CN101432644A - Birefringent film and method for producing same - Google Patents
Birefringent film and method for producing same Download PDFInfo
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- CN101432644A CN101432644A CNA2007800151226A CN200780015122A CN101432644A CN 101432644 A CN101432644 A CN 101432644A CN A2007800151226 A CNA2007800151226 A CN A2007800151226A CN 200780015122 A CN200780015122 A CN 200780015122A CN 101432644 A CN101432644 A CN 101432644A
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Abstract
Disclosed is a thin birefringent film wherein a refractive index is controlled three-dimensionally. Specifically disclosed is a birefringent film containing at least one polycyclic compound having a -SO3M group and/or a -COOM group (wherein M represents a counter ion), and having an index ellipsoid satisfying the following relation: nx > nz > ny. Since this birefringent film has high in-plane birefringence, it enables to obtain a desired retardation with a remarkably thinner thickness when compared with the conventional birefringent films.
Description
Technical field
The present invention relates to a kind of slim birefringent film and manufacture method thereof, this slim birefringent film contains at least a kind to have-SO
3M base and/or-polycyclic compund of COOM base, and three-dimensional ground control refractive index.
Background technology
Liquid crystal indicator (hereinafter referred to as LCD) is the electrooptics characteristic display text that utilizes liquid crystal molecule and the element of image, and extensively popularization and application is in mobile phone and mobile computer, LCD TV etc.But LCD is optically anisotropic liquid crystal molecule because of utilization has, so there is following problem: even show excellent display characteristic in a certain direction, but in the deepening of other direction picture or become not distinct.For addressing the above problem, at present birefringent film is widely used among the LCD.Before, as one of birefringent film, disclosed refractive index ellipsoid and satisfy nx nz the birefringent film (for example, with reference to patent documentation 1) of ny relation.Birefringent film with index of refraction relationship like this is to be pasted with the shrinkability film by the polymeric membrane both sides, is extended in the mode that expands along thickness direction and makes.Therefore, previous birefringent film is easy to thickening, thereby causes being difficult to reach the slimming of LCD.Therefore expectation addresses the above problem.
[patent documentation 1] Jap.P. spy opens the 2006-072309 communique
Summary of the invention
Order of the present invention is to provide a kind of slim birefringent film, its three-dimensional ground control refractive index.
Present inventors make great efforts research in order to address the above problem.It found that, can reach above-mentioned purpose by birefringent film shown below, and finally finish the present invention.
Birefringent film of the present invention, its refractive index ellipsoid satisfies nx〉nz〉relation of ny, and contain at least a kind and have-SO
3M base and/or-polycyclic compund (herein, M represents counter ion counterionsl gegenions) of COOM base.
In preferred embodiment, above-mentioned birefringent film birefraction (Δ n[590]) in the face at wavelength 590nm place is more than 0.05.
In preferred embodiment, the thickness of above-mentioned birefringent film is 0.05 μ m～10 μ m.
In preferred embodiment, above-mentioned birefringent film contains with the represented acenaphthene of following general formula (I) [1,2-b] quinoxaline (acenaphtho[1,2-b] quinoxaline) derivant also.
(in the formula, i, j, k, l are respectively 0～4 integer independently, and m, n are respectively 0～6 integer independently, R
1, R
2The alkyl of representing carbon number 1～6 respectively, M represent to distinguish identical counter ion counterionsl gegenions that also can be different; I, j, k, l, m and n are not 0 simultaneously).
[changing 1]
In preferred embodiment, above-mentioned birefringent film phase difference value (Re[590]) in the face at wavelength 590nm place is 20nm～1000nm.
In preferred embodiment, the difference of the phase difference value of above-mentioned birefringent film phase difference value (Re[590]) and thickness direction in the face at wavelength 590nm place (Rth[590]) is 10nm～800nm.
In preferred embodiment, the Nz coefficient of above-mentioned birefringent film is greater than 0 and less than 1.
According to alternate manner of the present invention, can provide a kind of stacked film.This stacked film possesses above-mentioned birefringent film and base material at least.
According to alternate manner of the present invention, can provide a kind of manufacture method of birefringent film.This manufacture method comprises the operation of following (1)～(3):
(1) preparation contains solvent and at least a kind and has-SO
3M base and/or-polycyclic compund (M represents counter ion counterionsl gegenions) of COOM base and show the operation of the solution of nematic crystal phase;
(2) prepare at least one surface by the operation of the base material of hydrophilicity-imparting treatment;
(3) base material of in above-mentioned operation (2), being prepared on the surface of hydrophilicity-imparting treatment, be coated on prepared solution in the above-mentioned operation (1), and make its dry operation.
In preferred embodiment, above-mentioned hydrophilicity-imparting treatment is that corona treatment, plasma treatment, alkali treatment or binding layer are handled.
In preferred embodiment, above-mentioned base material is glass substrate or polymeric membrane.
According to alternate manner of the present invention, can provide a kind of polarization plates.Above-mentioned polarization plates possesses above-mentioned birefringent film and polaroid at least.
[effect of invention]
Birefringent film of the present invention is because of its refractive index ellipsoid satisfies nx〉nz ny relation and represent birefraction in the higher face, so compare with existing birefringent film, thickness that can be extremely thin obtains desired phase difference value.Again, the manufacture method of birefringent film of the present invention for be coated with the method for carrying out dry productivity excellence again on base material, can be made and satisfy nx〉nz〉the slim birefringent film of ny relation.
Embodiment
[summary of A. birefringent film of the present invention]
The refractive index ellipsoid of birefringent film of the present invention satisfies nx〉nz〉relation of ny.Again, birefringent film of the present invention is served as reasons to contain and is at least aly had-SO
3M base and/or-polycyclic compund of COOM base forms.That is, containing at least a kind has-SO
3M base and/or-polycyclic compund of COOM base.Herein, M represents counter ion counterionsl gegenions.Above-mentioned-SO
3M basis representation sulfonic group or sulfonate, above-mentioned-COOM basis representation carboxylic acid group or carboxylate.
In this manual, so-called " birefringent film " is meant in face and/or along thickness direction to show birefringent film, and it is interior and/or be 1 * 10 along the birefraction of thickness direction to be included in the face at wavelength 590nm place
-4Above film.So-called " nx〉nz〉ny " represent that the refractive index that the birefringence face invagination rate of penetrating is become maximum direction (being the slow axis direction) is made as nx, will be in face be made as ny, the optical anisotropy of the birefringent film the when refractive index of thickness direction is made as the situation of nz with the refractive index of slow axis direction vertical direction (being the heading direction of principal axis).
