Detailed description of the invention
Below, by showing concrete mode, the present invention is described in detail, but the present invention is not limited to exemplified concrete mode.
First embodiment of the present invention relates to a kind of manufacture method of anisotropy pigmented film, and the method comprises: use die applicator on substrate, be coated with the operation of anisotropy pigmented film formation composition, it is characterized in that,
Described die applicator has the front die lip that is positioned at die applicator front line direction side and is positioned at the rear die lip with above-mentioned front line direction opposition side;
Two die lips have and substrate die lip lower surface in opposite directions separately;
Using the length along described front line direction of the lower surface of described front die lip as A, and using the length along described front line direction of the lower surface of described rear die lip as B time, A ﹥ B;
The viscosity of anisotropy pigmented film formation composition is more than 10cP.
By the manufacture method of present embodiment, although can obtain that there is high orientation, polarizing properties is excellent and the reason of the uniform anisotropy pigmented film of the generation of thickness inequality or coating striped can be suppressed to determine, be presumed to following reason.
Using the length along front line direction of the lower surface of rear die lip as B, and using the lower surface of front die lip along the length of front line direction as A, and during A ﹥ B, after reducing die lip coating fluid pearl in the whirlpool that produces.On the other hand, the anisotropy pigmented film formation composition flowed out by die slit portion from slit width (such as, more than 50 μm) when being stretched to coating film thickness (such as, several μm) of anisotropy pigmented film formation composition, bear large elongation deformation.In addition, when the viscosity of anisotropy pigmented film formation composition is more than particular value, this stress caused by elongation deformation can act on effectively.That is, though with the shearing force not grow of substrate interface, also can obtain good state of orientation.
In addition, due to A ﹥ B, the coating fluid pearl of rear die lip is appropriate, and relative to the coating fluid pearl of front die lip, the coating fluid pearl of rear die lip be appropriate, and therefore, the coating fluid pearl of rear die lip can not superfluous delay, and the coating fluid being applicable to coated face can keep appropriate.Due to this character, when substrate is coated with anisotropy pigmented film formation composition, can be inhibited and produces the even spread film of thickness inequality or coating striped.
(anisotropy pigmented film)
Anisotropy pigmented film is in the electromagnetic property on any 2 directions in total 3 direction in the three-dimensional coordinate system in 2 directions in the thickness direction being selected from film and any normal surface, has anisotropic blooming.As electromagnetic property, the electrical properties etc. such as optical property, resistance and electric capacity such as absorption and refraction can be enumerated.As having the optically anisotropic films such as absorption and refraction, such as, there are linear polarization layer, rotatory polarization layer, phase retardation film and electric anisotropy film etc.Anisotropy pigmented film in present embodiment, except being suitable as the use of anisotropy pigmented film, is also suitable as phase retardation film and the use of electric anisotropy film.
Transmitance in the visible wavelength region of the anisotropy pigmented film obtained by present embodiment is preferably more than 25%, and more preferably more than 35%, particularly preferably more than 40%.In addition, the upper limit of transmitance is not special to be limited, as long as it be the upper limit corresponding to purposes, such as, when degree of polarization height, and preferably less than 50%.When transmitance is more than particular value, being useful as following optical element, particularly, is useful as the liquid crystal display optical element for color displays.
When being used as polarization element by the anisotropy pigmented film of present embodiment gained, the orientation characteristic of anisotropy pigmented film can be represented with dichroic ratio.When dichroic ratio is more than 8, there is the function as polarization element, but preferably more than 25, more preferably more than 30, particularly preferably more than 35.In addition, dichroic ratio is more high more preferred, and no maximum.By making dichroic ratio be more than particular value, be useful as following optical element, particularly polarization element.
Dichroic ratio (D) described in present embodiment refers to when being orientated to consistent by anisotropy pigment, shows with following formula table.
D=Az/Ay
In addition, the absorbance of Az for observing when the polarisation of light direction injecting anisotropy pigmented film parallels with the differently-oriented directivity of anisotropy pigment, Ay is the absorbance of its polarization direction for observing time vertical.As long as respective absorbance uses the value under Same Wavelength, be just not particularly limited, any wavelength can be selected according to object, but when representing the degree of orientation of anisotropy pigmented film, preferably use the value under the maximum absorption wavelength of anisotropy pigmented film.
When the anisotropy pigmented film of present embodiment gained uses as polarization element, available degree of polarization represents the orientation characteristic of anisotropy pigmented film.Degree of polarization refers to that singleton transmittance is more than 36%, usual more than 95%, preferably more than 98%, more preferably more than 99%.In addition, degree of polarization is more high more preferred, and maximum is 100%.When degree of polarization is more than above-mentioned numerical value, be useful as following optical element, particularly polarization element.
As long as respective transmitance uses the value under Same Wavelength, be just not particularly limited, any wavelength can be selected according to object, but when representing the degree of orientation of anisotropy pigmented film, preferably use the value under the maximum absorption wavelength of anisotropy pigmented film.
