liquid crystal display device comprising the ninth circularly polarizing plate or the tenth elliptically polarizing plate of the present invention.
- the present invention will be described in detail.
- the optical film of the present invention requires the structural units represented by the formulas (a) and (b) (hereinafter, referred to as the structural unit (a) and the structural unit (b), respectively) as essential structural units. Accordingly, at least one of the arbitrary structural units represented by the formulas (c), (d) and (e) (hereinafter, referred to as structural unit (c), structural unit (d) and structural unit (e), respectively). At least from polyesters.
- the optical film may be an optically isotropic film or an anisotropic film, and has both an isotropic region and an anisotropic region in the film. May be something. However, in consideration of application as an optical element, an element having optical anisotropy is preferable.
- polyester In order to impart optical anisotropy to the optical film, it is necessary to orient polyester.
- a means for orienting a method of stretching a film or a method of using liquid crystallinity can be considered.However, in consideration of the fact that the thickness of an optical film can be reduced and realization of various alignment states, the polyester of the present invention can be used. Most preferably, it is a liquid crystalline polyester having a liquid crystal state.
- the orientation of the polyester is preferably fixed.
- a method for fixing the orientation there are a method of fixing the orientation formed in the liquid crystal phase in a glassy state, a method of fixing by photo-crosslinking and thermal cross-linking, and a method of using both together.
- a method of fixing the orientation formed in the liquid crystal phase in a glassy state there are a method of fixing by photo-crosslinking and thermal cross-linking, and a method of using both together.
- a method of introducing a reactive functional group into the terminal and / or side chain of the polyester of the present invention or adding a crosslinking agent may be mentioned.
- the polyester having liquid crystallinity suitably used in the present invention will be described in detail.
- the polyester of the present invention comprises, as essential structural units, structural units represented by the formulas ( a ) and (b) (hereinafter referred to as structural units ( a ) and (b), respectively).
- Arbitrary structural units represented by the above formulas (c), (d) and (e) hereinafter referred to as structural units (c), structural units (d) and structural units (e), respectively).
- It is a main chain type polyester which is also constituted.
- Many main-chain polyesters composed of aromatic or cycloaliphatic are known. 1,1,1-Bicyclohexyl-4,4, dicarboxylic acid and ortho-aromatic diol compound represented by catechol
- a main-chain polyester synthesized from a product that exhibits liquid crystallinity has not been studied at all.
- the structural unit (a) is an essential component for exhibiting liquid crystallinity and reducing the wavelength dispersion of birefringence, and includes 1,1,1-bicyclohexyl-4,4, dicarboxylic acid or a functional derivative thereof (for example, dimethyl Dialkyl esters such as esters, diphenyl Units derived from esters or acid chlorides such as dichloride).
- a corresponding diester of 4,4, -biphenyldicarboxylic acid (for example, dimethyl ester) is subjected to nuclear hydrogenation using a catalyst.
- a catalyst a nickel-based catalyst, ruthenium, palladium, rhodium-based catalyst or the like is preferably used.
- the reaction temperature is preferably from room temperature to 200 ° C.
- the reaction pressure is from normal pressure to 2 OMPa.
- the polyesters of the invention the structural units (a) from 5 to 50 mole 0/0, including preferably 1 5 to 45 mole 0/0, more preferably in a proportion of 20-40 mol 0/0.
- the polyester of the present invention has the structural unit (b) as an essential structural unit together with the structural unit (a).
- the structural unit (b) is an essential component for fixing the orientation of the liquid crystal phase in a glassy state under cooling.
- W in the structural unit (b) represents a divalent group selected from the group consisting of groups represented by the formula (w), and the substituent Rb is a hydrogen atom, F, Cl, Br, CF 3 , A phenyl group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, q is 1 to 4, and formula (b) is composed of two or more different structural units. May be.
- the structural unit (b) include catechol, 3-methylcatechol, 4-methinole force teconore, 3-ethinole force teconore, 4-ethinole force teconore, 3-n-propyl force teconore, and 4-n-propynolecate Cornole, 3-iso—propinoleca teconore, 4_iso—propinolecate konore, 3-n—puchinore force tekonore, 4-n—butinole force leverage, 3-t butylinole force force tekonore, 41-t butylinole force Tecosole, 3,5-g-t-petit / recatechol, 4-n-pentinole-force teconore, 3-funoleolocateco-1 / re, 4-funoreolocatechol, 3,4-diphnorelocatechol, 3,4,4 5, 6-Tetra-Funoleolocateconore, 3-Chlor
- Boriesuteru of the present invention 5 to 50 mol% of structural units (b), comprises preferably from 1 5 to 45 mole 0/0, more preferably in a proportion of 20-40 mol%.
- the polyester of the present invention may contain the structural unit (c) as an optional structural unit in addition to the structural units ( a ) and (b).
- Structural unit (c) is a structural unit that contributes to the development of liquid crystallinity and stabilization of the liquid crystal state.
- X in the structural unit (c) represents a divalent group selected from the group consisting of the group represented by the formula (X), and the substituent R c is a hydrogen atom, F, Cl, Br, CF 3 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, r is 1 to 4, and formula (c) is composed of two or more different structural units. You may.
