CN100388023C - Polarization film and its manufacturing method, polarization sheet and optical laminating body - Google Patents
Polarization film and its manufacturing method, polarization sheet and optical laminating body Download PDFInfo
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- CN100388023C CN100388023C CNB2004100851611A CN200410085161A CN100388023C CN 100388023 C CN100388023 C CN 100388023C CN B2004100851611 A CNB2004100851611 A CN B2004100851611A CN 200410085161 A CN200410085161 A CN 200410085161A CN 100388023 C CN100388023 C CN 100388023C
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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Abstract
Provided is a polarizing film free of the unevenness in hue. The polarizing film is obtained by treating a polyvinyl alcohol film in order of swelling, dyeing, boric acid treatment and rinse treatment, subjecting the film to uniaxial stretching in a boric acid treatment step and/or a step before the same and further maintaining the tension acting on the film respectively substantially constant in the respective steps after the stretching treatment, wherein the polyvinyl alcohol film is successively treated in order of the swelling treatment, the dyeing treatment, the boric acid treatment and the rinse treatment, the film is subjected to the uniaxial stretching in the boric acid treatment step and/or the step before the same and further tension control of the film is performed in the respective steps after the stretching treatment, so that the travel of the film is stabilized and the unevenness of the hue can be reduced.
Description
[technical field]
The present invention relates to few polarization film of color spot and manufacture method thereof, the polaroid of lamination protective film on the single face of this polarization film at least; in addition, also relate to the optical laminate that phase-contrast film, brightness improving film, field angle is improved any independent or multiple being glued together in film and the Transflective film and constitute.
[background technology]
As polarization film, all be to use the film of orientation absorption dichromatism pigment on the polyvinyl alcohol film all the time.That is, with iodine as the iodine class polarization film of dichromatism pigment and known as dye class polarization film of dichromatism pigment etc. with the bitintability dyestuff.These polarization films are usually at its single face at least, preferably on the two sides, and the protective films such as the bonding triacetyl cellulose of tackifier that utilize the aqueous solution by polyvinyl alcohol resin to constitute, thus make polaroid.
Manufacture method as polarization film, for example, in patent documentation 1, put down in writing following method: make polyvinyl alcohol thin film dipped in water, and after making it to expand, dye with above-mentioned dichromatism pigment, and this film that stretches, then, be fixed on the film, the polyvinyl alcohol film is handled with boric acid in order to make iodine, after the washing, carry out drying again.
In addition, in patent documentation 2, put down in writing following method: utilize above-mentioned dichromatism pigment aqueous solution that the polyvinyl alcohol film of dry type uniaxial tension is dyeed, make it lax simultaneously, and this film that in boric acid aqueous solution, stretches, make polarization film.
Make the polarization film of high-polarization, the uniaxial tension of polyvinyl alcohol film is important.Wet type in the stretching stretches, generally can be by the front and back of dipping film in treating fluid, and change the rotational speed of nip rolls and carry out, specifically, the rotational speed that is higher than before the dipping by the rotational speed that makes the nip rolls behind the dipping stretches.At this moment, in order to stretch accurately, control impregnated in the rotational speed ratio of the nip rolls before and after the treating fluid, promptly carries out ratio control.
But,, on the polarization film of preparation, also can produce color spot even accurately carry out such proportional control.Such color spot descends the quality of polarization film.
[patent documentation 1] spy opens flat 10-153709 communique
[patent documentation 2] spy opens flat 2002-182035 communique
[summary of the invention]
[problem that invention will solve]
The major subjects that the present invention will solve provides the few polarization film of color spot.
[solving the method for problem]
The reason of present inventors in order to find out that thoroughly aforesaid color spot produces, carried out meticulous research repeatedly, the result considers in the operation after stretch processing, change the tension force of polyvinyl alcohol film, whether can be owing to the fluctuation of service of film, thereby cause producing color spot, and further study repeatedly, found that the following new fact: adopt Tension Control all adopting ratio to control in the operation processes before substituting in the operation after the stretch processing by being used in, the tension force that so just can suppress to be applied on the polyvinyl alcohol film changes, as a result, the operation of film becomes stable, just can reduce color spot.Thereby, finished the present invention.
Promptly, polarization film of the present invention is to make by following operation: successively the polyvinyl alcohol film is carried out expansion process, dyeing processing, boric acid processing and washing and handle, carry out uniaxial tension in the operation before boric acid treatment process and/or boric acid treatment process, and in each operation after stretch processing, the tension force that will be applied to respectively on the above-mentioned film keeps constant substantially.
In addition, the manufacture method of polarization film of the present invention is a method as described below: continuously, successively the polyvinyl alcohol film is carried out that expansion process, dyeing are handled, boric acid is handled and washing is handled, carry out uniaxial tension in the boric acid treatment process and/or in the operation before the boric acid treatment process, the method is characterized in that: in each operation after stretch processing, the tension force of above-mentioned film is controlled.
In each operation after above-mentioned stretch processing, the tension force of the per unit width of above-mentioned film is preferably 150N/m～2000N/m.
