CN103992606B - Polyvinyl alcohol film - Google Patents
Polyvinyl alcohol film Download PDFInfo
- Publication number
- CN103992606B CN103992606B CN201410262444.2A CN201410262444A CN103992606B CN 103992606 B CN103992606 B CN 103992606B CN 201410262444 A CN201410262444 A CN 201410262444A CN 103992606 B CN103992606 B CN 103992606B
- Authority
- CN
- China
- Prior art keywords
- film
- polyvinyl alcohol
- degree
- pva
- light polarizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Mechanical Engineering (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention relates to a kind of polyvinyl alcohol film.The present invention provides a kind of film, its raw material that can be used as manufacturing the light polarizing film with high polarity energy, and comprises the polyvinyl alcohol of high polymerization degree.Polyvinyl alcohol film, it is characterised in that comprise the polyvinyl alcohol that the degree of polymerization is 5100～10000, swellbility is 200～the degree of delay of 240%, the central part of width is 10～40nm.In this polyvinyl alcohol film, the saponification degree of the most above-mentioned polyvinyl alcohol is 98 moles of more than %, and the thickness of preferably polyethylene alcohol film is 10～120 μm.
Description
Technical field
The present invention relates to the polyvinyl alcohol film that can use as the raw material of the good light polarizing film of polarizing properties.
Background technology
Liquid crystal indicator (LCD), at its initial stage of development, is used for the miniature instrument of desk top computer and wrist-watch etc.
In, but in recent years, start to use it for notebook computer, liquid crystal display, color liquid crystal projector, LCD TV, vehicle-mounted
The broad range of navigation system, portable phone, the spendable metrical instrument of indoor and outdoor etc..On the other hand, especially at LCD TV
Deng purposes in, people require all the more the raising of the raising of display quality, such as contrast, even for as LCD component it
The Polarizer of one, is also strongly required the raising of polarizing properties.
The Polarizer commonly used at present has the single or double in light polarizing film and fits three cellulose acetate membrane or acetic acid
The composition of the protecting film such as cellulose butyrate film, described light polarizing film is for comprising polyvinyl alcohol (hereinafter sometimes referred to as PVA)
Base film is implemented uniaxial tension, is used the dyeing of iodine or dichroic dye to process, use the fixing process etc. of boron compound and obtain
Light polarizing film.Method as the polarizing properties improving this Polarizer, it is proposed that the structure of the PVA as raw material is changed
Good method, the method for the physical property of PVA film that controls, the various methods such as method of manufacturing condition of research Polarizer, it contributes to
The raising of LCD contrast.
Such as in patent documentation 1, describe the polarisation comprising the PVA that the degree of polymerization is more than 2500, preferably 6000～10000
Film has the optical characteristics of excellence.Using the PVA that the degree of polymerization is high, this is advantageous approach for improving polarizing properties, but is difficult to
Industrially implement.
It addition, as other method of raising polarizing properties, such as recorded the manufacturer of light polarizing film in patent documentation 2
Method, its use PVA mesentery as base film, the pass of described PVA mesentery consolute temperature (X) in the hot water and Equilibrium swelling ratio (Y)
It is for the scope shown in following formula.
Y ＞-0.0667X+6.73 (I)
X ≥ 65 ・・・・(II)
But, the degree of polymerization of the PVA used in foregoing invention is preferably the scope of 3500～5000, comparative example described as follows
Shown in, even if this manufacture method to be directly applied to high polymerization degree PVA, find that the polarizing properties of the light polarizing film obtained does not fills
Point.That is, in order to industrially manufacture the light polarizing film of the PVA comprising high polymerization degree, comprehensive and the structure of PVA, the thing of PVA film are needed
The relevant knowledge such as property find the condition of optimal raw material.
Patent documentation 1: Japanese Unexamined Patent Publication 1-105204 publication
Patent documentation 2: Japanese Unexamined Patent Publication 7-120616 publication.
Summary of the invention
Therefore, it is an object of the invention to provide can be used as manufacturing have high polarity can light polarizing film raw material,
And comprise the film of the PVA of high polymerization degree.
The knowledge of the physical property that inventor etc. play the structure about PVA and PVA film to greatest extent is studied.Result
Finding that following PVA film achieves above-mentioned purpose, thus complete the present invention, described PVA film is characterised by, comprises the degree of polymerization and is
The PVA of 5100～10000, swellbility is 200～240%, and the degree of delay of the central part of width is 10～40nm.