Specifically, according to JISZ8701, by the values Y under D65 light source 2 ° of visuals field of Tz and Ty, calculate and correct transmitance and the spectral luminous efficiency correction transmitance relative to the axial polarisation of the polarisation of anisotropy pigmented film relative to the spectral luminous efficiency of the axial polarisation of the absorption of anisotropy pigmented film, and calculate degree of polarization according to following formula.
Degree of polarization (P) (%)={ (Yy-Yz)/(Yy+Yz) }
1/2× 100
Yz: correct transmitance relative to the spectral luminous efficiency of the axial polarisation of the absorption of anisotropy pigmented film
Yz: correct transmitance relative to the spectral luminous efficiency of the axial polarisation of the polarisation of anisotropy pigmented film
By the thickness of the anisotropy pigmented film of present embodiment gained, in dry film thickness, preferred more than 10nm, more preferably more than 50nm.On the other hand, preferably less than 30 μm, more preferably less than 1 μm.By making the thickness of anisotropy pigmented film in proper range, there is the trend obtaining the even orientation of molecule in film and homogeneous film thickness.
In present embodiment, insoluble process can be carried out to anisotropy pigmented film.Insolublely mean that the dissolubility by reducing the compound in anisotropy pigmented film controls this compound from the stripping anisotropy pigmented film, thus improve the treatment process of membrane stability.Specifically, such as, the process ion of low valence mumber being replaced to the ion (such as, monovalent ion is replaced to multivalent ion) higher than its valence mumber can be enumerated maybe the ion of low valence mumber is replaced to there is the organic molecule of multiple ionic group or the process of polymer.As such processing method, such as, the known methods such as the treatment process that thin Tian Fengzhu " theoretical manufacture dyeing chemistry " (skill report hall, nineteen fifty-seven) 435 ~ 437 pages etc. can be used described.
Preferably, the anisotropy pigmented film of the method process gained recorded according to Japanese Patent Laid-Open 2007-241267 publication etc., and become relative to water-insoluble anisotropy pigmented film, from the viewpoint of the easiness and durability etc. of post processing, be preferred.
(anisotropy pigmented film formation composition)
For the anisotropy pigmented film formation composition used in being formed at anisotropy pigmented film, as long as it embodies above-mentioned anisotropy when forming film and have aftermentioned character, be just not particularly limited.In present embodiment, by being coated on the film forming of substrate carrying out anisotropy pigmented film, therefore, the anisotropy pigmented film formation composition comprising such anisotropic material and solvent is used.
(viscosity of anisotropy pigmented film formation composition)
The viscosity of the anisotropy pigmented film formation composition in present embodiment, as long as it is at more than 10cP, is just not particularly limited.The viscosity of anisotropy pigmented film formation composition suitably can adjust according to the characteristic of contained pigment, solvent and additive etc., makes the polarizing properties of obtained anisotropy pigmented film be desired value.
The viscosity of the anisotropy pigmented film formation composition in present embodiment is generally more than 10cP, preferred more than 15cP, more preferably more than 20cP, particularly preferably more than 25cP.In addition, preferred below 100cP, more preferably below 80cP, particularly preferably below 60cP.By making viscosity in above-mentioned scope, the stress caused by elongation deformation using anisotropy pigmented film formation composition during specific die applicator to bear can carry out useful effect, and has following trend: can obtain having high orientation and the excellent anisotropy pigmented film of polarizing properties.
The viscosity measured refers to according to following measured value: use レ オ メ ー タ ー VAR-50 (manufacture of REOLOGICA company), parallel-plate (diameter 40mm, gap 0.8mm), measures temperature 25 DEG C, shear rate 1000s
-1under shear (pre-shear) in advance after 5 seconds, spend and make shear rate from 1000s in 180 seconds
-1be changed to 100s
-1, carry out shear rate sweep measuring.
The method of the anisotropy pigmented film formation composition viscosity in adjustment present embodiment is not particularly limited, and can adjust according to the addition of pigment, solvent and additive etc. and combination etc.
Improve viewpoint from the wetability of substrate surface, the pH of the anisotropy pigmented film formation composition in present embodiment is preferably less than 7.Application step can be carried out with single sheet type or carries out in the mode of roller to roller, but as mentioned above, when carrying out with single sheet type, is preferably suitable for present embodiment.
For anisotropy pigmented film formation composition, the anisotropy pigmented film formed after solvent evaporation forms the viewpoint of high-orientation, is preferably the state of liquid crystalline phase as composition.In addition, in present embodiment, the state of liquid crystalline phase refers to, the state described in 1 ~ 16 page of " basis of liquid crystal and application " (this positive good work in He Jiaotian city of pine, 1991).Particularly, the nematic phase preferably described in the 3rd page.
As material, as long as it can form anisotropy pigmented film, pigment or transparent material can be enumerated.