Above-mentioned polycyclic compund is the organic compound that has 2 above aromatic rings and/or heterocycle in the molecular structure, preferably has the organic compound of 3～8 aromatic rings and/or heterocycle, more preferably has the organic compound of 4～6 aromatic rings and/or heterocycle.If as above-mentioned polycyclic compund, then can obtain not have and absorb or absorb less transparent birefringent film in the visible region.
Birefringent film so is because of refractive index ellipsoid satisfies nx〉nz〉relation of ny, and show birefraction in the higher face, so to compare thickness extremely thin with existing birefringent film, can obtain desired phase difference value.According to inventor's etc. deduction, it is generally acknowledged that birefringent film of the present invention shows that the reason of higher birefringence is: contain-SO
3M base and/or-polycyclic compund of COOM base easily forms condensed matter in solution, and it is higher to form the order of this condensed matter state, therefore also shows high orientation by the formed film of above-mentioned solution.Contained in the polycyclic compund in the present invention ,-SO
3M base and/or-the COOM base act as birefringent film: improve the dissolubility of polycyclic compund on the one hand, thereby can adopt solvent casting method to come film forming solvent; Three-dimensional ground control refractive index on the other hand, thereby obtain to satisfy nx〉nz〉refractive index ellipsoid of ny relation.
Birefringent film of the present invention in the face at wavelength 590nm place birefraction (Δ n[590]=nx-ny), be preferably more than 0.05, more preferably 0.1～0.5, be preferably 0.2～0.4 especially.Moreover, above-mentioned Δ n[590] can suitably be adjusted into above-mentioned scope according to the molecular structure of polycyclic compund.Before, do not obtained refractive index ellipsoid and satisfied nx nz ny relation and Δ n[590] be the birefringent film more than 0.05.According to the present invention, can contain by use-SO
3M base and/or-polycyclic compund of COOM base, and obtain to satisfy the birefringent film of above-mentioned characteristic first.
The thickness of above-mentioned birefringent film is preferably 0.05 μ m～10 μ m, and more preferably 0.1 μ m～8 μ m are preferably 0.1 μ m～6 μ m especially.Can be by being made as the thickness of above-mentioned scope, for example when being used in the situation of liquid crystal indicator, and obtain improving the useful phase difference value scope of display characteristic.
[B. polycyclic compund]
If employed polycyclic compund has-SO among the present invention
3M base and/or-compound of COOM base, then can use the polycyclic compund that is fit to arbitrarily.Above-mentioned polycyclic compund is preferably the compound (that is, lyotropic liquid crystal, lyotropic liquid crystal) that shows liquid crystal phase with solution state.With regard to the aspect of orientation excellence, above-mentioned liquid crystal phase is preferably the nematic crystal phase.
Above-mentioned birefringent film, be preferably contain with the represented acenaphthene of following general formula (1) also [1,2-b] quinoxaline derivant as polycyclic compund.In the formula, i, j, k, l are respectively 0～4 integer independently, and m, n are respectively 0～6 integer independently, R
1, R
2The alkyl of representing carbon number 1～6 respectively, M represent to distinguish identical counter ion counterionsl gegenions that also can be different.Wherein, i, j, k, l, m, and n be not 0 simultaneously.Above-mentioned birefringent film, also can by contain more than 2 kinds with above-mentioned general formula (I) represented and-SO
3M base and/or-composition of the different polycyclic compund of the position of substitution of COOM base and forming.
[changing 2]
Such polycyclic compund can form stable liquid crystal phase in solution, can utilize solvent casting method and obtained to have in the higher face birefraction and do not had in the visible region by solution and absorb or absorb less transparent birefringent film.
In the above-mentioned general formula (I), M is counter ion counterionsl gegenions, is preferably hydrogen ion (hydrogen atom), Na
+, K
+Deng alkali metal ion (alkali metal atom), alkaline-earth metal ions (alkaline earth metal atom), other metallic ion (other metallic atom) or displacement or the ammonium ion of displacement not.As above-mentioned other metallic ion, for example can enumerate: Ni
2+, Fe
3+, Cu
2+, Ag
+, Zn
2+, Al
3+, Pd
2+, Cd
2+, Sn
2+, Co
2+, Mn
2+, Ce
3+Deng.For example, when birefringent film of the present invention was the situation that is formed by aqueous solution, above-mentioned M was the deliquescent group of selecting to improve to water at first, after film forming, for the water tolerance that improves film also can be substituted by insoluble or is insoluble in the group of water.
Above-mentioned acenaphthene is [1,2-b] quinoxaline derivant also, and is as described below, can by with acenaphthene also [1,2-b] quinoxaline carboxylic acid's derivant carry out sulfonation with sulfuric acid, oleum or chlorosulfonic acid and obtain.
[changing 3]
In the formula, i, j, k, l are respectively 0～4 integer independently, and m, n are respectively 0～6 integer independently, R
1, R
2The alkyl of representing carbon number 1～6 respectively, M represent to distinguish identical counter ion counterionsl gegenions that also can be different.Wherein, i, j, k, l, m, and n be not 0 simultaneously.
Perhaps, acenaphthene is [1,2-b] quinoxaline derivant also, as described belowly also can make benzene-1, and the sulfonic derivative of the sulfonic derivative of 2-diamines and/or carboxy derivatives and acenaphthene quinone and/or carboxy derivatives carry out condensation reaction and obtain.
[changing 4]
In the formula, i, j, k, l are respectively 0～4 integer independently, and m, n are respectively 0～6 integer independently, R
1, R
2The alkyl of representing carbon number 1～6 respectively, M represent to distinguish identical counter ion counterionsl gegenions that also can be different.Wherein, i, j, k, l, m, and n be not 0 simultaneously.
[each rerum natura of C. birefringent film]
Above-mentioned birefringent film is preferably more than 85% in the transmitance at wavelength 590nm place, more preferably more than 90%.
Above-mentioned birefringent film phase difference value (Re[590]) in the face at wavelength 590nm place can be set at appropriate value according to purpose.Above-mentioned Re[590] be more than the 10nm, to be preferably 20nm～1000nm, more preferably 50nm～500nm is preferably 100nm～400nm especially.In this manual, the phase difference value in the face (Re[λ]) be illustrated under 23 ℃, phase difference value in the face that wavelength X (nm) is located.When film thickness is made as d (nm), Re[λ] can be according to Re[λ]=(nx-ny) * d obtains.