- Preferred examples of the structural unit (c) include 4-hydroxybenzoic acid, 2-methyl-4-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3,5-Dimethyl-1-hydroxybenzoic acid, 2-ethyl-4-hydroxybenzoic acid, 3-ethyl-4-hydroxybenzoic acid, 2-t-butyl-4-hydroxybenzoic acid, 3-t-butyl-4- Hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, 2-fluoro-4-hydroxybenzoic acid, 3-fluoro-4-hydroxybenzoic acid, 2,3-difluoro-4-hydroxybenzoic acid, 2 2,6-difluoro-4-hydroxybenzoic acid, 3,5-difluoro-4-hydroxybenzoic acid, 2,3,5,6-tetrafluoro-1-4-hydroxybenzoic acid, 2-chloro-4- Dorokishi benzoic acid, 3 one black port one 4-hydroxybenz
- the polyesters of the invention 0-5 0 mol% of structural units (c), preferably 0-4 0 mole 0/0, more preferably in a proportion of 0-3 5 mol 0/0.
- the polyester of the present invention can contain a structural unit (d) as an optional structural unit in addition to the structural units (a) and (b).
- the structural unit (d) is a structural unit that contributes to the development of liquid crystallinity and stabilization of the liquid crystal state.
- Y in the structural unit (d) represents a divalent group selected from the group consisting of groups represented by the formula (y), and the substituent R d represents a hydrogen atom, F, Cl, Br, CF 3 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, s is 1 to 4, and formula (d) is composed of two or more different structural units. You may.
- Preferred examples of the structural unit (d) include terephthalic acid and 2-fluoroterephthalate 2,5-difluoroterephthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 2,6-difluoroterephthalic acid, 2,3,5,6-tetrafluoroterephthalenoic acid, 2-chloroterephthalenoic acid, 2,5-dichloroterephthalenoic acid, 2-promoterephthalic acid, 2,5-dibutamate moterephthalenoic acid, 2-trifleoleolomethinole terephthalenoleic acid, 2-methylterephthalic acid, 2 , 5-dimethyl terephthalic acid, 2-methoxy terephthalic acid, 2,5-dimethoxy terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4, -biphenylene resin Nolev
- the polyesters of the invention may contain the structural unit (e) as an optional structural unit in addition to the structural units (a) and (b).
- the structural unit (e) is a structural unit that contributes to the development of liquid crystallinity and stabilization of the liquid crystal state.
- Z in the structural unit (e) represents a divalent group selected from the group consisting of groups represented by the formula (z), and the substituent R e is water
- Preferred examples of the structural unit (e) include hydroquinone, fluorofluoroquinone, 2,3-diphnorolohydroquinone, 2,5-diphnorolohydroquinone, 2,3,5,6-tetrafluorohydroquinone, chlorohydr ⁇ quinone, 2,3-Dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6-tetrachlorohydroquinone, bromohydrinoquinone, 2,5-dibutyl bromohydroquinone, 2,3,5,6-tetrabromohydroquinone , Trifluoromethylinolehydroquinone, cyanohydroquinone, 2,3-dicyanohydroquinone, methinolehydroquinone, 2,5-dimethylhydroquinone, 2,6-dimethylhydroquinone, 2,3,5-trimethylhydroquinone, 2,3,
- the polyesters of the invention the structural unit (e) 0 to 45 mol%, preferably from 0 to 35 mole 0/0, more preferably in a proportion of 0-30 mol%.
- the structural units (a) 1 to 4 5 molar 0/0, preferably 2-42 mol 0/0, more preferably from 5 to 40 mole 0/0, (b). 1 to 45 mole 0/0, preferably 2-4 2 mol 0/0, more preferably from 5 to 40 mole 0/0, (c). 10 to 50 mole 0/0, preferably from 16 to 44 mole 0 /.
- yo Ri preferably include a liquid crystalline polyester composed of 0-20 mol%.
- the structural units (a) 1 ⁇ 50 mol 0/0, preferably 5-50 mol 0/0, more preferably 1 0 to 50 mol%, (b).
- the molecular weight of the polyester of the invention is a compound of phenol tetrachloro E Tan mixed solvent (60Z40 weight ratio), an intrinsic viscosity [77 i nh] measured at 30 ° C, usually 0.0 5 to 2.0, preferably 0 07-1.0, more preferably 0.1-0.5. If the value of 77 inh is lower than 0.05, the strength may be weakened, which may cause a practical problem. If it is higher than 2.0, the fluidity in the liquid crystal state may decrease, and it may be difficult to obtain a uniform alignment.
- the polyester of the present invention exhibits a liquid crystal phase at the time of melting, and can fix the orientation of the liquid crystal phase by cooling to a temperature below the glass transition temperature.
- the glass transition temperature Tg of these polyesters is preferably 40 ° C or higher, particularly preferably 60 ° C or higher, and the upper limit is not particularly limited, but is usually 300 ° C. Or less, and more preferably 200 ° C. or less.
- the polyester of the present invention can be obtained by polycondensing a monomer component corresponding to the above structural unit.
- the polymerization method is not particularly limited, and it can be synthesized by applying a polymerization method known in the art, for example, a melt polymerization method or a solution polymerization method.
- a predetermined amount of a structural unit (a) a forming monomer (for example, 1,1, -bicyclohexyl-4,4′-dicarboxylic acid) and a structural unit (b) Forming monomer (eg, catechol diacetate), optional component, structural unit (c) Forming monomer (eg, 4-acetoxybenzoic acid), structural unit (d) Forming monomer (eg, terephthalic acid), structural unit (e)
- a forming monomer for example, methylhydroquinone diacetate
- an inert gas such as nitrogen.
- the polymerization conditions are not particularly limited, but the temperature is usually 150 to 350 ° C., preferably 200 to 300 ° (the reaction time is 30 minutes or more, preferably about 1 to 40 hours.