In the present invention, above-mentioned boric acid treatment process can also comprise the operation of a plurality of boric acid treatment process, in this case, above-mentioned film can stretch boric acid treatment process initial or from initial to the 2nd step, in the boric acid treatment process after the boric acid treatment process of having carried out stretching to each operation of washing step, carry out Tension Control, and make each self-sustaining substantially constant of tension force of above-mentioned film.
In addition, polaroid of the present invention is the polaroid of bonding protective film on the single face of above-mentioned polarization film at least.This protective film can possess phase-contrast film, brightness improving film, field angle and improve any one function in film and the Transflective film.Perhaps; polaroid of the present invention also can be on the above-mentioned polaroid of bonding protective film on single face at least, bondingly is selected from that phase difference film, brightness improving film, field angle improve at least a in film and the Transflective sheet and the optical laminate that makes.
[effect of invention]
According to the present invention, owing to, the tension force that is applied on the above-mentioned film is maintained fixed substantially by carrying out Tension Control in each operation after stretch processing, thereby inhibition tension change, therefore, make stableization of film, have the effect that can reduce the film color spot.By polaroid of the present invention, optical laminate are applied to liquid crystal indicator, can obtain slim high-quality LCD.
[embodiment]
Below, the present invention is described in detail.
Form the polyvinyl alcohol resin of polyvinyl alcohol film of the present invention, generally can enumerate the resin that the polyvinyl acetate resinoid is carried out saponification and obtain.Saponification degree be 85 moles of % or more than, be preferably 90 moles of % or more than, 99 moles of %～100 mole % more preferably.As the polyvinyl acetate resinoid, except polyvinyl acetate, can enumerate vinyl acetate and the interpolymer that can carry out the monomer of copolymerization with it as vinyl acetate list aggressiveness, for example, ethane-acetic acid ethyenyl interpolymer etc.As other monomers that can carry out copolymerization, for example, can enumerate unsaturated carboxylic acid, olefines, vinyl ethers, unsaturated sulfonic acid class etc.The degree of polymerization of polyvinyl alcohol resin is 1000～10000, is preferably about 1500～5000.
Can also carry out modification to these polyvinyl alcohol resins, for example, can use by aldehydes and carry out modified polyethylene alcohol formal, polyvinyl acetal, polyvinyl butyral etc.Usually, as the parent material of polarization film, used thickness is 20 μ m～100 μ m, be preferably this film that does not stretch of polyvinyl alcohol resin film of 30 μ m～80 μ m.Industrial, thin-film width is that 1500mm～4000mm is practical.
Successively this non-stretched film is carried out expansion process, dyeing processing, boric acid processing, washing processing, carry out drying at last, the thickness of prepared polyvinyl alcohol polarization film is for example about 5～50 μ m.
Polarization film of the present invention is the polyvinyl alcohol single axle drawn membrane of dead axle absorption dichromatism pigment, and its manufacture method roughly is divided into 2 kinds.The 1st kind of method is in air or inert gas, polyvinyl alcohol film is carried out uniaxial tension after, carry out successively that expansion process, dyeing are handled, boric acid is handled and washing is handled, and carries out dry method at last.The 2nd kind of method is in aqueous solution, successively the polyvinyl alcohol film that does not stretch being carried out expansion process, dyeing processing, boric acid processing and washing handles, in the operation before boric acid treatment process and/or boric acid treatment process, carry out the wet type uniaxial tension, carry out dry method at last again.
In any one method, uniaxial tension can carry out in 1 operation, also can carry out in 2 or above operation, preferably carries out in a plurality of operations.Drawing process can adopt known method, for example, by between 2 nip rolls of handle thin films, producing the stretching of the roll shop building that difference stretches, the hot roll pulling method of putting down in writing as No. 2731813 communiques of patent, tentering pulling method etc.In addition, the order of operation is order as described above basically, for the amount for the treatment of fluid and treatment conditions etc. without limits.
In addition, can certainly insert the operation that does not have record in the above-mentioned operation for other purposes.Example as such operation, after can being set forth in boric acid and handling, the dip treating (iodide processing) of being undertaken by not borated iodide aqueous solution or contain dip treating (zinc processing) operation that the aqueous solution of zinc chloride carries out etc. by boronic acid containing not.
Expansion process for the foreign matter of removing film surface, remove plastifier in the film, provide the easy dyeing in the subsequent handling, the plasticized of film etc. to carry out.Treatment conditions are set in the scope of defectives such as the excessive dissolution that can reach these purposes and not cause the base material film, the forfeiture transparency.When oriented film was expanded, film flooded in for example 20 ℃～70 ℃, preferred 30～60 ℃ aqueous solution.The dip time of film is 30 seconds～300 seconds, more preferably about 60～240 seconds.Under situation about the raw films that does not the most stretch being expanded, film floods in for example 10 ℃～50 ℃, preferred 20～40 ℃ aqueous solution.The dip time of film is 30 seconds～300 seconds, more preferably about 60～240 seconds.