In addition, in anisotropy pigmented film formation composition, as required, also sticker resin, monomer, curing agent and additive etc. can be mixed into.Form as anisotropy pigmented film formation composition can be solution shape or gel.Anisotropy pigmented film formation composition can be the state that pigment etc. dissolves in a solvent or disperses.
(pigment)
For pigment, usually use dichroism pigment.As dichroism pigment, the pigment presenting liquid crystal and the pigment etc. presenting thermotropic liquid crystal can be enumerated, can use any number of.
In present embodiment, in order to control orientation, preferably there is the pigment of liquid crystalline phase.Herein, the pigment with liquid crystalline phase means the pigment demonstrating lyotropic liquid crystalline in a solvent, when forming anisotropy pigmented film formation composition, can present liquid crystalline phase or not present liquid crystalline phase, but preferred liquid crystal phase as above.
In addition, in order to make anisotropy pigmented film formation composition present liquid crystalline phase and aftermentioned wet type membrane formation process can be supplied to, for pigment, the pigment of preferred water soluble or organic solvent, particularly, preferred water colo(u)r.Preferred pigment is the compound that the inorganic value defined in " organic conceptional diagram-basis and application " (first Tian Shansheng work, three publish altogether, 1984) is less than organic value further.In addition, under the free state of non-salify, its molecular weight is preferably more than 200, and particularly preferably more than 300, and preferably less than 1500, particularly preferably less than 1200.In addition, water-solublely refer at room temperature, compound usually dissolves 0.1 quality %, more than preferred dissolution 1 quality % in water.
In present embodiment, pigment can be used alone one or be used in combination of two or more.During by two or more combination, in order to make anisotropy pigmented film formation composition present liquid crystalline phase, as long as at least one pigment is the pigment presenting liquid crystalline phase.
As pigment, specifically, azo system pigment, stilbene system pigment, cyanine system pigment, phthalocyanine system pigment and fused polycyclic system pigment (perylene system, oxazines system can be enumerated) etc.
Such as, Japanese Patent Laid-Open 2006-079030 publication can be enumerated, Japanese Patent Laid-Open 2010-168570 publication, Japanese Patent Laid-Open 2007-302807 publication, Japanese Patent Laid-Open 2008-081700 publication, Japanese Patent Laid-Open 09-23012 publication, Japanese Patent Laid-Open 2007-272211 publication, Japanese Patent Laid-Open 2007-186428 publication, Japanese Patent Laid-Open 2008-69300 publication, Japanese Patent Laid-Open 2009-169341 publication, Japanese Patent Laid-Open 2009-161722 publication, Japanese Patent Laid-Open 2009-173849 publication, Japanese Patent Laid-Open 2010-039154 publication, Japanese Patent Laid-Open 2010-180314 publication, Japanese Patent Laid-Open 2010-266769 publication, Japanese Patent Laid-Open 2011-012152 publication, Japanese Patent Laid-Open 2011-016922 publication, Japanese Patent Laid-Open 2010-100059 publication, Japanese Patent Laid-Open 2011-141331 publication and Japan Patent JP-A 08-511109 publication, the pigment that Japan Patent spy table 2001-504238 publication and Japanese Patent Laid-Open 2006-48078 publication etc. is described.
Further, in these pigments, in the scope being easy to drop on present embodiment to make the viscosity of anisotropy pigmented film formation composition and can high molecules align be obtained in anisotropy pigmented film, preferred azo system pigment.Azo system pigment refers to the pigment with at least more than one azo group.Azo group number in its a part is preferably more than 2, and preferably less than 6.In addition, more preferably less than 4.By making the quantity of azo group be suitable numerical value, there is following trend: wavelength dispersibility is low, and can obtain in visibility region on a large scale in have absorption tone and manufacture transfiguration easy.
In azo system pigment, have with each pigment of the bisazo of following formula (A) structure, trisazo-and four azos under free acid form, due to wavelength dispersibility low and can obtain in visibility region on a large scale in there is the tone of absorption, be therefore preferred.
[changing 1]
In above-mentioned formula (A), E
1represent any organic group; R
20and R
21separately represent hydrogen atom, substituent alkyl can be had maybe can have substituent phenyl; P and q is independently the integer of more than 1, less than 5, and p+q represents more than 2, less than 6.
Further, in the structure of above-mentioned formula (A), have with each pigment of the bisazo of following formula (B) structure, trisazo-and four azos under free acid form, due to wavelength dispersibility low and can obtain in visibility region on a large scale in there is the tone of absorption, and high dichroism can be obtained when forming anisotropy pigmented film, be therefore particularly preferred.
[changing 2]
In above-mentioned formula (B), E
2represent any organic group; R
22and R
23separately represent hydrogen atom, substituent alkyl can be had maybe can have substituent phenyl.
Pigment in present embodiment directly can use with free acid form, and a part of acidic group also can be used to obtain the pigment of salt form.In addition, also can be the pigment that salt form pigment mixes with free acidity pigment.In addition, during manufacture, for the pigment obtained with salt form, directly can use, also can convert thereof into desired salt form.As the switching method of salt form, known method can be used arbitrarily, such as, can following methods be enumerated.