- the polymerization reaction is preferably carried out under normal pressure, but in the latter half of the polymerization, the reaction may be accelerated by reducing the pressure or under high vacuum.
- amines such as 4-dimethylaminopyridine, alkali metal salts, Ti, Zn, Sn, Pb, Ge, V, As, Sb, or their metal salts or metal oxides.
- the molecular weight of the polyester of the present invention can be easily adjusted by controlling the polymerization time, the polymerization temperature, the polymerization pressure, etc. as in the ordinary condensation reaction.
- One example of producing the polyester of the present invention by a solution polymerization method includes a direct polymerization method using an activator.
- structural unit (c) forming monomer for example, 4-hydroxybenzoic acid
- structural unit (e) A monomer to be formed (eg, methylhydroquinone) is dissolved in pyridine or the like, and an activating agent such as arylsulfonyl chloride, dimethylformamide, diphenylphosphoric acid, or zirconium dimethylformamide is used as the activating agent.
- an activating agent such as arylsulfonyl chloride, dimethylformamide, di
- Another example of the solution polymerization method for producing the polyester of the present invention is an acid chloride method in which a carboxylic acid is activated.
- a structural unit (a) a monomer to be formed for example, 1,1'-bicyclohexyl-1,4,4, dicarboxylic dichloride
- b) Forming monomer for example, catechol
- structural unit (d) Forming monomer for example, terephthalic acid dichloride
- structural unit (e) Forming monomer for example, methylhydroquinone
- the above monomers are used in halogenated hydrocarbon solvents such as 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, dimethylsulfoxide (DMSO), dimethyl Soluble in polar solvents such as formamide (DMF) and N-methylpyrrolidone (NMP), and ethereal solvents such as tetrahydrofuran (THF) and dioxane, and acid acceptors such as triethylamine and tripropylamine.
- halogenated hydrocarbon solvents such as 1,2-dichloroethane, chloroform, 1,1,2,2-tetrachloroethane, dimethylsulfoxide (DMSO), dimethyl Soluble in polar solvents such as formamide (DMF) and N-methylpyrrolidone (NMP), and ethereal solvents such as tetrahydrofuran (THF) and dioxane, and acid acceptors such as triethy
- an organic solvent-alkali aqueous solution two-phase system is often used.
- the desired polyester can be easily obtained by dissolving in a halogenated hydrocarbon solvent such as described above and stirring vigorously near room temperature.
- phase transfer catalyst such as quaternary ammonium salt (ammonium salt, arsonium salt, phosphonium salt, sulfonium salt) such as tertiary amine or tetraammonium chloride.
- quaternary ammonium salt ammonium salt, arsonium salt, phosphonium salt, sulfonium salt
- tertiary amine or tetraammonium chloride such as tertiary amine or tetraammonium chloride.
- the polyester of the present invention obtained as described above varies depending on the composition ratio of the structural units constituting the polyester, and cannot be unconditionally determined. However, it can form a nematic phase or a smectic phase in a normal liquid crystal state. Furthermore, when the polyester in the liquid crystal state is cooled at an arbitrary cooling rate, phase transition to the crystal layer does not substantially occur, and at a temperature lower than the glass transition temperature, the molecular alignment state in the liquid crystal state, specifically, Has the characteristic that the molecular orientation state in the nematic phase and the smectic phase can be maintained as it is. Further, the polyester of the present invention may be used as a composition by mixing with other liquid crystal polymers, non-liquid polymers, and the like.
- a liquid crystal composition having a chiral nematic phase (cholesteric phase) as a liquid crystal phase can be obtained.
- the polyester of the present invention can obtain an optical film in which the orientation of a nematic phase or a smectic phase is fixed by utilizing the property of maintaining the molecular orientation state in a liquid crystal state as it is.
- an alignment substrate described below.
- Specific examples of the alignment substrate include polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketonesulfide, polyetherenolesnorefon, polysnorrefon, polyphenylenesanolefide, and the like.
- Polyphenylene oxide Polyethylene terephthalate, Polybutylene terephthalate, Polyethylene naphthalate, Polyacetal, Polycarbonate, Polyarylate, Acrylic resin, Methacrylic resin, Polyvinyl alcohol, Polyethylene, Polypropylene, Poly (4-methylpentene-11) resin, Norbornene resin , Triase Cellulose plastics such as chill cellulose, epoxy resin, phenol resin, plastic film substrate made of polymer liquid crystal, etc .; metal substrate of aluminum, iron, copper, etc .; blue plate glass, alkali glass, alkali-free glass, borosilicate glass Glass substrates such as flint glass and quartz glass; various substrates such as ceramic substrates; various semiconductor substrates such as silicon wafers.
- a film provided with another film on the substrate for example, an organic film such as a polyimide film, a polyamide film, or a polyvinyl alcohol film, or a film provided with an obliquely deposited film of silicon oxide or the like can be preferably used.
- the plastic film substrate may be uniaxially or biaxially stretched.
- these various substrates may be subjected to an alignment treatment as necessary.
- the alignment treatment applied to various substrates include a rubbing method, an oblique vapor deposition method, a micro group method, a stretched polymer film method, a LB (Langmuir-Boutlet jet) film method, a transfer method, and a light irradiation method (photoisomerization). , Photopolymerization, photodecomposition, etc.), peeling method and the like.
- a rubbing method and a light irradiation method are preferable in the present invention from the viewpoint of easiness of the manufacturing process.