In the expansion process operation, owing to be easy to generate that the film broad ways expands and on film, produce problem such as CREASE MARK, the preferred CREASE MARK that uses known wide cut devices such as tentering roll (expander roll), spiral roll (spiral roll), roll (crown roll), cloth guider (cross guider), curved rod (bend bar), expanding folder (tenter clip) to eliminate film on one side, on one side handle thin films.In order to reach in solution the purpose of handle thin films stably, utilize the current in the shower control expansion solutions in the water, perhaps adopting EPC device (marginal position control device: detect the edge of film and prevent the device of film complications) etc. simultaneously is of great use.In this operation,, for example, preferably take the methods such as speed of carrying roll before and after the control and treatment because film is sagging for the film of eliminating throughput direction also along the direction expansion expansion of film operation.In addition, employed expansion process liquid, except pure water, can also use the aqueous solution of the boric acid (opening described in the flat 10-153709 communique) that adds 0.01 weight %～10 weight %, chloride (opening as described in the flat 06-281816 communique), mineral acid, inorganic salts, water-miscible organic solvent, alcohols etc. as the spy as the spy.
The operation of utilizing the dichromatism pigment to dye is in order to reach the dichromatism pigment to be adsorbed on the film, and the purpose that makes it orientation etc. is carried out.Treatment conditions are set in reach these purposes and do not cause in the scope of base material film excessive dissolution, defectives such as the forfeiture transparency etc.When using iodine as the dichromatism pigment, for example, under 10 ℃～45 ℃, preferred 20 ℃～35 ℃ temperature, and in weight ratio, under the concentration of iodine/KI/ water=0.003～0.2/0.1～10/100, carry out 30 seconds～600 seconds, be preferably 60～300 seconds dip treating.Can use other iodide, for example zinc iodide etc. replaces potassium iodide.In addition, other iodide and potassium iodide can also be used simultaneously.In addition, can also with compound such as the coexistences such as boric acid, zinc chloride, cobalt chloride beyond the iodide.When adding boric acid, containing on the iodine this point, be different from following boric acid and handle.With respect to the water of 100 weight portions,, just can regard staining trough as long as contain 0.003 weight portion or above iodine.
When using water-soluble dichroic dye as the dichromatism pigment, for example, under 20 ℃～80 ℃, preferred 30 ℃～70 ℃ temperature, and in weight ratio, under the concentration of dichroic dye/water=0.001～0.1/100, carry out 30 seconds～600 seconds, preferred 60 seconds～300 seconds dip treating.Employed dichroic dye aqueous solution can also contain dyeing assistant etc., for example, can contain inorganic salts, surfactants etc. such as sodium sulphate.Dichroic dye can be used separately, also two kinds or above dichroic dye can be used simultaneously.
As mentioned above, can also be in staining trough oriented film.The method that stretching utilization makes the nip rolls before and after the staining trough have difference is carried out.In addition, also can with expansion process similarly in dyeing liquor and/or solution gateway place tentering roll, spiral roll, roll, cloth guider, curved rod etc. are set.
It is by containing with respect to 100 weight parts waters in the aqueous solution of 1～10 weight portion boric acid of having an appointment, the polyvinyl alcohol film with the dichromatism pigment dyeing being flooded implement that boric acid is handled.When the dichromatism pigment is iodine, preferably contain the iodide of 1～30 weight portion of having an appointment.
As iodide, can enumerate potassium iodide, zinc iodide etc.In addition, can also with compound such as the coexistences such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulphate beyond the iodide.
It is in order to implement by the purpose of crosslinked preventing hydration and color and luster adjusting (preventing to have green etc.) etc. that this boric acid is handled.To turn to by crosslinked waterproof under the situation of purpose, as required, except boric acid, can also use glyoxal, crosslinking chemical such as glutaraldehyde, perhaps use above-mentioned crosslinking chemical with boric acid.
In addition, also the boric acid processing that with the preventing hydration is purpose is called titles such as preventing hydration processing, crosslinking Treatment, localization process sometimes.In addition, also the boric acid that is adjusted to purpose with color and luster is handled titles such as being called complementary color is handled, the processing of dyeing again sometimes.
It is purpose according to handling that this boric acid is handled, and the concentration by suitably changing boric acid and iodide and the temperature for the treatment of fluid are carried out.
With the preventing hydration is the boric acid processing and difference especially of the boric acid processing that is adjusted to purpose with color and luster of purpose, and implements under following condition.
Raw films is expanded, under the situation that dyeing, boric acid are handled, handling when boric acid is when turning to purpose with crosslinked waterproof, use contains the boric acid treating fluid of about 3～10 weight portion boric acid, about 1～20 weight portion iodide with respect to 100 weight portions, usually, under 50 ℃～70 ℃, preferred 55 ℃～65 ℃ temperature, carry out.Dip time was generally about 30～600 seconds, was preferably 60～420 seconds, more preferably 90～300 seconds.