The Rth[590 of above-mentioned birefringent film] can satisfy nx at refractive index ellipsoid〉nz〉be set at appropriate value in the scope of ny relation.The difference of the phase difference value of above-mentioned birefringent film phase difference value (Re[590]) and thickness direction in the face at wavelength 590nm place (Rth[590]) is preferably 10nm～800nm, and more preferably 10nm～400nm is preferably 10nm～200nm especially.In this manual, the phase difference value of the phase difference value of thickness direction (Rth[the λ]) thickness direction that is meant under 23 ℃, locates in wavelength X (nm).When film thickness is made as d (nm), Rth[λ] can be according to Rth[λ]=(nx-nz) * d obtains.
The Nz coefficient of above-mentioned birefringent film is preferably more than 0 and less than 1, and more preferably 0.1～0.8, be preferably 0.1～0.7 especially, most preferably be 0.1～0.6.If the Nz coefficient is in above-mentioned scope, birefringent film then of the present invention can be used in the optical compensation of liquid crystal cell of various drive patterns.In this manual, so-called Nz coefficient is meant according to Rth[590]/Re[590] value calculated.
The wavelength dispersion value (D) of above-mentioned birefringent film is preferably more than 1.05, and more preferably 1.06～1.15, most preferably be 1.07～1.12.In this manual, wavelength dispersion value (D) is for according to following formula: D=Re[480]/Re[550] value calculated.Before, in the birefringent film that the polymeric membrane extension is made, obtained to show so steep wavelength interdependence.Birefringent film of the present invention, its phase difference value of being measured with short-wavelength light serve as fully greater than the phase difference value of being measured with long wavelength light.Therefore, showing the wavelength interdependence of steep phase differential, also is the feature of birefringent film of the present invention.
[method for making of D. birefringent film]
In the first embodiment, the method for birefringent film of the present invention following by comprising (1)～(3) operation is made.
(1) preparation contains solvent and at least a kind and has-SO
3M base and/or-polycyclic compund (M represents counter ion counterionsl gegenions) of COOM base, and show the operation of the solution of nematic crystal phase;
(2) prepare at least one surface by the operation of the base material of hydrophilicity-imparting treatment;
(3) base material of in above-mentioned operation (2), preparing on the hydrophilicity-imparting treatment surface, be coated on the solution of preparation in the above-mentioned operation (1), and make its dry operation.
If by above-mentioned method for making, then can obtain to have at least the stacked film of birefringent film and base material.
Employed in the above-mentioned operation (1) have-SO
3M base and/or-polycyclic compund (M represents counter ion counterionsl gegenions) of COOM base, can from above-claimed cpd, suitably select to be fit to the person.In above-mentioned operation (1), above-mentioned solution is preferably-SO
3M base and/or-the different polycyclic compund more than 2 kinds of the position of substitution of COOM base is dissolved in the solvent and prepares.The kind of contained polycyclic compund in the above-mentioned solution except that, being preferably more than 2 kinds the kind that trace contains as impurity, more preferably 2 kinds～6 kinds, is preferably 2 kinds～4 kinds especially.
Above-mentioned solvent is used to dissolve above-mentioned polycyclic compund so that it shows the nematic crystal phase.Above-mentioned solvent is selected arbitrarily.Above-mentioned solvent for example can be inorganic solvents such as water, also can be organic solvents such as alcohols, ketone, ethers, ester class, aliphatics and aromatic hydrocarbon based, halogenated hydrocarbons, amide-type, Cellosolve class.As above-mentioned solvent, for example can enumerate: normal butyl alcohol, 2-butanols, cyclohexanol, isopropyl alcohol, the tert-butyl alcohol, glycerine, ethylene glycol, acetone, methyl ethyl ketone, methylisobutylketone, cyclohexanone, cyclopentanone, 2 pentanone, methyl-n-butyl ketone, diethyl ether, tetrahydrofuran, diox, methyl phenyl ethers anisole, ethyl acetate, butyl acetate, methyl lactate, normal hexane, benzene,toluene,xylene, chloroform, methylene chloride, ethylene dichloride, dimethyl formamide, dimethyl acetamide, methyl Cellosolve, ethyl Cellosolve etc.These solvents can use separately, perhaps mix more than 2 kinds and use.
Be preferably especially, above-mentioned solvent is a water.The conductance of above-mentioned water is preferably below the 20 μ S/cm, and more preferably 0.001 μ S/cm～10 μ S/cm are preferably 0.01 μ S/cm～5 μ S/cm especially.The lower limit of the conductance of above-mentioned water is 0 μ S/cm.Can be made as above-mentioned scope by conductance with water, and the birefringent film that acquisition has higher interior birefraction.
The polycyclic compund concentration of above-mentioned solution can be according to the kind of use polycyclic compund, suitably preparation in the scope that shows the nematic crystal phase.Polycyclic compund concentration in the above-mentioned solution is preferably 5 weight %～40 weight %, and more preferably 5 weight %～35 weight % are preferably 5 weight %～30 weight % especially.By solution concentration being made as above-mentioned scope, this solution can form stable mesomorphic state.Can be according to confirm, discern above-mentioned nematic crystal phase with the optical mode of the viewed liquid crystal phase of polarizing microscope.
Above-mentioned solution can further contain the adjuvant that is fit to arbitrarily.As above-mentioned adjuvant, for example can enumerate: surfactant, plastifier, thermal stabilizer, light stabilizer, lubricant, antioxidant, ultraviolet light absorber, fire retardant, colorant, antistatic agent, phase solvation, crosslinking chemical, and tackifier etc.The addition of above-mentioned adjuvant is preferably with respect to 100 parts by weight solution, for greater than below 0 and 10 weight portions.
Above-mentioned solution can further contain surfactant.Surfactant is in order to improve wetting state, the coating of polycyclic compund to substrate surface.Above-mentioned surfactant is preferably non-ionic surfactant.The addition of above-mentioned surfactant is greater than below 0 and 5 weight portions with respect to 100 parts by weight solution preferably.
" hydrophilicity-imparting treatment " in the so-called above-mentioned operation (2) is the processing of instigating the water contact angle reduction of base material.Above-mentioned hydrophilicity-imparting treatment is coated with wetting state, the coating of the substrate surface of polycyclic compund in order to raising.Above-mentioned hydrophilicity-imparting treatment is compared the processing that reduces more than 10% before being preferably and making the water contact angle of base material under 23 ℃ and handle, and more preferably reduces by 15%～80% processing, is preferably especially and reduces by 20%～70% processing.Moreover this reduction ratio (%) is according to formula: { contact angle before (contact angle after the contact angle-processing before handling)/processing } * 100 are obtained.
And then above-mentioned hydrophilicity-imparting treatment is compared the processing that reduces more than 5 ° before being preferably and making the water contact angle of base material under 23 ℃ and handle, and more preferably reduces by 10 °～65 ° processing, is preferably especially and reduces by 20 °～65 ° processing.