- the optical film of the present invention can be obtained by applying a polyester uniformly on the substrate as described above, followed by a uniform orientation process and a process of fixing the orientation state.
- the application of the polyester to the oriented substrate can be usually performed in a solution state in which the composition is dissolved in various solvents or in a molten state in which the composition is melted. From the viewpoint of the manufacturing process, it is desirable to apply a solution in which a polyester is dissolved in a solvent and applied. The solution application will be described below.
- the polyester of the present invention is dissolved in a solvent to prepare a solution having a predetermined concentration. Since the film thickness of the film (the film thickness of the layer formed of polyester) is determined at the stage of applying the polyester to the substrate, it is necessary to precisely control the concentration, the thickness of the coating film, and the like.
- the solvent varies depending on the composition ratio of the polyester of the present invention and the like, it cannot be said unconditionally, but usually, chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, cyclobenzene, Halogenated hydrocarbons such as ortho-dichlorobenzene, Phenoenoles such as phenol and parachlorophenol, aromatic hydrocarbons such as benzene, tonolen, xylene, methoxybenzene, 1,2-dimethoxybenzene, alcohols such as isopropyl alcohol and tert-butyl alcohol, glycerin, ethylene glycol Glycols such as triethylene glycol, ethylene glycolone monomethinoleate, glycolenes such as ethylene glycolone resin, ethylcellosolve, butylcellosolve, acetone, methyl chlor
- the concentration of the solution cannot be unconditionally determined because it depends on the solubility of the polyester to be used and the final thickness of the target liquid crystal layer, but is usually used in the range of 3 to 50% by weight, preferably 5 to 50% by weight. It is in the range of 30% by weight.
- a polyester solution adjusted to a desired concentration using the above-mentioned solvent is then applied onto the above-described oriented substrate. Coating methods include spin coating, roll coating, printing, dipping and pulling, curtain coating, Meyer bar coating, doctor blade, knife coating, die coating, gravure coating, and microgravure coating. Offset gravure coating, lip coating, spray coating, etc. can be used.
- the solvent is removed, and a layer of the composition having a uniform thickness is formed on the alignment substrate.
- the solvent removal conditions are not particularly limited, and the solvent is usually removed by drying at room temperature, drying in a drying oven, or blowing hot or hot air.
- heat treatment is usually performed at a temperature of 500 ° C. to 300 ° C., preferably 100 ° C. to 260 ° C. to orient the polyester in a liquid crystal state.
- the heat treatment time varies depending on the composition ratio of the polyester composition and the like, which cannot be generally determined, but is usually in the range of 10 seconds to 120 minutes, preferably 30 seconds to 60 minutes. If the time is shorter than 10 seconds, uniform alignment may be insufficient in a liquid crystal state. If the time is longer than 120 minutes, productivity may decrease, which is not desirable. In this way, first, uniform alignment can be obtained over the entire surface of the alignment substrate in a liquid crystal state.
- a magnetic field or an electric field may be used to uniformly orient the polyester.
- the uniform orientation formed by the heat treatment is then cooled to a temperature equal to or lower than the glass transition temperature of the polyester, whereby the uniformity of the orientation can be fixed without any loss.
- the cooling temperature is not particularly limited as long as it is lower than the glass transition temperature.
- uniform orientation can be fixed by cooling to a temperature lower by 10 ° C. than the glass transition temperature or room temperature.
- the cooling means There is no particular limitation on the cooling means, and the cooling is carried out by simply bringing the material into the atmosphere below the glass transition temperature from the heating atmosphere in the heat treatment step, for example, to room temperature.
- forced cooling such as air cooling or water cooling or slow cooling may be performed.
- the above-mentioned substrate is peeled off from the film, and the liquid crystal layer is used alone.
- liquid crystal layer is laminated and used on another substrate different from the substrate,
- an optical film is used while being formed on a substrate.
- the substrate is transparent and optically isotropic, or when used as an optical film
- the substrate is a necessary member for the element, it can be used as it is as a target optical film.
- the optical film of the present invention obtained by fixing polyester on a substrate in an oriented state can be peeled off from the substrate and used by being laminated on another optically more suitable substrate.
- the following method can be employed.
- a liquid crystal layer on a substrate (hereinafter, referred to as a first substrate) and a substrate (hereinafter, referred to as a second substrate) suitable for an intended optical film are attached using, for example, an adhesive or an adhesive. .
- the first substrate is peeled off at the interface with the liquid crystal layer of the present invention, and the film can be transferred to a second substrate side suitable for an optical film to obtain an optical film.
- the second substrate used for transfer is not particularly limited as long as it has an appropriate flatness, but a glass substrate or a transparent plastic film having optical isotropy is preferably used.
- a plastic film include polymethyl methacrylate, polystyrene, polycarbonate, polyether sulfone, polysulfone, polyimide, polyphenylene sulfide, polyarylate, amonorerez polyolefin, polyethylene terephthalate, triacetinol cellulose, norbornene.
- Base resin or epoxy resin are preferably used.
- an optically anisotropic film can be used if it is a necessary member for an optical film.
- a film include a retardation film obtained by uniaxially or biaxially stretching the above-mentioned plastic film, a liquid crystal film in which the orientation of various liquid crystal states is fixed as in the present invention, and a polarizing film. is there.
- the adhesive or pressure-sensitive adhesive for adhering the second substrate used for transfer and the liquid crystal layer of the present invention is preferably an optical grade adhesive, acryl-based, epoxy-based, ethylene-vinyl acetate copolymer-based, rubber Systems, urethane systems, and mixtures thereof can be used.