In addition, the film that stretches is in advance dyeed, when boric acid is handled, the temperature of boric acid treating fluid is generally 50～85 ℃, is preferably 55 ℃～80 ℃.
Can also after handling, the boric acid that with the preventing hydration is purpose carry out being adjusted to the boric acid processing of purpose with color and luster.For example, when dichroic dye is iodine,, use to contain the boric acid of 1～5 weight portion of having an appointment, the boric acid treating fluid of about 3～30 weight portion iodide, generally under 10 ℃～45 ℃ temperature, carry out with respect to 100 weight portions for this purpose.Dip time was generally about 3～300 seconds, was preferably 10～240 seconds.
Handle with the boric acid that with the preventing hydration is purpose and to compare, it generally is to carry out under lower boric acid concentration, higher iodide concentration and lower temperature that the boric acid that is adjusted to purpose with color and luster is handled.
These boric acid are handled and also can be carried out in a plurality of operations, carry out in 2～5 operations mostly usually.At this moment, the aqueous solution of employed each boric acid treatment trough is formed, temperature can be identical with above-mentioned scope, also can be different.Above-mentioned is that the boric acid of purpose is handled and handled with the boric acid that color and luster is adjusted to purpose and also can carry out in a plurality of operations respectively with the preventing hydration.
In the boric acid treatment process, also can similarly carry out the stretching of film with dyeing process.Last accumulation draw ratio is approximately 4.5～7.0 times, is preferably 5.0～6.5 times.
After boric acid is handled, wash processing.For example, wash processing as follows: will be adjusted to purpose and to carry out the polyvinyl alcohol that boric acid handles thin film dipped in water with preventing hydration and/or color and luster, and, perhaps flood simultaneously and spray with the form spray water of spray.Water temperature in washing is handled is generally about 2～40 ℃, and dip time can be 2-120 about second.After the washing, in drying oven, under about 40～100 ℃ temperature, carry out about 60～600 seconds drying.
In the present invention, in each operation after stretch processing, carry out Tension Control, make the basic respectively maintenance of tension force of film constant.
In the dyeing treatment process, finish under the situation of stretching, carry out Tension Control in boric acid treatment process afterwards and the washing treatment process.Finish in the operation before dyeing process under the situation of stretching, in the later operation that comprises dyeing treatment process and boric acid treatment process, carry out Tension Control.
When the boric acid treatment process comprises a plurality of boric acid treatment process, preferably initial or from the most initial beginning above-mentioned film that up to the boric acid treatment process in the 2nd step, stretches, and the boric acid treatment process after the boric acid treatment process of carrying out stretch processing is carried out Tension Control up to each operation of washing step; Perhaps preferably from beginning the above-mentioned film that up to the boric acid treatment process in the 3rd step, stretches at first, and the boric acid treatment process after the boric acid treatment process of carrying out stretch processing is up to each operation of washing step, carry out Tension Control, but industrial, more preferably initial or from beginning the above-mentioned film that up to the boric acid treatment process in the 2nd step, stretches at first, and the boric acid treatment process after the boric acid treatment process of carrying out stretch processing is carried out Tension Control up to each operation of washing step.
After carrying out the boric acid processing, carrying out also can in these operations, carrying out Tension Control under the situation that above-mentioned iodide are handled or zinc is handled.
Tension force in each operation can be identical, also can be different.In Tension Control, the tension force of film is restriction especially not, and it suitably is set at per unit width 150N/m～2000N/m, is preferably the scope of 600N/m～1500N/m.If tension force is lower than 150N/m, on film, be easy to produce CREASE MARK etc.On the other hand, if tension force surpasses 2000N/m, will produce the problem that the life-span is reduced.In addition, the tension force of this per unit width is to be calculated by near the width of the film the operation inlet and the tension value of tension detector.
In addition, when carrying out Tension Control, the situation that exists minority to stretch, shrink inevitably, but in the present invention, in stretch processing, do not comprise these situations.
Fig. 1 shows an example of this Tension Control.That is, as shown in Figure 1,, nip rolls 2,3 is set respectively, utilizes these nip rolls 2,3, carry polyvinyl alcohol film 4 along the direction of arrow in the inlet and the exit of treatment trough 1.At the within and without of treatment trough 1, a plurality of guiding rolls have been arranged.Wherein, on the free roll 5 that the binder roll 2 that is close in the porch is provided with later, the equipment tension detector.
As tension detector, generally can use commercially available detecting device, and utilize principles such as difference formula transformer mode, strain gage type to detect tension force.Carry out tension monitoring so continuously.For example, the tension value that detects is transferred into control system 6.In control system 6, when the tension value that detects breaks away from setting value, measure its numerical value, transmit signals to the drive unit (for example, servomotor etc.) that drives exit nip rolls 3, and controlling and driving, thereby make tension value keep constant.
The boric acid treatment process or before treatment process in, according to the relation of carrying out uniaxial tension, the ratio of the rotational speed of the binder roll of control setting before and after the treatment trough and carry out ratio control.Therefore, in the present invention,, make stableization of stretching and film, thereby make the polarization film that does not have color spot by control of associating ratio and Tension Control.