1) method: add the strong acid such as hydrochloric acid in the aqueous solution of the pigment obtained with salt form, after making pigment carry out acid out with the form of free acid, apparatus has in the aqueous slkali (such as, lithium hydroxide aqueous solution) of desired counter ion counterionsl gegenions and pigment acidic-group, thus carries out salt exchange.
2) method: in the aqueous solution of the pigment obtained with salt form, adds the excessive neutral salt (such as, lithium chloride) with desired counter ion counterionsl gegenions, under the form of cake of saltouing, carries out salt exchange.
3) method: the aqueous solution of the pigment obtained with salt form with storng-acid cation exchange resin process, and after making pigment carry out acid out with the form of free acid, apparatus has the aqueous slkali of desired counter ion counterionsl gegenions (such as, lithium hydroxide aqueous solution) in and pigment acidic-group, thus carry out salt exchange.
4) method: the storng-acid cation exchange resin making prior apparatus have the aqueous slkali of desired counter ion counterionsl gegenions (such as, lithium hydroxide aqueous solution) to process acts on the aqueous solution of the pigment obtained with salt form, thus carries out salt exchange.
In addition, the acidic-group that the pigment in present embodiment has is free acid form or salt form, and it depends on the pKa of pigment and the pH of pigment aqueous solution.
As the example of above-mentioned salt form, the alkali-metal salt such as Na, Li and K can be enumerated, the ammonium salt that can be replaced by alkyl or hydroxyalkyl, or the salt of organic amine.As the example of organic amine, the low-grade alkylamine that carbon number 1 ~ 6 can be enumerated, the low-grade alkylamine of carbon number 1 ~ 6 be optionally substituted by a hydroxyl group and by the low-grade alkylamine etc. of the carbon number 1 ~ 6 of carboxyl substituted.When for these salt form, its kind is not limited to a kind, can mix multiple.
In addition, pigment can be used alone, but also can by two or more in them and use, can also with the pigment beyond the mode not reducing degree of orientation above-mentioned Exemplary pigments used in combination.So, the anisotropy pigmented film with respective form and aspect can be manufactured.
As the example of mixing pigment during other pigment of mixing, C.I. directly Huang 12 can be enumerated, C.I. direct Huang 34, C.I. direct Huang 86, C.I. direct Huang 142, C.I. direct Huang 132, C.I. Indian yellow 25, C.I. direct orange 39, C.I. direct orange 72, C.I. direct orange 79, C.I. acid orange 28, C.I. directly red 39, C.I. directly red 79, C.I. directly red 81, C.I. directly red 83, C.I. directly red 89, C.I. acid red 37, C.I. direct purple 9, C.I. direct purple 35, C.I. direct purple 48, C.I. direct purple 57, C.I. direct indigo plant 1, C.I. direct indigo plant 67, C.I. direct indigo plant 83, C.I. direct indigo plant 90, C.I. direct green 42, C.I. direct green 51 and C.I. direct green 59 etc.
(solvent)
As solvent, as long as it can dissolve or disperse above-claimed cpd, be just not particularly limited.Particularly, be easy to be formed associated state as lysotropic liquid crystal in a solvent from the viewpoint of pigment, be suitable for using water, there is the blended organic solvent of water or their mixture.As the object lesson of organic solvent, one or more the mixed solvent in cellosolve classes such as the di-alcohols such as the alcohols such as methyl alcohol, ethanol, isopropyl alcohol and glycerine, ethylene glycol and diethylene glycol, methyl cellosolve and ethyl cellosolve etc. can be enumerated.
In above-mentioned, from the viewpoint of the association promoted between the part that the Organics such as the aromatic ring of pigment are high, preferred water, methyl alcohol and ethanol, particularly preferably water.
As the pigment concentration in anisotropy pigmented film formation composition, can to select according to membrance casting condition, but preferably more than 0.01 quality %, more preferably more than 0.1 quality %, and preferably below 50 quality %, more preferably below 30 quality %.When pigment concentration is too low, the pigment in composition associates insufficient, and the anisotropy pigmented film of gained cannot obtain the anisotropy such as sufficient dichroic ratio; When pigment concentration is too high, there is following situation: viscosity uprises, be difficult to carry out uniform film coated, and can anisotropic material be separated out in anisotropy pigmented film formation composition.
In anisotropy pigmented film formation composition, also as required, the additives such as surfactant, levelling agent, coupling agent and pH adjusting agent can be mixed into.By adding additive, existing and increasing the situation such as wetability and coating.
As surfactant, any one in anionic property, cationic and nonionic surfactant can be used.It adds concentration and is not particularly limited, but as being used for fully obtaining additive effect and the amount not hindering molecularly oriented, surfactant concentration in anisotropy pigmented film formation composition usual preferably more than 0.01 quality %, more preferably more than 0.1 quality %.In addition, preferably below 5 quality %, more preferably below 1 quality %, particularly preferably below 0.5 quality %.