- the adhesive any of thermosetting, photo-curing, and electron beam-curing adhesives can be used without any problem as long as they have optical isotropy.
- the peeling method is a method of mechanically peeling using a hole or the like, a method of peeling by applying ultrasonic waves in a poor solvent, a difference in thermal expansion coefficient between an oriented substrate and the film.
- the method include a method in which the film is separated by applying a temperature change using the method, a method in which the first substrate itself, or a method in which the alignment film on the first substrate is dissolved and removed. Since the releasability differs depending on the composition ratio of the polyester used and the adhesion to the first substrate, a method most suitable for the system should be adopted.
- As an application of these technologies as described in Japanese Patent Application Laid-Open No. 8-2784891, by using a removable substrate as the second substrate, an optical system in which the second substrate is finally removed is also used. Films are also preferred, and optical films can be made very thin.
- the optical film of the present invention may be further provided with a protective layer such as a transparent plastic film or a photo-cured film for the purpose of protecting the surface, increasing the strength, and improving environmental reliability.
- a protective layer such as a transparent plastic film or a photo-cured film for the purpose of protecting the surface, increasing the strength, and improving environmental reliability.
- the optical parameters that characterize the optical film of the present invention described above include the film thickness d, the in-plane retardation value ( ⁇ ⁇ d), the retardation value in the film thickness direction (m n ⁇ d), and the like. Examples include the wavelength dispersion value of the birefringence ⁇ n. Although these optical parameters vary depending on the use of the film, they cannot be unconditionally determined, but the film thickness d is usually 0.1! To 20 ⁇ , preferably in the range of 0.2 ⁇ to 15 ⁇ , and particularly preferably in the range of 0.3 ⁇ to 10 im.
- the in-plane retardation value is usually in the range of 10 nm to 400 nm, preferably 20 nm, for a monochromatic light of 590 nm. 2200 ⁇ , particularly preferably in the range of 50 nm to 100 nm.
- the in-plane retardation value means the product of the in-plane birefringence and the film thickness ( ⁇ ⁇ d).
- the retardation value in the film thickness direction is generally in the range of 10 nm to 400 m for monochromatic light of 590 nm. Preferably in the range of 20 nm to 200 nm, particularly preferably 50 n n! In the range of ⁇ 1000 nm.
- the retardation value in the film thickness direction is the product of the birefringence in the film thickness direction (the difference between the refractive index in the film thickness direction and the refractive index in the film plane) and the film thickness ( ⁇ ⁇ d ).
- the wavelength dispersion value of the birefringence ⁇ n is represented by the birefringence value ( ⁇ (450 nm)) for the light at the measurement wavelength of 450 nm and the birefringence for the light at the measurement wavelength of 590 nm as shown in the following equation (2). It is defined by the D value expressed as a ratio to the value ( ⁇ (590 nm)).
- the D value of the polyester of the present invention is mainly governed by the amount of 1,1, -bicyclohexyl-4,4,1-dicarboxylic acid unit introduced into the polymer, but usually 1.00 ⁇ D ⁇ 1. 1,2, preferably 1,02 ⁇ D ⁇ 1.10, more preferably 1.04 ⁇ D ⁇ 1.09, and 1,1, -bicyclohexyl-4,4'-dicarboxylic acid unit As the amount increases, the D value decreases. Therefore, the polyester of the present invention can freely control the D value by controlling the amount of 1,1, -bicyclohexyl_4,4, dicarboxylic acid unit.
- an optical film in which a twisted structure such as twisted nematic orientation ⁇ cholesteric orientation is fixed by blending an optically active low molecular weight or high molecular weight substance with the polyester of the present invention is possible.
- Optical films with fixed twisted nematic orientation can be applied to optical compensation films for liquid crystal displays, etc.
- Optical films with fixed cholesteric orientation can use the property of selectively reflecting circularly polarized light. .
- Both twisted nematic and cholesteric orientations are essentially similar in that they have a swist deformation inside, but they are distinguished here because the degree of twisting is different and the effect obtained is different.
- the optical parameters that characterize the optical film in which the twisted nematic orientation ⁇ cholesteric orientation of the present invention is fixed include the film thickness d, the in-plane retardation value ( ⁇ ⁇ d) and the wavelength of birefringence ⁇ n described above.
- the twist angle tilt rotation speed
- the twist angle is usually in a range of 0 to 720 degrees (equivalent to 2 rotations), preferably 0 to 540 degrees. It is in the range of less than (equivalent to 1.5 rotations), particularly preferably in the range of 0 to 360 degrees (equivalent to one rotation).
- the direction of the alignment vector of the liquid crystal molecules forming the film changes sequentially in the film thickness direction. Therefore, the twist angle referred to in the optical film of the present invention is defined as the angle at which the alignment vector rotates from one surface to the other surface of the liquid crystal layer.
- the torsion angle is usually in the range of 360 ° or more (equivalent to one rotation) and 720 ° or less (equivalent to 20 rotations), preferably 540 °. Degrees or more (equivalent to 1.5 rotations) in the range of 5400 degrees or less (equivalent to 15 rotations), particularly preferably 360 degrees or more (equivalent to 1 rotation) 360 degrees or less (equivalent to 1 rotation) (Equivalent to rotation).
- An optical film having the property of selectively reflecting circularly polarized light can be used as a color polarizing plate ⁇ cholesteric polarizing plate by incorporating it alone or in combination with a 1Z 4 wavelength plate into a liquid crystal display device. .