With bonding agent bonding protective film on the one side at least of the polarization film of making like this, thereby make polaroid.
As protective film, the film that can enumerate film that the acetylcellulose resinoid by triacetyl cellulose and diacetyl cellulose and so on constitutes, constitute by the polyester resin of polyethylene terephthalate and poly-naphthalenedicarboxylic acid diethylester, polybutylene terephthalate and so on, the film that constitutes by poly-carbonic acid resinoid, the film that constitutes by the cycloolefin resinoid.As commercially available thermoplasticity cycloolefin resinoid, for example, have " Topas " (registered trademark) of selling, " Arion " (registered trademark) of selling by JSR company, " Zeonor " and " Zeonex " (registered trademark) of selling by Japanese Zeon company by the Ticona society of Germany, by " Apel " (registered trademark) of Mitsui Chemicals (strain) sale etc.The film that will obtain with this cycloolefin resinoid system film is made protective film, during the system film, suitably adopts known method such as solvent casting, extrusion by melting.The cycloolefin based resin film of system film also is commercially available, for example, and by ponding chemical industry (strain) (Sekisui Chemical Co., Ltd.) " the エ ス シ-Na " of Xiao Shouing and " SCA40 " etc.
The thickness of protective film is preferably thin, if but problem such as thickness is too thin, and strength degradation, processability variation on the other hand, if too thick, will produce the transparency and descend, and perhaps the firm time that needs behind the lamination is elongated.Therefore, the suitable thickness of protective film is preferably 10～150 μ m, more preferably 20～100 μ m for for example about 5～200 μ m.
In order to improve the cohesive between bonding agent and polarization film and/or the protective film; can also on polarization film and/or protective film, carry out surface treatments such as corona treatment, flame treatment, plasma treatment, ultraviolet ray irradiation, bottom coating processing, saponification processing.
On protective film, can also be separately or prevent dodging surface treatments such as (anti-glare) processing, antireflection (anti-reflection) processing, hard conating processing, antistatic treatment, antifouling processing in combination.In addition, the protective seam on protective film and/or protective film surface can also contain ultraviolet light absorber and plasticizers such as benzenephosphonic acid ester type compound, p phthalic acid esterification's compound such as benzophenone compound, benzotriazole compound.
This protective film can also be bonded on the single face of polarization film, also can be bonded in two-sided on.
Polarization film and protective film adopt bonding agents such as hydrosolvent class bonding agent, organic solvent class bonding agent, hot melt class bonding agent, solvent-free class bonding agent to carry out lamination.As hydrosolvent class bonding agent, for example, can enumerate polyvinyl alcohol resin aqueous solution, water system two component urethanes emulsion binders etc., as organic solvent class bonding agent, for example, can enumerate two component urethanes bonding agents etc., as solvent-free class bonding agent, for example, can enumerate one-pack type urethanes bonding agent etc.By saponification processing etc. the adhesive surface with polarization film is carried out under the situation of acetylcellulose class film as protective film that water wettability handles using, the polyvinyl alcohol resin aqueous solution is suitable to bonding agent.For the polyvinyl alcohol resin that uses as bonding agent, the alcotex that makes except the polyvinyl acetate as vinyl acetate list aggressiveness being carried out saponification handle, also have to vinyl acetate and with it the multipolymer of other monomers of copolymerization carry out that saponification is handled and the vinyl alcohol-based copolymer that makes, further those hydroxyls carried out partially modified modified polyvinylalcohol base polymer etc.In this bonding agent, can also use polyaldehyde, soluble epoxide compound, melamine compounds etc. as adjuvant.
Method for bonding polarization film and protective film; restriction especially for example, can be set forth on the surface of polarization film or protective film coating adhesive equably; another layer film on folded again on the coated face, and by roll etc. carry out bonding, carry out dry method etc. again.
Usually, bonding agent is after preparation, is coated with under 15～40 ℃ temperature, and tack temperature is generally about 15～30 ℃.Carry out dried after bonding, thereby remove the water equal solvent that in bonding agent, contains, but the baking temperature of this moment is generally 30～85 ℃, is preferably 40～80 ℃.Then, can also 15～85 ℃, be preferably 20～50 ℃, more preferably under 35～45 ℃ the temperature environment, carry out the curing about 1～90 day usually, bonding agent is solidified.If this set time is long, the throughput rate variation, therefore, be about 1～30 day set time, is preferably 1～7 day.
Like this, can pass through adhesive phase, make the single face of polarization film or two-sided the polaroid of bonding protective film.
In the present invention, protective film can also have function as phase-contrast film, as the function of brightness improving film, as the function of reflective film, as the function of Transflective film, as the function of diffusion film, as the optical functions such as function of optical compensating film.In this case; for example by on the protective film surface; optically functional films such as the function of lamination phase-contrast film, brightness improving film, reflective film, Transflective film, diffusion film, optical compensating film; can possess such function; in addition, bring such function can also for protective film itself.In addition, can also make protective film itself have multiple function as the diffusion film of the function with brightness improving film etc.