In the case of Gai, the saponification degree of the most above-mentioned PVA be 98 moles of more than %.
Additionally, it is preferred that the thickness of PVA film is 10～120 μm.
The present invention also comprises the manufacture method of above-mentioned PVA film, and it is by containing the PVA that the degree of polymerization is 5100～10000 and water
Film forming stock solution carry out film forming as raw material.
The present invention the most also comprises and carries out above-mentioned PVA film dyeing, stretches and the light polarizing film that obtains.
The PVA film of the present invention can use as the raw material of the good light polarizing film of polarizing properties.The light polarizing film obtained can
Being effective to the making of Polarizer, described Polarizer is desk top computer, wrist-watch, notebook computer, liquid crystal display, liquid
The liquid crystal of brilliant color projecting apparatus, LCD TV, vehicle-mounted navigation system, portable phone, the spendable metrical instrument of indoor and outdoor etc.
The component parts of display device.
Detailed description of the invention
The present invention explained in detail below.
In order to tackle the good polarizing properties of the light polarizing film as the object of the invention, the polymerization of the PVA used in the present invention
Degree needs to be 5100～10000, preferably 5200～9500, more preferably 5400～9200.If the degree of polymerization of PVA is less than
5100, then when manufacturing light polarizing film, it is difficult to performance high polarity energy.On the other hand, if the degree of polymerization of PVA is more than 10000, then
The productivity ratio of PVA reduces.Should illustrate, in the present invention, the degree of polymerization of so-called PVA refers to according to described in following embodiment
The degree of polymerization (viscometric degree of polymerization) that measures of method.
It addition, the saponification degree of PVA is preferably 98 moles of more than %, more preferably 99 moles more than %, and then preferably 99.5
Mole more than %, most preferably 99.8 moles more than %.If the saponification degree of PVA is less than 98 moles of %, then in the manufacture work of light polarizing film
In sequence, having PVA to be prone to dissolution, the PVA of dissolution is attached on film make the possibility of the hydraulic performance decline of light polarizing film.
The PVA used in the present invention can manufacture by polyvinylesters based polymer is carried out saponification, described poly-second
Alkenyl esters based polymer obtains by being polymerized by vinyl esters.Vinyl esters can enumerate vinylacetate, vinyl formate,
Propionate, vinyl butyrate, pivalic acid vinyl acetate, vinyl neodecanoate (バ サ テ ィ ッ Network acid PVC ニ Le), lauric acid
Vinyl acetate, stearic acid vinyl ester, vinyl benzoate etc., can select one kind or two or more from which.Wherein, from obtaining easily
Property, PVA manufacture easiness, cost angularly consider, vinylacetate is preferably used.Polymerization temperature is not particularly limited,
When using methanol as polymer solvent, preferable polymerization temperature is preferably near the boiling point of methanol to be about 60 DEG C.
As long as not damaging the effect of the present invention, PVA is not limited to the saponified of the homopolymer of vinyl esters.Can also be such as
With the ratio less than 5 moles of % by unsaturated carboxylic acid or derivatives thereof, unsaturated sulfonic acid or derivatives thereof, carbon number on PVA
Be 2～30 alpha-olefin etc. carry out the modified PVA of graft copolymerization;By vinyl esters and unsaturated carboxylic acid or derivatives thereof,
Unsaturated sulfonic acid or derivatives thereof, carbon number be 2～30 alpha-olefin etc. carry out copolymerization with the ratio less than 15 moles of % and form
Modified polyvinyl ester saponified;With aldehydes such as formalin, butyraldehyde, benzaldehydes by the part crosslinking of the hydroxyl of PVA
Pioloform, polyvinyl acetal based polymer etc..
By by above-mentioned PVA film forming, the PVA film of the present invention can be obtained.Film build method is except melting aqueous PVA
Beyond the method for extrusion, it is also possible to use casting filming therapy, wet type membrane formation process (discharging in poor solvent), gel membrane formation process
(after temporary transient for PVA aqueous solution cooling gel, extraction remove solvent), be cast into embrane method (キ ャ ス ト embrane method) and (make PVA water
Solution flows on substrate, is dried) and by the method etc. of these Combination of Methods.Wherein, from available good PVA film
Angle considers, preferred molten is extruded into embrane method and casting filming therapy.The solvent used during film forming is preferably used water.