- the hybrid orientation is fixed by blending the polyester of the present invention alone or another low molecular weight or high molecular weight substance.
- the hybrid orientation is a structure in which the alignment vector on one surface of the liquid crystal layer is close to horizontal alignment, but the alignment vector gradually tilts with respect to the film surface as it approaches the other surface. Is what you have. In other words, it has a structure in which the magnitude of the vector of the liquid crystal molecules projected onto the film surface of the director changes in the film thickness direction.
- the optical parameters that characterize the optical film of the present invention in which the hybrid orientation is fixed include the above-mentioned film thickness d, in-plane retardation value (A n. D) when observed from the film normal direction, and In addition to the wavelength dispersion value of the birefringence ⁇ n, the in-plane retardation value and the angle between the normal direction of the film and the in-plane retardation value when observed at an angle of 40 degrees from the film normal direction to the projection vector direction.
- the orientation vector changes continuously in the film thickness direction.
- the above ⁇ ⁇ d ratio is used.
- the surface retardation value when observed from an angle of 40 degrees from the normal direction of the film can have two values, large and small, but it is defined to use the larger value.
- This ⁇ .n ⁇ d ratio is usually 0.85 or more and 1.5 or less, preferably 1 or more and 1.4 or less, and more preferably 1.1 or more and 1.35 or less.
- the optical film of the present invention as described above is, of course, excellent in the alignment ability, easy to fix the liquid crystal alignment to glass, and excellent in the ability to maintain the liquid crystal alignment state. Therefore, it can be widely used for various optical elements requiring high-temperature durability, such as retardation films, viewing angle improving films, color capturing films, optical rotator films, and cholesteric polarizing plates.
- a circularly polarizing plate or an elliptically polarizing plate can be produced by laminating the optical film of the present invention with a polarizing plate.
- the ellipticity at a wavelength of 550 nm is 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more.
- the number of optical films of the present invention may be one, or two or more.
- the optical film of the present invention may be used for both of the two films, or one of the plastic films may be uniaxially or biaxially stretched.
- an optical film having a hybrid alignment is used as an optical film having a quarter-wave retardation, it can be used as a circularly polarizing plate capable of improving viewing angle characteristics. '
- these circularly polarizing plates and elliptically polarizing plates can be used for forming various devices such as liquid crystal display devices and organic EL display devices.
- it can be preferably used for various types of reflective, transflective, and transmissive liquid crystal display devices in which a polarizing plate is disposed on one or both sides of a liquid crystal cell, and for antireflection of an organic EL display device.
- the circularly polarizing plate or the elliptically polarizing plate of the present invention is mounted on a liquid crystal cell or the like, parameters such as a retardation value and an intersection angle with the polarizing plate are appropriately adjusted according to the liquid crystal cell to be optically compensated. By adjusting, a display device having good characteristics can be obtained. [Best Mode for Carrying Out the Invention]
- the liquid crystalline polyester was dissolved in deuterated trifluoroacetic acid and measured by 1 H-NMR at 40 OMHz (UNITY I NOVA 40 OMHz manufactured by Varian).
- the measurement was performed using PerkinE DSm-7 manufactured by 1mer.
- the refractive index was measured with an Nabe line (measurement wavelength: 59 O nm) using an Abbe refractometer (Type 4 manufactured by Atago Co., Ltd.).
- the value of the birefringence ( ⁇ (45 O nm)) with respect to the light having a measurement wavelength of 450 nm and the light having a measurement wavelength of 590 nm represented by the above formula (2)
- the value of D defined by the ratio to the value of birefringence ( ⁇ n (590 nm)) was calculated.
- the ratio of the in-plane retardation value when observed from an angle of 40 degrees from the film normal direction and when observed from the angle of the film normal direction was defined as the ⁇ n ⁇ d ratio.
- the in-plane retardation value when observed from an angle of 40 degrees from the normal direction of the film may be large or small, but the larger value is used.
- a surface shape measuring device Dektak 3030ST manufactured by Japan Vacuum Engineering Co., Ltd. was used.
- interference wave measurement UV-visible, near-infrared spectrophotometer V-570, manufactured by JASCO Corporation
- a method of determining the film thickness from the refractive index data were also used.
- This polyester has an intrinsic viscosity of 0.23 dLZg, a nematic phase as a liquid crystal phase, an isotropic-liquid crystal phase transition temperature of 270 ° C, and a glass transition point of 80 ° C. It was found that the alignment of the nematic liquid crystal phase was completely fixed below the temperature.
- the 8 weight 0/0 phenol Roh tetrachloro E Tan (60/40 weight ratio) of polyester mixed solvent solution was prepared.
- the solution was applied to glass having a rubbing polyimide film by spin coating, and dried on a hot plate at 55 ° C. for 20 minutes. After heat treatment at 220 ° C for 20 minutes in a clean oven, The film was taken out of the clean oven and cooled naturally to obtain an optical film in which the orientation of the nematic phase was fixed. The obtained optical film was transparent and uniform with no alignment defects.
- the liquid crystal layer in the optical film had the homogenous orientation fixed, and the in-plane retardation as viewed from the normal direction of the film was 157 nm.
- the D value of this polymer was 1.090.
- Example 1 Examination was performed using the same method as in Example 1 except that the type of monomer and the charging ratio were changed. Table 1 shows the results.