For example; by carrying out as speciallyying permit No. 2841377 communique, No. 3094113 described stretch processing such as communique of special permission; perhaps by carrying out as speciallyying permit No. 3168850 described processing of communique, bring function can for above-mentioned protective film as phase-contrast film.In addition; open 2002-169025 communique or spy as the spy and open the described method of 2003-29030 communique and form micropore by utilizing; by overlapping selection reflection kernel wavelength different 2 layers or above cholesteric, bring the function of brightness improving film can for above-mentioned protective film again.By on above-mentioned protective film, utilizing precipitation or sputter etc. to form metallic film, can bring function as reflective film or Transflective film.By on above-mentioned protective film, being coated with the resin solution that contains particulate, can bring function as diffusion film.In addition,, and make it directed, can bring function as optical compensating film by liquid-crystal compoundss such as coating デ イ ス コ テ イ Star Network liquid-crystal compoundss on above-mentioned protective film.In addition, can also use suitable adhesive, with brightness improving film, trade names such as trade name: DBEF (ス リ-エ system (strain) produce): commercially available optically functional films such as WV film field angle improved thin film, trade name: Sumikalight (registered trademark) (Sumitomo Chemical (strain)) such as (Fuji's photograph film (strain) productions) equiphase difference film directly are bonded on the polarization film.
Below, by illustrative embodiments the present invention is described more specifically, but the present invention is not limited to these embodiment.In an embodiment, if not otherwise specified, the % of expression content or use amount and part all are weight basis.
In addition, optical property is meant: make among the UV visual spectrophotometric UV2450 of manufacturing in (strain) Tianjin, island, be provided as optional accessory " film hanger rack of polariscope is housed ", and the UV visual spectrum of the polaroid of mensuration transmission direction and absorption direction, color and luster when 2 polaroids are arranged in the intersection Nicol, with JIS-Z8729 is standard, calculates and try to achieve quadrature color and luster, quadrature L
*, quadrature a
*, quadrature b
*
[embodiment 1]
With thickness is polyvinyl alcohol film (the Network ラ レ PVC ニ ロ Application VF-PS#7500 of 75 μ m, the degree of polymerization 2400,99.9 moles of % of saponification degree or more than) place 30 ℃ pure water, lax and make film keep tense situation in order to make film, flooded about 130 seconds, film is expanded fully.
Then, on one side the processing of will thin film dipped weight ratio at iodine/potassium iodide/water dyeing in the aqueous solution that is 0.02/1.5/100, uniaxial tension carries out on one side.Then, will thin film dipped weight ratio at potassium iodide/boric acid/water be in 10/5/100 60 ℃ aqueous solution to carry out boric acid handle on one side, carry out uniaxial tension on one side, be original 5.9 times up to the stretching ratio of accumulating.Further under 40 ℃, be about 30 seconds of dipping in 10/3/100 the aqueous solution with film in the weight ratio of potassium iodide/boric acid/water again, carry out the 2nd hypoborous acid and handle.After carrying out the processing of the 2nd hypoborous acid, wash about 10 seconds with 10 ℃ pure water.
The 2nd hypoborous acid handle and the washing treatment process in, on one side detect separately tension force, control tension force (Tension Control) on one side, the tension force of 2 grooves is all remained on 1250N/m.After the washing, drying is 2 minutes under 60 ℃, and making thickness is the iodine class polarization film of 28 μ m.
Two sided coatings polyvinyl alcohol bonding agent at this polarization film; and protective film [carried out the triacetylcellulose film that saponification is handled from the teeth outwards; " Off ジ ッ Network (registered trademark) T80UNL ", Fuji's photograph film (strain) are produced; thickness 80 μ m] be bonded on the two sides; drying is 5 minutes under 60 ℃, thereby makes polaroid.
Measure 31 points at the off-line place that polaroid quadrature color and luster equates on the flow direction of film,, try to achieve the standard deviation of quadrature b ' value.The result is: standard deviation is 0.2, and gained polaroid color spot is few.
[embodiment 2]
Except as described below carrying out operated boric acid processing of the 2nd step and the Tension Control similarly to Example 1.
On one side will thin film dipped weight ratio at potassium iodide/boric acid/water being to carry out boric acid in 60 ℃ of aqueous solution of 10/5/100 to handle, Yi Bian carry out uniaxial tension, be original 5.9 times up to the draw ratio of accumulating.Further, under 60 ℃, be about 30 seconds of dipping in 10/5/100 the aqueous solution in the weight ratio of potassium iodide/boric acid/water with film, carry out the 2nd hypoborous acid and handle.
Handle and wash in the treatment process at the 2nd hypoborous acid, on one side detection tension force separately, tension force controlled on one side.
The result of standard deviation who tries to achieve quadrature b ' value is as follows: standard deviation is 0.2, and gained polaroid color spot is few.
[embodiment 3]
Except as described below carrying out must be operated boric acid processing of the 3rd step and the Tension Control similarly to Example 1.