And then above-mentioned hydrophilicity-imparting treatment is preferably the processing that the water contact angle of base material under 23 ℃ is made as 5 °～60 °, more preferably is made as 5 °～50 ° processing, is preferably the processing that is made as 5 °～45 ° especially.Above-mentioned scope be can be made as by water contact angle and birefraction and the less birefringent film of difference in thickness in the higher face obtained to show base material.
Above-mentioned hydrophilicity-imparting treatment can adopt the method that is fit to arbitrarily.Above-mentioned hydrophilicity-imparting treatment for example can be dry process, also can be wet processed.As dry process, for example can enumerate: corona treatment, plasma treatment, and discharge process such as glow discharge processing, ionization activity line processing such as flame treatment, ozone treatment, UV ozone treatment, UV treatment and electron beam treatment etc.As wet processed, for example can enumerate: make ultrasonic treatment, alkali treatment, binding layer processing of water or acetone equal solvent etc.These processing can be used separately, use more than 2 kinds also capable of being combined.
Be preferably, above-mentioned hydrophilicity-imparting treatment is that corona treatment, plasma treatment, alkali treatment or binding layer are handled.If above-mentioned hydrophilicity-imparting treatment then can obtain to have high orientation and the less birefringent film of difference in thickness.For the condition of above-mentioned hydrophilicity-imparting treatment for example processing time and intensity etc., the mode that can become above-mentioned scope by the water contact angle that makes base material is suitably adjusted.
Above-mentioned corona treatment is following processing typically: by apply high frequency, high voltage and current between dielectric medium roller that is grounded and insulated electrode, and make in the base material corona discharge that ionization produced by interelectrode air generation insulation breakdown, by this substrate surface is carried out modification.Above-mentioned plasma treatment is following processing typically: produce glow discharge in inorganic gas such as low-pressure inert gas or oxygen, halogen gas, in the low-temperature plasma that a part of ionization that makes base material pass through gas molecule produces, by this substrate surface is carried out modification.Above-mentioned ultrasonic cleaning treatment is following processing typically: shine ultrasonic in water or the organic solvent again by base material be impregnated in, and remove the pollutant of substrate surface, and improve the wetting state of base material.Above-mentioned alkali treatment is typically for following processing: by base material is immersed in alkaline matter is dissolved in the alkali treatment liquid in water or the organic solvent, and substrate surface is carried out modification.Above-mentioned binding layer is handled typically for the binding layer agent being coated the processing of substrate surface.
The solution that employed in the present invention base material is used for containing above-mentioned polycyclic compund and solvent flows casting equably.Above-mentioned base material can be selected the base material that is fit to arbitrarily.As above-mentioned base material, for example can enumerate: sheet metals such as glass substrate, quartz base plate, polymeric membrane, plastic base, aluminium or iron, ceramic substrate, silicon chip etc.Above-mentioned base material is preferably glass substrate or polymeric membrane.
As above-mentioned glass substrate, can select the substrate that is fit to arbitrarily.Be preferably, above-mentioned glass substrate is the substrate that is used for liquid crystal cell, for example contains soda-lime (blue or green plate) glass or the low alkali borax acid glass of alkali composition.Above-mentioned glass substrate also can directly use commercially available product.As commercially available glass substrate, for example can enumerate: the glass number that Corning company makes: 1737, the glass number of Asahi Glass (thigh) manufacturing: the glass code that AN635, NH Techno Glass Corporation make: NA-35 etc.
As the resin that forms above-mentioned polymeric membrane, can select the resin that is fit to arbitrarily.Be preferably, above-mentioned polymeric membrane contains thermoplastic resin.As above-mentioned thermoplastic resin, can enumerate: polyolefin resin, cyclic olefine resin, polyvinyl chloride resin, cellulose-based resin, phenylethylene resin series, polymethylmethacrylate, polyvinyl acetate (PVA), polyvinylidene chloride resin, polyamide-based resin, polyacetal are that resin, polycarbonate-based resin, polybutylene terephthalate are that resin, PET series resin, polysulfones are that resin, polyethersulfone are that resin, polyetheretherketone are that resin, polyarylate are that resin, polyamidoimide are that resin, polyimide are resin etc.Above-mentioned thermoplastic resin can be used singly or in combination of two or more thereof.Use after the polymer modification that above-mentioned thermoplastic resin also can carry out being fit to arbitrarily again.As above-mentioned polymer modification, for example can enumerate: the modification of copolymerization, crosslinked, molecular end and stereoregularity etc.
Employed in the present invention base material is preferably the polymeric membrane that contains cellulose-based resin.Its reason is: can obtain polycyclic compund the wetting state excellence, have higher interior birefraction and the less birefringent film of difference in thickness.
Above-mentioned cellulose-based resin can adopt the resin that is fit to arbitrarily.Above-mentioned cellulose-based resin is preferably part or all cellulose organic ester or cellulose mixed organic acid ester that is replaced by acetyl group, propiono and/or butyl of cellulosic hydroxyl.As above-mentioned cellulose organic ester, for example can enumerate: cellulose acetate, cellulose propionate, cellulose butyrate etc.As above-mentioned cellulose mixed organic acid ester, for example can enumerate: cellulose acetate propionate, acetylbutyrylcellulose etc.Above-mentioned cellulose-based resin for example can be opened the method for being put down in writing in 2001-188128 communique [0040]～[0041] and obtains according to the Jap.P. spy.
Employed in the present invention base material can directly use commercially available polymeric membrane.Perhaps, can use the base material of commercially available polymeric membrane being implemented to extend secondary processing such as processing and/or shrink process.As the commercially available polymeric membrane that contains cellulose-based resin, for example can enumerate: Fuji Photo Film Co., Ltd. the FujitacSeries of Zhi Zaoing (trade name: ZRF80S, TD80UF, TDY-80UL), KonicaMinolta Opto, the trade name " KC8UX2M " that Inc. makes etc.
The thickness of above-mentioned base material is preferably 20 μ m～100 μ m.Because of the thickness with base material is made as above-mentioned scope, so the operability of base material and coating excellence.
Solution coat speed in the above-mentioned operation (3) is preferably more than the 50mm/s, more preferably more than the 100mm/s.Can be suitable for the shear strength that polycyclic compund is orientated and in solution used in the present invention, apply by coating speed being made as above-mentioned scope, thereby obtain to have higher interior birefraction and the less birefringent film of difference in thickness.