- FIG. 1 shows the iH-NMR spectrum of the polyester of Example 2
- FIG. 2 shows the 1 H-NMR spectrum of the polyester of Example 10. All of these polyesters show a uniform nematic liquid crystal phase above the glass transition temperature, and even when cooled below the glass transition temperature, no transition to a crystalline phase is observed. It could be immobilized.
- a 8% by weight phenol / tetrachloroethane (60Z40% by weight) mixed solvent solution of the polyester obtained in Example 7 was prepared.
- the solution was applied on a base glass by a spin coating method and dried on a hot plate at 55 ° C. for 20 minutes. After heat treatment at 200 ° C for 20 minutes in a clean oven, the film was taken out of the clean open and cooled naturally to obtain an optical film in which the orientation of the nematic phase was fixed.
- the obtained optical film was transparent and uniform with no alignment defects. When the optical film was observed under crossed Nicols, no in-plane retardation was observed when viewed from the front, and a retardation occurred when viewed obliquely.
- the liquid crystal layer in the optical film had a fixed homeotropic aperture.
- the refractive index in the in-plane direction was 1.533, and the refractive index in the film thickness direction was 1.5. It was 655, and the result of measuring the film thickness was 2. O / xm. Therefore, the retardation in the film thickness direction was calculated to be 244 nm.
- a solution was prepared by dissolving 9.82 g of the polymer 1 used in Example 3 and 0.18 g of the polymer A obtained in Synthesis Example 1 in 80 g of N-methyl-2-pyrrolidone.
- 0.02 g (0.1% by weight based on the total weight of the polymer) of a fluorinated surfactant (Megafactor F 142D manufactured by Dainippon Ink and Chemicals, Inc.) was added.
- This solution was applied on polyimide film (Kapton, manufactured by DuPont) rubbed with rayon cloth by a bar coating method, and the solvent was dried and removed at 55 ° C in a clean oven. Heat treatment with C for 20 minutes formed a twisted nematic orientation structure.
- Example 3 the film was used in Example 3 to determine the wavelength dispersion value D of the birefringence of this Film 1.
- 80 g of 9.18 g of polymer used and 0.18 g of Bolimer B obtained in Synthesis Example 2 was dissolved in N-methyl-2-pyrrolidone, and an optical film having no twist was prepared in the same manner as in Example 1. The D value was determined.
- Film 1 is formed on an opaque and optically anisotropic polyimide film, it cannot be used as an optical film as it is.
- a UV curable adhesive (UV-340, manufactured by Toagosei Co., Ltd.) is applied to the air interface side of Film 1 to a thickness of about 5 ⁇ m, and an 80 ⁇ m optical A triacetyl cellulose film (Fujitac T8 OSZ, manufactured by Fuji Photo Film Co., Ltd.), which is an isotropic film, was laminated, and the adhesive was cured by UV irradiation at about 600 mJ.
- the liquid crystal layer was transferred onto the triacetyl cellulose film by peeling off the polyimide film from the laminate in which the triacetyl cellulose film / adhesive layer liquid crystal layer / polyimide film was integrated. Further, a UV curable adhesive (11_340, manufactured by Toagosei Co., Ltd.) is applied to a thickness of about 5 ⁇ on the surface of the liquid crystal layer on the side from which the polyimide film has been peeled off. The adhesive was cured by irradiating it with UV light (high pressure mercury lamp) of 0 mJ, and an overcoat layer was provided to obtain an optical film. When the ⁇ d and the twist angle of the optical film were measured, they were 19.3 nm and 64 °, respectively.
- UV light high pressure mercury lamp
- a polymerization reactor equipped with a stirrer, a nitrogen inlet tube, and a liquid trap was charged with 15.00 g of the polyester obtained in Example 1 and 5.00 g of the polyester obtained in Synthesis Example 1, and reacted. After the atmosphere in the vessel was replaced with nitrogen, the vessel was melted at 250 ° C. and stirred for 1 hour. The glass transition temperature of the obtained polyester composition was 70 ° C. As a result of observation by a polarizing microscope, this polymer showed a cholesteric liquid crystal phase above the glass transition temperature, and no transition to a crystal phase was observed even when cooled below the glass transition temperature. The liquid crystal orientation could be fixed.
- a solution was prepared by dissolving 16.00 g of the polymer used in Example 7 and 4.00 ⁇ of the polymer A obtained in Synthesis Example 3 in 80 ⁇ of 1 ⁇ , N-dimethylacetamide.
- This solution was applied by spin coating onto a polyphenylene sulfide film (Tollina, manufactured by Toray Industries, Inc.) rubbed with rayon cloth and placed in an oven 55. After the solvent was removed by drying at C, heat treatment was further performed at 230 ° C for 10 minutes to form a hybrid orientation structure. After the heat treatment, take it out of the oven and let it cool naturally The hybrid alignment structure was fixed in the glassy state (Film 2).
- Film 2 is formed on an opaque and optically anisotropic polyphenylene sulfide film, it cannot be used as an optical film as it is.
- a UV curable adhesive (UV-3400, manufactured by Toagosei Co., Ltd.) is applied to the air interface side of the finolem 2 to a thickness of about 5 ⁇ m, and an 80 ⁇ m optically isotropic A triacetyl cellulose film (Fujitak T80 SZ, manufactured by Fuji Photo Film Co., Ltd.) as a film was laminated, and the adhesive was cured by UV irradiation at about 600 mJ.
- the polyphenylene sulfide film is peeled off from the laminate in which the triacetyl cellulose film / adhesive layer / liquid crystal layer / polyphenylene sulfide film is integrated, so that the liquid crystal layer is formed on the triacetyl cellulose film.