On one side be in 55 ℃ of aqueous solution of 10/5/100 with thin film dipped weight ratio at potassium iodide/boric acid/water, carry out uniaxial tension on one side, further on one side will thin film dipped weight ratio be to carry out the 2nd preventing hydration processing in 60 ℃ of aqueous solution of 10/5/100 at potassium iodide/boric acid/water, carrying out uniaxial tension on one side, is original 5.9 times up to the draw ratio of accumulating.Further under 40 ℃, be about 30 seconds of dipping in 10/3/100 the aqueous solution with film in the weight ratio of potassium iodide/boric acid/water, carry out the 3rd hypoborous acid and handle.Handle and wash in the treatment process at the 3rd hypoborous acid, on one side detection tension force separately, tension force controlled on one side.
The result of standard deviation who tries to achieve quadrature b ' value is as follows: standard deviation is 0.2, and gained polaroid color spot is few.
[embodiment 4]
Except as described below carrying out must be operated boric acid processing of the 3rd step and the Tension Control similarly to Example 1.
On one side will thin film dipped weight ratio be to carry out the boric acid processing in 45 ℃ of aqueous solution of 1.5/2/100, Yi Bian carry out uniaxial tension at potassium iodide/boric acid/water.Then, will thin film dipped weight ratio at potassium iodide/boric acid/water be in 10/5/100 60 ℃ aqueous solution, to carry out 2nd hypoborous acid handle on one side, carry out uniaxial tension on one side, be original 5.9 times up to the draw ratio of accumulating.Further under 40 ℃, be about 30 seconds of dipping in 10/3/100 the aqueous solution with film in the weight ratio of potassium iodide/boric acid/water, carry out the 3rd hypoborous acid and handle.Handle and wash in the treatment process at the 3rd hypoborous acid, on one side detection tension force separately, tension force controlled on one side.
The result of standard deviation who tries to achieve quadrature b ' value is as follows: standard deviation is 0.2, and gained polaroid color spot is few.
[comparative example 1]
Except in the 2nd hypoborous acid treatment process and washing treatment process, carrying out ratio control, and pulling out the nip rolls in the porch of each solution and exit than being set at 1, promptly set beyond the condition that can not cause stretching and relax, make polarization film similarly to Example 1.But, work in-process, the tension force of film changes brokenly.The polaroid that uses above-mentioned polarization film to make, the standard deviation of its quadrature b ' value is 0.7, color spot is more than embodiment 1～4.
[description of drawings]
[Fig. 1] is the note figure of an example of demonstration Tension Control of the present invention.
[symbol description]
1. treatment trough
2. nip rolls
3. nip rolls
4. polyvinyl alcohol film
5. free roll
6. control system
Claims (5)
1. polarization film, make by following operation: successively the polyvinyl alcohol film is carried out expansion process, dyeing processing, boric acid processing and washing and handle, described boric acid treatment process comprises a plurality of boric acid treatment process, initial or from the initial beginning described film that up to the boric acid treatment process in the 2nd step, stretches, and the boric acid treatment process after the boric acid treatment process of carrying out stretch processing is constant with tension force basic maintenance in the scope of 600N/m～1500N/m of described film up to each operation of washing step.
2. the manufacture method of a polarization film that comprises the steps, continuously, successively the polyvinyl alcohol film is carried out expansion process, dyeing is handled, boric acid is handled and washing is handled, carry out uniaxial tension in the operation before boric acid treatment process and/or boric acid treatment process, it is characterized in that: described boric acid treatment process comprises a plurality of boric acid treatment process, initial or from the initial beginning described film that up to the boric acid treatment process in the 2nd step, stretches, and the boric acid treatment process after the boric acid treatment process of carrying out stretch processing is carried out Tension Control and is made tension force basic maintenance in the scope of 600N/m～1500N/m of described film constant up to each operation of washing step.
3. polaroid, its by at least on the single face of the described polarization film of claim 1 bonding protective film make.
4. polaroid as claimed in claim 3, wherein above-mentioned protective film possess and are selected from phase-contrast film, brightness improving film, field angle and improve any one function in film and the Transflective film.