As with the method for above-mentioned solution coat, can suit to adopt the coating method that uses the coating machine that is fit at substrate surface.As above-mentioned coating machine, for example can enumerate: anti-roll-coater, dextrorotation roll-coater, intaglio plate coating machine, knife type coater, rod coater, channel mould coating machine, slotted eye coating machine, curtain type coating machine, fountain type coating machine, air doctor blade coating machine, coating roller, dip coater, bead coater, knife type coater, cast coater, Bracewell coater, rotary coating machine, extrusion coater, hot-melt coater etc.Above-mentioned coating machine is preferably anti-roll coater, dextrorotation roll-coater, intaglio plate coating machine, rod coater, channel mould coating machine, slotted eye coating machine, curtain type coating machine, reaches the fountain type coating machine.If use the coating method of above-mentioned coating machine, then can obtain the less birefringent film of difference in thickness.
Make the method for above-mentioned solution drying, can suitably adopt suitable method.Drying means for example can be enumerated following drying means: make hot blast or cold wind round-robin air circulating type constant temperature oven, utilize microwave or far infrared etc. well heater, be used for thermoregulator warm-up mill, heat pipe roller (heat pipe roll) or metal tape etc.
Make the temperature of above-mentioned solution drying, below the isotropy phase inversion temperature for above-mentioned solution, be preferably from low temperature and slowly heat up so that its drying to high temperature.Above-mentioned baking temperature is preferably 10 ℃～80 ℃, more preferably 20 ℃～60 ℃.If the said temperature scope then can obtain the less birefringent film of difference in thickness.
Make the time of above-mentioned solution drying, visual baking temperature or solvent species are done suitably to select, and for obtaining the less birefringent film of difference in thickness, for example are 1 minute～30 minutes, are preferably 1 minute～10 minutes.
The manufacture method of birefringent film of the present invention is preferably, and further comprises operation (4) afterwards in above-mentioned operation (1)～(3):
(4) make contain be selected from from aluminium salt, barium salt, lead salt, chromic salts, strontium salt, and molecule in have the solution of at least a kind of compound salt the group that the compound salt of 2 above amidos formed, the operation that contacts with the film that is obtained in the above-mentioned operation (3).
In the present invention, above-mentioned operation (4) is for so that the birefringent film that is obtained is insoluble or be insoluble in water.As above-claimed cpd salt, for example can enumerate: aluminum chloride, barium chloride, lead chloride, chromium chloride, strontium chloride, 4,4 '-tetramethyl two amido diphenyl methane hydrochlorides, 2,2 '-two pyridine hydrochlorides, 4,4 '-two pyridine hydrochlorides, melamine hydrochloride, tetramine yl pyrimidines hydrochloride etc.If compound salt so then can obtain the birefringent film of water tolerance excellence.
Contain the concentration of compound salt of the solution of above-claimed cpd salt, be preferably 3 weight %～40 weight %, be preferably 5 weight %～30 weight % especially.Can contact with the solution of the compound salt that contains above-mentioned scope concentration by making birefringent film, and the film of acquisition excellent in te pins of durability.
As make in the above-mentioned operation (3) the method that contacts with the solution that contains above-claimed cpd salt of the birefringent film that obtains, for example can adopt following any means: contain the method for the solution of above-claimed cpd salt in this birefringent film surface coated, this birefringent film be immersed in method in the solution that contains above-claimed cpd salt etc.When adopting these methods, be preferably with water or the birefringent film that obtained of solvent cleaning arbitrarily, and then make its drying, can obtain the duplexer of adaptation excellence at the interface of base material and birefringent film by this.
[purposes of E. birefringent film]
The purposes of birefringent film of the present invention is not particularly limited, and can enumerate typically: the λ of liquid crystal indicator/4 plates, λ/2 plates, the visual angle enlarges film, flat-panel monitor antireflection film.In the first embodiment, above-mentioned birefringent film also can be stacked and as polarization plates with polaroid.Below, be illustrated with regard to this polarization plates.
[F. polarization plates of the present invention]
Polarization plates of the present invention has above-mentioned birefringent film and polaroid at least.Above-mentioned polarization plates can comprise the stacked film that has base material and birefringent film at least, also can comprise other birefringent film or protective seam arbitrarily.On practicality, between each layer of the component parts of above-mentioned polarization plates, be provided with the adhesive layer that is fit to arbitrarily, and be pasted with polaroid and each component parts.
If as above-mentioned polaroid natural light or polarisation are converted to the polaroid of linear polarization, then can adopt suitable polaroid.It is the extension film of principal ingredient that above-mentioned polaroid is preferably with the polyvinyl alcohol resin that contains iodine or dichroic dye.The thickness of above-mentioned polaroid is generally 5 μ m～50 μ m.
If above-mentioned adhesive layer makes the face of adjacent part engage with face and with in the practicality for the sufficient adhesive power and the adhesive layer of chien shih one bodyization when gluing, then can select the adhesive layer that is fit to arbitrarily.As the material that forms above-mentioned adhesive layer, for example can enumerate: tackifier, bonding agent, binding layer agent.Above-mentioned adhesive layer can be following sandwich construction: be formed with binding layer agent layer on the adherend surface, be formed with adhesive layer or adhesive phase more thereon; Also can be can't cognitive thin layer (being also referred to as hairline) with naked eyes.The adhesive layer that is configured in polaroid one side can be identical respectively with the adhesive layer that is configured in opposite side, also can be different.
The angle that the polaroid of above-mentioned polarization plates and birefringent film attach can suitably be set according to purpose.Above-mentioned polarization plates, for example, as antireflection film the time, the slow axis direction angulation of the absorption axes direction of above-mentioned polaroid and above-mentioned birefringent film is preferably 25 °～65 °, more preferably 35 °～55 °.When enlarging film as the visual angle, the slow axis direction angulation of the absorption axes direction of the above-mentioned polaroid of above-mentioned polarization plates and above-mentioned birefringent film is actually parallel or is actually vertically.In this manual, so-called " being actually parallel " is meant that the absorption axes direction of polaroid and the slow axis direction angulation of birefringent film comprise 0 ° ± 10 ° scope, are preferably 0 ° ± 5 °.So-called " being actually vertical " is meant that the absorption axes direction of polaroid and the slow axis direction angulation of birefringent film comprise 90 ° ± 10 ° scope, are preferably 90 ° ± 5 °.
[embodiment]
And then, utilize following examples that the present invention is illustrated.Moreover the present invention is not limited only to these embodiment.Moreover employed in an embodiment each analytical approach is as described below.
(1) Determination of thickness method:
When thickness during, use film to measure with spectrophotometer [ProductName " internsified multichannel photodetectorMCPD-2000 " of big tomb electronics (thigh) manufacturing] less than 10 μ m.