- a UV curable adhesive UV-3400, manufactured by Toagosei Co., Ltd.
- UV-3400 UV-3400, manufactured by Toagosei Co., Ltd.
- the adhesive was cured by irradiation with UV light (a high-pressure mercury lamp), and an overcoat layer was provided to obtain an optical film.
- Example 31 was carried out in the same manner as in Example 31 except that a polyimide film was used as an alignment substrate, and heat treatment was performed at 230 ° C for 10 minutes and at 190 ° C for 6 minutes. The results are shown in Table 3 and FIG.
- the absorption axis of the polarizing plate and the alignment axis in the optical film 1 were shifted by 60 degrees, and the alignment axis in the optical film 1 and the alignment axis in the optical film 2 were further shifted by 15 degrees.
- Ellipsometry of the laminate 2 with an ellipsometer revealed that the ellipticity at a wavelength of 550 nm was 0.98, which confirmed that the laminate 2 was a circularly polarizing plate.
- the overcoat layer side of the polarizing plate (SRW-862AP manufactured by Sumitomo Chemical Co., Ltd.) and the optical film 3 manufactured according to Example 24 was laminated using an adhesive layer of about 25 / zm, and the laminate 3 was formed. Obtained. At this time, the absorption axis of the polarizing plate and the orientation axis on the side of the optical film 3 in the optical film 3 were shifted by 45 degrees. Ellipsometry of the laminate 3 by ellipsometry confirmed that the ellipticity at a wavelength of 550 nm was 0.10 and that the laminate 3 was an elliptically polarizing plate having a different ellipticity depending on the wavelength.
- a glass substrate provided with an ITO transparent electrode and a glass substrate provided with an aluminum reflective electrode having fine irregularities were prepared.
- a polyimide alignment film SE-7992, manufactured by Nissan Chemical Co., Ltd.
- SE-7992 manufactured by Nissan Chemical Co., Ltd.
- the two substrates were stacked via a 2.4-um spacer so that the alignment films faced each other.
- the orientation of the substrate was adjusted so that the rubbing directions of the two alignment films were antiparallel.
- Liquid crystal (Merck ZLI-1695) is injected into the gap between the substrates And a liquid crystal layer was formed.
- a twist-free ECB type liquid crystal cell having a value of ⁇ nd of 150 nm was produced.
- the circularly polarizing plate of Example 34 was adhered to the side of the glass substrate provided with the ITO transparent electrode via an adhesive layer of about 25 m.
- a voltage was applied from the white display of 0 V to the black display of 6 V to the manufactured reflective liquid crystal display device, and the display characteristics were evaluated. It was confirmed that the display was possible.
- the contrast ratio of the reflected luminance was measured using a measuring instrument (CM-350d manufactured by Minolta)
- the contrast ratio from the front was 20.
- the experiment was performed without a color filter. However, if a color filter is provided in the liquid crystal cell, a good multi-color or full-color display can be performed.
- BHDC 1, 1 bicyclohexyl l ⁇ 4, '4' dicarboxylic acid
- TPA ⁇ phthalic acid
- 6A2NA 6-acetoxy 2-naphthoic acid
- PPS Polyphenylene Sulfide
- the optical film of the present invention can easily fix the orientation of liquid crystal, can realize small wavelength dispersion of birefringence, and is industrially inexpensive and can be easily manufactured. Optical characteristics can be accurately adjusted to a desired value, a desired alignment state is fixed, and a uniform and large area can be achieved.
- FIG. 1 shows the result of measuring the 1 H—NMR spectrum of the liquid crystalline polyester of Example 2.
- FIG. 2 shows the result of measuring the 1 H—NMR spectrum of the liquid crystalline polyester of Example 10
- FIG. 3 shows the results of measuring the viewing angle dependency of the in-film retardation of the optical films of Examples 31 and 32 at a measurement wavelength of 590 nm.
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Abstract
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JPH04359015A (ja) * | 1991-06-04 | 1992-12-11 | Chisso Corp | ビシクロヘキサンジカルボン酸のポリエステル |
JP2001011163A (ja) * | 1999-07-01 | 2001-01-16 | Nippon Mitsubishi Oil Corp | 液晶性ポリエステル組成物 |
JP2003048966A (ja) * | 2001-08-09 | 2003-02-21 | New Japan Chem Co Ltd | 飽和環状脂肪族2級アルコールを原料とする脂環式ポリエステルの製造方法 |
JP2003119261A (ja) * | 2001-10-15 | 2003-04-23 | Mitsui Chemicals Inc | 新規なポリエステル樹脂 |
-
2004
- 2004-03-10 WO PCT/JP2004/003124 patent/WO2004081622A1/ja active Application Filing
- 2004-03-10 KR KR1020057016923A patent/KR20050121203A/ko not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04359015A (ja) * | 1991-06-04 | 1992-12-11 | Chisso Corp | ビシクロヘキサンジカルボン酸のポリエステル |
JP2001011163A (ja) * | 1999-07-01 | 2001-01-16 | Nippon Mitsubishi Oil Corp | 液晶性ポリエステル組成物 |
JP2003048966A (ja) * | 2001-08-09 | 2003-02-21 | New Japan Chem Co Ltd | 飽和環状脂肪族2級アルコールを原料とする脂環式ポリエステルの製造方法 |
JP2003119261A (ja) * | 2001-10-15 | 2003-04-23 | Mitsui Chemicals Inc | 新規なポリエステル樹脂 |
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KR20050121203A (ko) | 2005-12-26 |
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