5. optical laminate, its by with the described polaroid of claim 3 be selected from phase-contrast film, brightness improving film, field angle and improve bonding the making of at least a film in film and the Transflective film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP318417/2003 | 2003-09-10 | ||
| JP2003318417A JP4323269B2 (en) | 2003-09-10 | 2003-09-10 | Manufacturing method of polarizing film |
| JP318417/03 | 2003-09-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1595211A CN1595211A (en) | 2005-03-16 |
| CN100388023C true CN100388023C (en) | 2008-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100851611A Active CN100388023C (en) | 2003-09-10 | 2004-09-08 | Polarization film and its manufacturing method, polarization sheet and optical laminating body |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4323269B2 (en) |
| KR (1) | KR101093318B1 (en) |
| CN (1) | CN100388023C (en) |
| TW (1) | TWI358548B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101852879A (en) * | 2009-03-30 | 2010-10-06 | 住友化学株式会社 | The manufacture method of light polarizing film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4522320B2 (en) * | 2005-05-31 | 2010-08-11 | 株式会社エフ・ティ・エスコーポレーション | Method for producing transparent heat insulation laminate |
| JP4697964B2 (en) * | 2006-02-24 | 2011-06-08 | 日東電工株式会社 | Polarizer manufacturing method and cleaning apparatus |
| JP4339350B2 (en) | 2006-11-20 | 2009-10-07 | 日東電工株式会社 | Manufacturing method of polarizer |
| JP2008180765A (en) * | 2007-01-23 | 2008-08-07 | Sumitomo Chemical Co Ltd | Manufacturing method of polarizing film |
| JP5548444B2 (en) * | 2009-12-29 | 2014-07-16 | 住友化学株式会社 | Manufacturing method of polarizing plate |
| JP5490750B2 (en) * | 2010-09-03 | 2014-05-14 | 日東電工株式会社 | Manufacturing method of thin polarizing film |
| JP4691205B1 (en) * | 2010-09-03 | 2011-06-01 | 日東電工株式会社 | Method for producing optical film laminate including thin high-performance polarizing film |
| JP2014115673A (en) * | 2010-09-03 | 2014-06-26 | Nitto Denko Corp | Laminate |
| JP5969180B2 (en) * | 2011-08-02 | 2016-08-17 | 日東電工株式会社 | Processed film manufacturing method and apparatus |
| JP5932760B2 (en) * | 2013-11-29 | 2016-06-08 | 住友化学株式会社 | Polarizer and polarizing plate including the same |
| WO2016021432A1 (en) * | 2014-08-04 | 2016-02-11 | 住友化学株式会社 | Production method for polarizing film |
| KR20160023429A (en) * | 2014-08-22 | 2016-03-03 | 스미또모 가가꾸 가부시키가이샤 | Preparing method for polarizer |
| JP5945037B2 (en) * | 2014-09-29 | 2016-07-05 | 住友化学株式会社 | Polarizer |
| CN106226857A (en) * | 2016-08-31 | 2016-12-14 | 武汉优光科技有限责任公司 | A kind of ultra broadband THREE-IN-ONE COMPOSITE ACHROMATIC phase delay chip |
| JP7083611B2 (en) * | 2017-09-26 | 2022-06-13 | 住友化学株式会社 | Film transport method and transport device, and processed film manufacturing method and manufacturing device |
| CN112327539B (en) * | 2020-11-25 | 2022-10-14 | 合肥德瑞格光电科技有限公司 | Preparation method of polaroid for TFT-LCD |
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| JPH10153709A (en) * | 1996-11-22 | 1998-06-09 | Tokai Rubber Ind Ltd | Production of polarizer film |
| JP2001174634A (en) * | 1999-12-15 | 2001-06-29 | Sumitomo Chem Co Ltd | Method of producing polarizing film |
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| JP2002182035A (en) * | 2000-12-19 | 2002-06-26 | Nitto Denko Corp | Polarizing film, method for producing the same and polarizing plate using the same |
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2003
- 2003-09-10 JP JP2003318417A patent/JP4323269B2/en not_active Expired - Fee Related
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2004
- 2004-08-30 TW TW093126078A patent/TWI358548B/en active
- 2004-09-07 KR KR1020040071082A patent/KR101093318B1/en active IP Right Grant
- 2004-09-08 CN CNB2004100851611A patent/CN100388023C/en active Active
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| JPH10153709A (en) * | 1996-11-22 | 1998-06-09 | Tokai Rubber Ind Ltd | Production of polarizer film |
| JP2001174634A (en) * | 1999-12-15 | 2001-06-29 | Sumitomo Chem Co Ltd | Method of producing polarizing film |
| CN1318755A (en) * | 2000-04-17 | 2001-10-24 | 黄精忠 | Continuous H-type polarization film producing process |
| JP2002182035A (en) * | 2000-12-19 | 2002-06-26 | Nitto Denko Corp | Polarizing film, method for producing the same and polarizing plate using the same |
| CN1409136A (en) * | 2001-10-03 | 2003-04-09 | 日东电工株式会社 | Method for producing polaroid and liquid crystal display with poloroid |
| CN1412580A (en) * | 2001-10-16 | 2003-04-23 | 日东电工株式会社 | Method for mfg. polaroid and liquid crystal display device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101852879A (en) * | 2009-03-30 | 2010-10-06 | 住友化学株式会社 | The manufacture method of light polarizing film |
| CN101852879B (en) * | 2009-03-30 | 2014-02-26 | 住友化学株式会社 | Process for producing a polarizing film |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI358548B (en) | 2012-02-21 |
| KR101093318B1 (en) | 2011-12-14 |
| CN1595211A (en) | 2005-03-16 |
| JP4323269B2 (en) | 2009-09-02 |
| TW200510762A (en) | 2005-03-16 |
| KR20050026860A (en) | 2005-03-16 |
| JP2005084505A (en) | 2005-03-31 |
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