(2) assay method of birefraction in transmitance (T[590]), the face (Δ n[590]), phase difference value (Re[λ], Rth[λ]):
The trade name " KOBRA21-ADH " of using prince's instrumentation machine (thigh) to make is measured under 23 ℃.Moreover mean refractive index is for using the value of utilizing Abbe refractometer [ProductName " DR-M4 " that Atago (thigh) makes] to be measured.
(3) assay method of electrical conductivity:
Working concentration is formed into the electrode of the aqueous solution cleaning solution conductoscope [ProductName " CM-117 " that capital of a country electronics industry (thigh) is made] of 0.05 weight %, then at the 1cm that is connected with electrode
3Fill test portion in the container, when represented electrical conductivity is shown as particular value, with this particular value as measured value.
(4) assay method of water contact angle:
Use solid-liquid interface resolver [ProductName " Drop Master 300 " that consonance interface science (thigh) is made], drips of solution is added on the base material, measure then through the contact angle after 5 seconds.Condition determination is that static contact angle is measured.Water uses ultrapure water, and drop is made as 0.5 μ l.With the mean value of the multiplicity of each base material 10 times as measured value.
[synthesis example 1]
＜acenaphthene is synthesizing of [1,2-b] quinoxaline-9-formic acid also 〉
The 500ml dimethyl formamide is added on through refining 10g acenaphthene and quinoline (acenaphthene quinoline) and 3 of 8.4g, in the potpourri of 4-diaminobenzoic acid.Reactant is at room temperature continued to stir 21 hours.Filter sediment and obtain crude product.This crude product is dissolved in through filtering once more in the dimethyl formamide of heating, cleans and make with extra care with dimethyl formamide and water.
[synthesis example 2]
＜2-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-ammonium formate, and 5-sulfo group-acenaphthene potpourri synthetic of [1,2-b] quinoxaline-9-ammonium formate also
Shown in following response path, with the 3g acenaphthene that obtained in the synthesis example 1 also [1,2-b] quinoxaline-9-formic acid be added in 30% oleum (15ml).Reactant was stirred 17.5 hours down at 70 ℃.The solution that obtained under 40 ℃～50 ℃, with the dilution of 33ml water, and then was stirred 12 hours.Filter sediment, obtain to contain 5-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-formic acid, and 2-sulfo group-acenaphthene potpourri of [1,2-b] quinoxaline-9-formic acid also.
This potpourri is dissolved in 2 liters of pure water (electrical conductivity: 1.7 μ S/cm), and then add ammonium hydroxide, come neutralizing acid with ammonium hydroxide.The aqueous solution that is obtained is inserted in the supply groove, use possesses three Lian Shiping film evaluating apparatus of the reverse osmosis membrane filtrator trade name " NTR-7430 " of day eastern electrician (thigh) manufacturing makes with extra care, and becomes 14.3 μ S/cm (1 weight % conversion) until the electrical conductivity of the waste liquid of this device.Secondly, use rotary evaporator to prepare above-mentioned refining aqueous solution, make the polycyclic compund concentration in the aqueous solution become 21.1 weight %.If observe the aqueous solution that this place obtains, then show the nematic crystal phase down at 23 ℃ with polarizing microscope.By the liquid chromatography analysis, to 2-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-ammonium formate and 5-sulfo group-acenaphthene also the mixing ratio of [1,2-b] quinoxaline-9-ammonium formate carry out quantitatively, ratio of components is 46:54.
[changing 5]
[synthesis example 3]
＜2-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-ammonium formate, 3-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-ammonium formate, 4-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-ammonium formate, and 5-sulfo group-acenaphthene potpourri synthetic of [1,2-b] quinoxaline-9-ammonium formate also
Shown in following response path, the 50g acenaphthene quinone is added in 20% oleum (150ml), stirred 12 hours down at 25 ℃.The solution that obtained under 40 ℃, with the dilution of 140ml water, and then was stirred 12 hours.Filter sediment, the pie that remains on the filter paper is outstanding turbid in 300ml acetic acid.Filter sediment once more, it is dissolved in the 200ml acetone.The solution that is obtained is diluted with the 700ml methylene chloride.Filter sediment once more, under not heating, it is carried out air drying, and obtain 1,2-titanium dioxide acenaphthylene-4-sulfonic acid and 1,2-titanium dioxide acenaphthylene-5-sulfonic acid.
To contain 3 of 1.5g in the 30ml acetic acid, the suspension of 4-diaminobenzoic acid is added in the acetic acid of 100ml and contains 1, and 2-titanium dioxide acenaphthylene-4-sulfonic acid and 1 is in the suspension (2.6g) of 2-titanium dioxide acenaphthylene-5-sulfonic acid.Institute is obtained reactant stirred 12 hours.Filter sediment.Pie on the filter paper is dissolved in the 300ml water.Filter this solution with glass fiber filter, dilute with the 300ml concentrated hydrochloric acid.Filter sediment, obtain also [1,2-b] quinoxaline-9-formic acid, 3-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-formic acid, and 5-sulfo group-acenaphthene potpourri of [1,2-b] quinoxaline-9-formic acid also of [1,2-b] quinoxaline-9-formic acid, 4-sulfo group-acenaphthene also of 2-sulfo group-acenaphthene.
This potpourri is dissolved in 1 liter of pure water (electrical conductivity: 1.7 μ S/cm), and then add ammonium hydroxide with neutralizing acid.The aqueous solution that is obtained is added in the supply groove, use possesses the waste liquid that day three Lian Shiping film evaluating apparatus of the reverse osmosis membrane filtrator trade name " NTR-7430 " that eastern electrician (strain) makes are made with extra care this device, becomes 252 μ S/cm (1 weight % conversion) until its electrical conductivity.Secondly, use rotary evaporator to prepare the refining aqueous solution of this warp, so that the polycyclic compund concentration in the aqueous solution becomes 23.5 weight %.If observe the aqueous solution that this place obtains, then show the nematic crystal phase down at 23 ℃ with polarizing microscope.By the liquid chromatography analysis, to 2-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-ammonium formate, 3-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-ammonium formate, 4-sulfo group-acenaphthene also [1,2-b] quinoxaline-9-ammonium formate, and 5-sulfo group-acenaphthene also [1,2-b] mixing ratio of quinoxaline-9-ammonium formate carries out quantitatively, and ratio of components is 23:25:25:27 as a result.