In addition, the unstability such as salt or aggegation etc. is made in order to what suppress the anisotropic material in anisotropy pigmented film formation composition, can before and after the mixing of the constituent of anisotropy pigmented film formation composition or mixing in either phase, add the pH adjusting agents etc. such as known acid/alkali.In addition, as additive other than the above, also can use " AdditiveforCoating ", EditedbyJ.Bieleman, Willey-VCH (2000) " described in known additive.
(substrate)
As the substrate of present embodiment, it is not particularly limited, but preferably has the substrate of good surface texture, contact angle characteristic and water absorption character.As the base material forming this substrate, such as, the inorganic material such as glass can be enumerated; The macromolecular materials etc. such as triacetate system resin, acrylic resin, polyester based resin, polycarbonate-based resin, PET system resin, triacetyl cellulose prime system resin, norbornene resin, cyclic polyolefin hydrocarbon system resin or carbamate system resin.These one or by two or more and use of can be used alone.Particularly, for substrate, preferably comprise the substrate of polymer base material, wherein this polymer base material contains macromolecular material.
As the water absorption rate of substrate, be generally less than 5%, preferably less than 3%, more preferably less than 1%.When water absorption rate is too high, there is following situation: when being formed the film of the anisotropic materials such as pigment by rubbing method, substrate absorbs water and substrate is bent, and is easy to produce coating defects.In addition, also there is following situation: after forming anisotropy pigmented film by rubbing method, substrate is swelling, produces optical defect.
In addition, " water absorption rate " in present embodiment is by using the test method of ASTMD570, is determined in the water of 23 DEG C and floods 4 little weight rates constantly and the value that obtains.
The viewpoint of certain orientation can be oriented in from anisotropic materials such as the pigments contained by anisotropy pigmented film better, on the surface of the formation anisotropy pigmented film of substrate, orientation process layer etc. can be set in advance.About the formation method of orientation process layer, 226th ~ 239 pages of " liquid crystal handbook " (Wan Shan Co., Ltd., Heisei distribution on October 30th, 12) can be adopted to wait the known method recorded.
In addition, as the shape of substrate, can be membranaceous (single sheet) or the continuous film (reel) of certain size.In addition, as the thickness of substrate, be generally more than 0.01mm, preferred more than 0.02mm, and be generally below 3mm, preferred below 2mm.
As the total light transmittance of substrate, be generally more than 80%, preferably more than 85%, more preferably more than 90%.In addition, " total light transmittance " in present embodiment is the value using integrating sphere look determinator to measure, and its be by diffuse transmission light and parallel rays through photosynthetic and value.
(die head)
Fig. 1 is the enlarged drawing of the die lip as die head 101 tip portion, be the die head 101 shown in Fig. 2 a-a ' direction on sectional drawing.In Fig. 1, by die head 101, the direction towards arrow D is coated with, and front line direction side is front side (upstream).Die head 101 in present embodiment is provided with front die 101a and rear die 101b.The inner surface of these front die 101a and rear die 101b is vacated predetermined distance and is arranged in opposite directions, forms the slit 106 of the anisotropy pigmented film formation composition 103 that spues.
As mentioned above, the die head 101 in present embodiment is designed to following form:
Its tip portion have be positioned at die applicator before die lip 102a and be positioned at the rear die lip 102b with described front line direction opposition side before line direction side;
Two die lips have and substrate die lip lower surface in opposite directions separately;
Using the length along described front line direction of the lower surface of described front die lip 102a as A, and using the length along described front line direction of the lower surface of described rear die lip 102b as B time, make A ﹥ B.
(A)
The length of A is generally more than 0.5mm, preferred more than 0.7mm, more preferably more than 1mm.On the other hand, the length of A is generally below 2.5mm, preferred below 2.0mm, more preferably below 1.5mm, further preferred below 1.2mm.
By making the length of A within the scope of these, there is following trend: the liquid measure that suitably can keep die lip and coated face, become good with liquid diffusion (liquid is connected) in coating when the coating of die lip starts, prevent the generation because of the coating striped in the coating caused by coating fluid deficiency.
(B)
The length of B is generally more than 0.03mm, preferred more than 0.05mm, more preferably more than 0.1mm.During by making lower limit within the scope of these, there is following trend: the damage preventing die lip, and when there is damage, preventing this damage or being attached to caused striped such as the dust of this scar, coating vacuole etc.
On the other hand, the length of B is generally below 2mm, preferred below 1mm, more preferably below 0.5mm, further preferred below 0.3mm.By making the upper limit within the scope of these, there is following trend: reduce the whirlpool resulting from the coating fluid pearl of rear die lip, and the anisotropy pigmented film flowed out by die slit portion can be made to be formed with composition acquisition elongation deformation, improve the wetting autgmentability of anisotropy pigmented film formation composition to die lip.