[changing 6]
[synthesis example 4]
＜9-methyl-acenaphthene is synthesizing of [1,2-b] quinoxaline also 〉
In being equipped with the reaction vessel of stirring machine, interpolation 1L glacial acetic acid and the 18.2g acenaphthene quinone through making with extra care stirred 15 minutes under the importing nitrogen bubble, added 3 of 12.2g then, and 4-two amido toluene continue stirring 3 hours under importing nitrogen, make its reaction by this.In the reactant liquor that is obtained, add ion exchange water, filter sediment then, obtain crude product.Use hot glacial acetic acid that the crude product that is obtained is carried out crystallization again, and obtain also [1,2-b] quinoxaline of the refining 9-methyl-acenaphthene of warp.
[synthesis example 5]
＜9-methyl-acenaphthene is [1,2-b] quinoxaline-2 also, 5-disulfonic acid synthetic 〉
Shown in following response path, with 9-methyl-acenaphthene of the 25g that obtained in the synthesis example 4 also [1,2-b] quinoxaline be added in 30% oleum (175ml), stirred 20 hours down at 120 ℃, make its reaction.One side remains on 40 ℃～50 ℃ with the solution that is obtained, and simultaneously adds the 350ml ionized water and dilutes, and then stirred 3 hours.Filter sediment, repeat to make for 3 times its outstanding turbid cleaning operation that filters after in 300g acetone then,, obtain also [1,2-b] quinoxaline-2 of 9-methyl-acenaphthene, the 5-disulfonic acid the solids fraction vacuum drying after filtering 12 hours.
[changing 7]
[synthesis example 6]
＜4,5-two amidos-2-methyl-benzene sulfonic acid synthetic 〉
Shown in following response path, with 3 of 30g, the 4-diaminotoluene is added in 4% oleum (200ml), stirs 4 hours down at 140 ℃, makes its reaction.One side obtains solution with institute and remains on 40 ℃～50 ℃, simultaneously adds the 400ml ionized water and dilutes, and then stirred 3 hours.After filtering sediment, carry out crystallization again with water, and obtain 4,5-diamido-2-toluene sulfonic acide.
[changing 8]
[synthesis example 7]
＜10-methyl-acenaphthene is synthesizing of [1,2-b] quinoxaline-9-sulfonic acid also 〉
In being equipped with the reaction vessel of stirring machine, add 1.5L glacial acetic acid and 18.2g acenaphthene quinone through making with extra care, under importing nitrogen, stirred 15 minutes, add then obtained in the 20.2g synthesis example 64,5-diamido-2-toluene sulfonic acide, under importing nitrogen, continue to stir 3 hours, make its reaction by this.In the reactant liquor that is obtained, add ion exchange water, filter sediment then, obtain crude product.Use glacial acetic acid that the acquisition crude product is carried out crystallization again, and obtain also [1,2-b] quinoxaline-9-sulfonic acid of the refining 10-methyl-acenaphthene of warp.
[changing 9]
[synthesis example 8]
＜acenaphthene is synthesizing of [1,2-b] quinoxaline-9-formic acid butyl amide also 〉
In being equipped with the reaction vessel of stirring machine, add 1.5L glacial acetic acid and 18.2g acenaphthene quinone, under importing nitrogen, stirred 15 minutes, add the N-butyl benzamide of 20.7g then through making with extra care, under importing nitrogen, continue to stir 3 hours, make its reaction by this.In the acquisition reactant liquor, add ion exchange water, filter sediment then, obtain crude product.Use glacial acetic acid that the crude product that is obtained is carried out crystallization again, and obtain also [1,2-b] quinoxaline-9-formic acid butyl amide of the refining acenaphthene of warp.
[synthesis example 9]
＜acenaphthene is synthesizing of [1,2-b] quinoxaline-9-formic acid butyl amide sulfonated bodies also 〉
Shown in following response path, with the 30g acenaphthene that obtained in the synthesis example 8 also [1,2-b] quinoxaline-9-formic acid butyl amide be added in 30% oleum (210ml), at room temperature stirred 48 hours, make its reaction.One side remains on 40 ℃～50 ℃ with the solution that is obtained, and simultaneously adds the 500ml ionized water and dilutes, and then stirred 3 hours.After filtering sediment, repeat 3 times,, obtain also [1,2-b] quinoxaline-9-formic acid butyl amide sulfonated bodies of acenaphthene the solids fraction vacuum drying at room temperature after filtering 12 hours with its outstanding turbid cleaning operation that filters again after in 400g acetone.
[changing 10]
[embodiment 1]
With thickness 80 μ m is polymeric membrane [the Fuji Photo Film Co. of principal ingredient with the Triafol T, Ltd. the trade name of Zhi Zaoing " ZRF80S "] be immersed in the aqueous solution that is dissolved with NaOH, alkali treatment (being also referred to as basification) is implemented on its surface.The water contact angle of above-mentioned polymeric membrane under 23 ℃ is 64.6 ° before the processing, is 26.5 ° after the processing.Secondly, use rod to be coated with machine [trade name " mayer rot HS1.5 " that Buschman company makes], the aqueous solution that on the surface of alkali treatment, is obtained in the above-mentioned synthesis example 2 of coating at above-mentioned polymeric membrane, in 23 ℃ constant temperature enclosure, one in the face of coating surface blowing one side makes its drying, makes its dry 3 minutes then in 40 ℃ air circulating type drying oven.Its result is, on the polymeric membrane surface that with the Triafol T is principal ingredient, obtains refractive index ellipsoid and shows nx〉nz〉the birefringent film A of ny relation.The characteristic of this birefringent film A is shown in table 1.
[embodiment 2]
Use the aqueous solution that is obtained in the above-mentioned synthesis example 3, with the method identical with embodiment 1 be coated with, drying, and on the polymeric membrane surface that with the Triafol T is principal ingredient, obtain refractive index ellipsoid and show nx nz the birefringent film B of ny relation.The characteristic of this birefringent film B is shown in table 1.
[embodiment 3]
9-methyl-the acenaphthene that makes the 10g that is obtained in the above-mentioned synthesis example 5 is [1,2-b] quinoxaline-2 also, and the 5-disulfonic acid is dissolved in the 500ml ion exchange water.With 5% ammonium hydroxide aqueous solution the aqueous solution that is obtained is neutralized to pH value=7, uses rotary evaporator that aqueous solution is concentrated into 29%, the preparation smears.Use rod to be coated with machine [trade name " mayer rot HS1.5 " that Buschman company makes], this smears is coated on the glass substrate of thickness 1.3mm, in 23 ℃ constant temperature enclosure, make its air dry.Its result is, at glass baseplate surface, obtains refractive index ellipsoid and shows nx〉nz〉the birefringent film C of ny relation.The characteristic of this birefringent film C is shown in table 1.
[embodiment 4]
9-methyl-the acenaphthene that makes the 10g that is obtained in the above-mentioned synthesis example 5 is [1,2-b] quinoxaline-2 also, and the 5-disulfonic acid is dissolved in the 500ml ion exchange water.With 5% ammonium hydroxide aqueous solution institute is obtained aqueous solution and be neutralized to pH value=7, use rotary evaporator that aqueous solution is concentrated into 25% then, the preparation smears.Use rod to be coated with machine [trade name " mayerrot HS1.5 " that Buschman company makes], this smears is coated on the glass substrate of thickness 1.3mm, in 23 ℃ constant temperature enclosure, make its air dry.Its result is, at glass baseplate surface, obtains refractive index ellipsoid and shows nx〉nz〉the birefringent film D of ny relation.The characteristic of this birefringent film D is shown in table 1.
[embodiment 5]
With 10-methyl-acenaphthene of the 10g that obtained in the above-mentioned synthesis example 7 also [1,2-b] quinoxaline-9-sulfonic acid be dissolved in the 500ml ion exchange water.With 5% ammonium hydroxide aqueous solution institute is obtained aqueous solution and be neutralized to pH value=8, use rotary evaporator that aqueous solution is concentrated into 18% then, the preparation smears.Use rod to be coated with machine [trade name " mayer rot HS1.5 " that Buschman company makes] this smears is coated on the glass substrate of thickness 1.3mm, in 23 ℃ constant temperature enclosure, make its air dry.Its result is, at glass baseplate surface, obtains refractive index ellipsoid and shows nx〉nz〉the birefringent film E of ny relation.The characteristic of this birefringent film E is shown in table 1.
[embodiment 6]
With the 10-methyl acenaphthene of the 10g that obtained in the above-mentioned synthesis example 7 also [1,2-b] quinoxaline-9-sulfonic acid be dissolved in the 500ml ion exchange water.With 5% ammonium hydroxide aqueous solution the aqueous solution that is obtained is neutralized to pH value=7, uses rotary evaporator that aqueous solution is concentrated into 18% then, the preparation smears.Use rod to be coated with machine [trade name " mayer rot HS1.5 " that Buschman company makes] this smears is coated on the glass substrate of thickness 1.3mm, in 23 ℃ constant temperature enclosure, make its air dry.Its result is, at glass baseplate surface, obtains refractive index ellipsoid and shows nx〉nz〉the birefringent film F of ny relation.The characteristic of this birefringent film F is shown in Table 1.
[embodiment 7]
With the acenaphthene of the 10g that obtained in the above-mentioned synthesis example 9 also [1,2-b] quinoxaline-9-carboxylic acid butyl amide sulfonated bodies be dissolved in the 500ml ion exchange water.With 5% ammonium hydroxide aqueous solution the aqueous solution that is obtained is neutralized to pH value=7, uses rotary evaporator that aqueous solution is concentrated into 15% then, the preparation smears.Use rod to be coated with machine [trade name " mayer rot HS1.5 " that Buschman company makes] this smears is coated on the glass substrate of thickness 1.3mm, in 23 ℃ constant temperature enclosure, make its air dry.Its result is, at glass baseplate surface, obtains refractive index ellipsoid and shows nx〉nz〉the birefringent film G of ny relation.The characteristic of this birefringent film G is shown in table 1.
[table 1]
[evaluation]
Shown in embodiment 1～7, can have-SO by containing at least a kind
3M base and/or-polycyclic compund of COOM base and the solution coat of solvent be at substrate surface, satisfies nx and obtain refractive index ellipsoid nz ny relation and show the birefringent film of higher interior birefraction.These birefringent films are compared with the birefringent film of existing polymeric membrane type, and thickness is extremely thin, can obtain specific phase difference value.
[utilizability on the industry]
As mentioned above, birefringent film of the present invention is because refractive index ellipsoid satisfies Nx〉nz〉relation of ny, and show birefringence in the higher face, so for example when using When liquid crystal indicator, can help largely the raising of display characteristic to reach Slimming. In addition, manufacturing method according to the invention is not even use special prolonging Stretch method and only with solution coat on base material, also can obtain to have the excellence as above-mentioned The birefringent film of characteristic, therefore extremely useful to the productivity that improves birefringent film.
Claims (12)
1. birefringent film, its refractive index ellipsoid satisfies nx〉nz〉relation of ny, and contain at least a kind and have-SO
3M base and/or-polycyclic compund of COOM base, wherein, M represents counter ion counterionsl gegenions.
2. birefringent film according to claim 1, wherein, described birefringent film is birefraction Δ n[590 in the face at wavelength 590nm place] be more than 0.05.
3. birefringent film according to claim 1 and 2, wherein, the thickness of described birefringent film is 0.05 μ m～10 μ m.
4. according to any described birefringent film in the claim 1～3, wherein, described birefringent film contains also [1,2-b] quinoxaline derivant of the acenaphthene shown in the following general formula (I),
In the formula, i, j, k, l are respectively 0～4 integer independently, and m, n are respectively 0～6 integer independently, R
1, R
2The alkyl of representing carbon number 1～6 respectively, M represent to distinguish identical counter ion counterionsl gegenions that also can be different, i, j, k, l, m, and n be not 0 simultaneously.
5. according to any described birefringent film in the claim 1～4, wherein, described birefringent film is phase difference value Re[590 in the face at wavelength 590nm place] be 20nm～1000nm.
6. according to any described birefringent film in the claim 1～5, wherein, described birefringent film is phase difference value Re[590 in the face at wavelength 590nm place] with the phase difference value Rth[590 of thickness direction] difference be 10nm～800nm.
7. according to any described birefringent film in the claim 1～6, wherein, the Nz coefficient of described birefringent film is greater than 0 and less than 1.
8. stacked film, it has each described birefringent film and base material in the claim 1～7 at least.
9. the manufacture method of a birefringent film, it comprises the operation of following (1)～(3):
(1) preparation contains solvent and at least a kind and has-SO
3M base and/or-polycyclic compund of COOM base and show the operation of the solution of nematic crystal phase, wherein, M represents counter ion counterionsl gegenions;
(2) prepare at least one surface by the operation of the base material of hydrophilicity-imparting treatment;
(3) base material of in described operation (2), being prepared on the surface of hydrophilicity-imparting treatment, be coated on the solution of preparation in the described operation (1), and make its dry operation.
10. the manufacture method of birefringent film according to claim 9, wherein, described hydrophilicity-imparting treatment is that corona treatment, plasma treatment, alkali treatment or binding layer (Anchor coat) are handled.
11. according to the manufacture method of claim 9 or 10 described birefringent films, wherein, described base material is glass substrate or polymeric membrane.
12. a polarization plates, it has each described birefringent film and polaroid in the claim 1～7 at least.
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