(relation of A and B)
For the length of A and B, as long as meet A ﹥ B, be just not particularly limited, ratio and the difference of its length are also not particularly limited.
Preferred more than the 0.1mm of length difference of A and B, more preferably more than 0.3mm.On the other hand, preferred below the 2.0mm of length difference of A and B, more preferably below 1.5mm.
In addition, the length ratio (A/B) of A and B is preferably more than 2, and more preferably more than 5, further preferably more than 10.On the other hand, A/B preferably less than 30, more preferably less than 25.
By making the length of A and B within the scope of these, there is following trend:
Suitably can keep the liquid measure of the coating fluid pearl of rear die lip and front die lip, reduce the whirlpool resulting from the coating fluid pearl of rear die lip, the anisotropy pigmented film flowed out by die slit portion can be made to be formed and to obtain elongation deformation with composition, and spread (liquid is connected) when the coating that can improve die lip starts with the liquid in coating and improve the wetting autgmentability of anisotropy pigmented film formation composition to die lip.
In addition, slit width is generally more than 10 μm, preferably more than 30 μm, more preferably more than 50 μm.On the other hand, slit width is generally below 0.5mm, preferred below 0.3mm, more preferably below 0.1mm.
During by making slit width within the scope of these, there is following trend: the stress formed caused by the elongation deformation of bearing with composition can act on effectively by anisotropy pigmented film, can obtain there is high orientation and the excellent anisotropy pigmented film of polarizing properties.In addition, also there is following trend: the film thickness distribution of anisotropy pigmented film becomes good, and the obstruction caused by foreign matter or coating striped can be suppressed.
In order to improve the wetability of die head in present embodiment and anisotropy pigmented film formation composition, following methods can be combined:
To the surface (forming the surface of slit, die lip face etc.) contacted with anisotropy pigmented film formation composition, method, the method that the film improving wetability is set on the surface contacted with anisotropy pigmented film formation composition of carrying out processing with plasma or acidic aqueous solution etc., the surface contacted with anisotropy pigmented film formation composition to be ground, make the method etc. that the surface that contacts with anisotropy pigmented film formation composition is parallel with line direction before coated face.
Parallelly with real estate not only comprise completely parallel, also comprise and there is the almost parallel of angular deviation a little.The angular deviation allowed is generally less than 5 °, preferably less than 3 °, more preferably less than 1 °, preferably 0.5 ° further.
Preferred front die lip is equal apart from the distance of real estate with rear die lip, but also can be different.In this case, become faster in order to the die applicator speed obtaining even spread film can be used in, the distance of front die lip and real estate can be made to be less than the distance of rear die lip and real estate.When the distance of front die lip and real estate is less than the distance of rear die lip and real estate, this difference is generally below 0.1mm, preferred below 0.05mm, more preferably below 0.01mm.Distance herein refers to the length of the shortest part between the substrate-side surface of die lip and real estate.
In addition, front die lip and rear die lip can be different as above from the distance of real estate, but in order to prevent both inconsistent or caused by this concave-convex surface the coating fluids caused by the concave-convex surface of die lip and substrate chaotic etc. and obtain uniform coated film, it is preferably more than 0.01mm independently of one another, more preferably more than 0.03mm, further preferred more than 0.05mm.
On the other hand, due to make the distance of front die lip and rear die lip and real estate as much as possible the short coating speed that makes become greatly, their distance is preferably below 0.3mm, more preferably below 0.2mm independently of one another, further preferred below 0.1mm.Distance herein refers to the length of the shortest part between die lip and real estate.
(die applicator)
Die applicator in present embodiment is the die applicator comprising above-mentioned die head.Die applicator in present embodiment also can be the die applicator of single sheet type or the die applicator of roll-to-roll mode.Below, by Fig. 2, the structure of the die applicator adopting single sheet type is described.
Fig. 2 is the stereogram of display die applicator form.Die applicator 100 is for the device using coating substrate S as the anisotropy pigmented film formation composition of coating fluid, and for the formation of forming anisotropy pigmented film contained in the optical element of liquid crystal cell.Die applicator 100 be provided with for mounting substrate S coating table 105, coating table 105 on substrate S on be coated with the die head 101 of anisotropy pigmented film formation composition and make die head drives structure 108a and the 108b of die head 101 movement.Mounting substrate S on the assigned position of coating table 105.In die head 101, between 2 die head blocks in opposite directions, be clamped with pad (Shim) (not shown).Form slit by 2 die head blocks and pad, to be spued anisotropy pigmented film formation composition from the discharge opening 104 on die head top by slit.
Die head drives structure is provided with the maintaining part 108a keeping the die head 101 and drive division 108b that maintaining part 108a direction in drawing can be made back and forth to drive.Die head 101 is held in following form by maintaining part 108a: keep certain intervals between the discharge opening of the anisotropy that spues pigmented film formation composition and substrate S.In addition, though do not show in figure, there is the location structure that suitably can change the interval between discharge opening and substrate S.
Drive division 108b is made up of various motor and encoder etc., and by driving maintaining part 108a, die head 101 can be made to move to direction in drawing.So, anisotropy pigmented film formation composition can be coated with by die head 101 on substrate S.
(manufacture method of anisotropy pigmented film)
The manufacture method of present embodiment has application step described later, but also can have other step.As other step, such as, washing step and supply step can be enumerated.In addition, when manufacturing liquid crystal cell, the drying steps etc. of the step forming other film such as alignment films or diaphragm on substrate, the dry film formed can be enumerated.
(application step)
Application step is the step being coated with anisotropy pigmented film formation composition and forming anisotropy pigmented film on substrate.One in the concrete form of following optical element is polarization element, and polarization element is the element comprising anisotropy pigmented film.There is its situation about being only made up of anisotropy pigmented film in polarization element, on the other hand, for objects such as raising polarizing properties and increase mechanical strengths, also can have other film etc.
Application step in present embodiment is the step of the film forming of being carried out anisotropy pigmented film by wet type membrane formation process.Wet type membrane formation process is following method: on substrate, apply anisotropy pigmented film formation composition by any means, and through dry solvent process, makes orientation and the lamination on substrate such as pigment.In present embodiment, adopt die applicator as application apparatus.When forming anisotropy pigmented film formation composition by wet type membrane formation process on substrate, in anisotropy pigmented film formation composition, or in solvent seasoning process, by pigment self-association, produce the orientation in small area.By giving outfield to this state, can in macro-regions, make it be orientated to certain orientation, obtain the anisotropy pigmented film with desired performance.In this respect, it is different from the method for the following principle of employing: dye with the solution comprising pigment to so-called polyvinyl alcohol (PVA) film etc. and extend, and making pigment carry out orientation by means of only extension process.In addition, outfield herein, can enumerate the impact of the orientation process layer implemented on substrate in advance, shearing force, elongation deformation and magnetic field etc., these can be used alone or combinationally use multiple.
In addition, substrate is coated with the process of anisotropy pigmented film formation composition, imparting outfield makes the process of the process of its orientation and dry solvent carry out successively or to carry out simultaneously.
The differently-oriented directivity of anisotropy pigmented film is usually consistent with coating direction, but also can be different from coating direction.In addition, for the differently-oriented directivity of the anisotropy pigmented film in present embodiment, such as, when for anisotropy pigmented film, differently-oriented directivity be polarisation through axle or absorb axle; When for phase retardation film, differently-oriented directivity is fast axle or slow axis.
During continuous coating anisotropy pigmented film formation composition, be not particularly limited to the method for die applicator supply anisotropy pigmented film formation composition, supply interval, but with the situation that can produce coating film thickness when stopping and changing when the supply operation that there is coating fluid becomes the beginning of numerous and diverse, coating fluid, therefore, when the film thickness of anisotropy pigmented film is thinner, particularly preferably anisotropy pigmented film formation composition is continuously supplied to die applicator and is coated with simultaneously.
In addition, in present embodiment, the coating of anisotropy pigmented film formation composition can be to be carried out being formed on the whole substrate of the process of lyophobic parts and/or liquid repellent part, coating or part coating continuously.
The die applicator used in present embodiment, as mentioned above, its Die top is by specifying with A and B specified, and side coating fluid can not superfluously be detained after coating, and can keep the coating fluid being applied to coated face in right amount.And this appropriate state is also stablized in coating, therefore, it is possible to improve coating speed when not producing defect on substrate.Thus, the shearing force be applied on the anisotropy pigmented film formation composition of coating can be improved, thus improve the polarizing properties of the anisotropy pigmented film after orientation and coating.
At this moment, from the productivitys such as volume production and the viewpoint presenting polarity, the speed of die applicator is preferably more than 5mm/s, more preferably more than 7mm/s, further preferred more than 10mm/s, particularly preferably more than 15mm/s.
On the other hand, the viewpoint of even spread anisotropy pigmented film formation composition from substrate, this speed is preferably below 200mm/s, more preferably below 150mm/s, further preferred below 100mm/s.
In addition, the coating temperature of anisotropy pigmented film formation composition is generally more than 0 DEG C, less than 80 DEG C, preferably less than 40 DEG C.In addition, the humidity during coating of anisotropy pigmented film formation composition is preferably more than 10%RH, more preferably more than 30%RH, and preferred below 80%RH.
Second embodiment of the present invention is the anisotropy pigmented film obtained by above-mentioned manufacture method.The explanation about anisotropy pigmented film of above-mentioned first embodiment record is quoted in the explanation of anisotropy pigmented film of the present embodiment.
3rd embodiment of the present invention is the optical element comprising above-mentioned anisotropy pigmented film.
(optical element)
Optical element in present embodiment utilizes the anisotropy of light absorption and obtains the polarization element of rectilinearly polarized light, circularly polarized light, elliptically polarized light etc., retardation element, has the element of the functions such as refraction ansiotropy or conduction anisotropy.These functions suitably can adjust according to the selection of film forming process, substrate or the composition containing organic compound (pigment or transparent material).In present embodiment, preferably use as polarization element.
(polarization element)
Polarization element in optical element is lamination anisotropy pigmented film formation composition and the polarization element obtained on substrate.In addition, also can be the polarization element with any film (layer).Such as, manufacture by forming anisotropy pigmented film formation composition at alignment layer surface.In the polarization element of present embodiment, except using alignment films and anisotropy pigmented film, also can as required, carry out lamination formation by the cover layer that is coated with or fits, adhesion coating or the layer (as the function of anti-reflection layer, alignment films, phase retardation film, the function increasing film as brightness, the function as reflectance coating, the function as semipermeable reflection film, layer etc. as the optical function such as function of diffusion barrier) etc. with various function and use as laminate.These have the layer of optical function, such as, can be formed according to the method for following form.
There is the layer of the function as phase retardation film, such as, formed by following methods: carry out the extension process that Japanese Patent Laid-Open 2-59703 publication, Japanese Patent Laid-Open 4-230704 publication etc. are recorded, or carry out the process of Japanese Patent Laid-Open 7-230007 publication record.
In addition, there is the layer of the function increasing film as brightness, such as, formed by following methods: the method recorded according to Japanese Patent Laid-Open 2002-169025 publication or Japanese Patent Laid-Open 2003-29030 publication forms micropore, or by being formed selecting the different cholesterol liquid crystal ply of more than 2 layers of the centre wavelength of reflection.
The layer had as the function of reflectance coating or semipermeable reflection film is formed by the metallic film of the gained such as evaporation or sputtering by using.Have as the function of diffusion barrier layer by above-mentioned protective layer coating comprise particulate resin solution and formed.
In addition, there is the layer of the function as phase retardation film or optical compensation films, make its orientation by the coating liquid crystal compounds such as plate-like liquid crystal compounds and nematic liquid crystal compound and formed.
When anisotropy pigmented film in present embodiment uses as the anisotropy pigmented film in the various display elements such as LCD or OLED etc., can on the surface of electrode base board etc. forming these display elements direct formation anisotropy pigmented film, and the member of formation of the substrate being formed with anisotropy pigmented film as these display elements to be used.
From by directly formed on the contour heat resistant substrate of glass obtain high-fire resistance polarization element in, polarization element is not only applicable to liquid crystal display or display of organic electroluminescence, also can be suitably used for the purposes that liquid crystal projection apparatus or vehicle-mounted display floater etc. need high-fire resistance.
4th embodiment of the present invention is the liquid crystal cell comprising above-mentioned optical element.
(liquid crystal cell)
The liquid crystal cell of present embodiment normally clamps the element of liquid crystal material in 2 plate bases.The basic comprising of liquid crystal cell, such as, can be as shown in Fig. 1 of the 45th page of Co., Ltd.'s census of manufacturing meeting " flat-panel monitor dictionary " (Uchida Tatsuo, the flat tree supervision in interior pond, December 25 calendar year 2001 issues).That is, the liquid crystal cell of present embodiment is following a kind of element:
At least be provided with a pair substrate configured in opposite directions, the inner side of each substrate be provided with a pair alignment films (making the oriented layer of liquid crystal material orientation), between substrate (liquid crystal cell) be inserted with liquid crystal layer (there is the layer of liquid crystal material) and on liquid crystal layer, apply the electrode (such as, ITO electrode etc.) of electric field;
And apply electric field and liquid crystal aligning is changed by electrode pair liquid crystal layer, thus control light through and blocking-up.
As the concrete display mode of liquid crystal cell, can enumerate and use census of manufacturing meeting " flat-panel monitor dictionary " (Uchida Tatsuo of Co., Ltd., the flat tree supervision in interior pond, December 25 calendar year 2001 issue) the 54th page to the TN pattern described in 83 pages, STN pattern, DSM pattern, ecb mode, VA pattern, π type liquid crystal cell, ocb mode, HAN pattern, phase transformation-cholesterol liquid crystal pattern, ECE pattern, Ferroelectric liquid Crystals pattern, anti-Ferroelectric liquid Crystals pattern, guest-principal mode liquid crystal mode, IPS pattern, composite high-molecular pattern, the liquid crystal cell of the various liquid crystal modes such as high molecule liquid crystal pattern and luminescence generated by light pattern, and the liquid crystal cell of present embodiment is applicable to any one in these.
Only however infringement as the function of liquid crystal cell, can according to its purposes, change the configuration of each inscape, shape and laminated order etc., omit a part of inscape, multiple inscape is integrally formed, increase other inscape etc., add suitably distortion and implement.
Such as, can form as following liquid crystal cell: not there is the reflective LCD element of the secondary light sources such as backlight, there is the infiltration type of front light and lateral margin light and semi-transmission type liquid crystal cell, not there is the black-and-white crystal element of micro filter or the liquid crystal cell of field sequence type.