Mainly comprise the volatile matter rate (point rate) of the film forming stock solution of PVA and solvent according to film build method or PVA point
Son is measured and is varied from, but preferably 50～95 mass %, more preferably 60～95 mass %, and then preferably 70～95 mass %.If
Volatile matter rate is less than 50 mass %, then the viscosity that there is film forming stock solution is too high, and filtration or froth breaking during modulation become difficulty, it is difficult to
Obtain the possibility of the PVA film of free from admixture or defect.If it addition, volatile matter rate is more than 95 mass %, then there is the viscous of film forming stock solution
Spend low, it is difficult to manufacture the possibility of the PVA film with target thickness or high thickness and precision.
When manufacturing the PVA film of the present invention, it is possible to use plasticizer.Plasticizer can enumerate glycerol, diglycerol, second two
Alcohol etc., but it is not limited to this.The usage amount of plasticizer is not particularly limited, and being commonly angled relative to PVA100 mass parts is 10～15 matter
In the range of amount part.
As the drying means of the PVA film after film forming, such as, can enumerate the contact being dried, using hot-rolling using hot blast
It is dried or uses being dried of infrared heater.Can be used alone a kind in these methods, it is also possible to by two or more group
Close and use.Baking temperature is not particularly limited, preferably in the range of 50～70 DEG C.Although it addition, drying time now
Also rely on concentration or the membrance casting condition of film forming stock solution, but about 45～75 minutes.
After dry PVA film damping moisture rate (moisture content) being regulated, only by the parallel both sides of film, preferable width side
To both sides fix, in the range of 100～140 DEG C, carry out heat treatment, thus utilize the stress reduced with moisture and produce,
Film can be applied stable stretching.Thus, it is possible to stably give the following low-level degree of delay of film.The now moisture rate of film
It is preferably 1～15 mass %, more preferably 1～10 mass %, and then preferably 2～6 mass %.The time of heat treatment limits the most especially
Fixed, it is different according to heat treatment temperature, but within substantially 5 minutes.
The thickness of the PVA film of the present invention so obtained is preferably 10～120 μm, more preferably 12～80 μm, and then preferably
15～75 μm, most preferably 20～60 μm.If thickness is less than 10 μm, then in following stretching process, have and be prone to film
The possibility of fracture.If it addition, thickness is more than 120 μm, then there is the film upper stress when stretching and become big, it is difficult to sufficiently draw
The possibility stretched.
The swellbility of the PVA film of the present invention needs to be 200～240%, preferably 205～235%, more preferably 210～230%.As
Really swellbility is less than 200%, then overtension when stretching, it is difficult to sufficiently stretch.If it addition, swellbility exceedes
240%, then water absorption is high, and therefore in the manufacturing process of following light polarizing film, film is prone to produce fold or butt curl, becomes
The reason of fracture during stretching.In order to swellbility be controlled in predetermined scope, such as, the PVA film after film forming can will be carried out heat
Temperature during process or Timing are in the most above-mentioned scope.The swellbility of PVA film may utilize the following side in embodiment project
Method is measured.
In the PVA film of the present invention, the degree of delay of the central part of width needs to be 10～40nm, more preferably 13～
37nm, and then preferably 17～33nm, most preferably 20～30nm.If degree of delay is less than 10nm, then manufacture dyeing during light polarizing film
Slow, be thus susceptible to produce dyeing inequality.If it addition, degree of delay is more than 40nm, even the lowest stretching ratio, it is possible to
Produce the fracture of film.The following method that the degree of delay of PVA film may utilize in the project of embodiment is measured.
In order to the degree of delay of PVA film being controlled in predetermined scope, except above-mentioned carries out heat treatment by after PVA film damping
Method beyond, it is also possible to enumerate the method utilizing known method stretching PVA film, but be not limited to these methods.Wherein, from inciting somebody to action
From the point of view of the degree of delay produced is fixing, after damping, preferably carry out heat-treating methods.Now, only parallel by PVA film
Both sides, the both sides in preferable width direction are fixed and carried out heat treatment is important.If not fixing film, or carry out fixing for surrounding
Heat treatment, then the stress of film is isotropic, degree of delay does not the most occur, it is impossible to realize purpose.
Then, for using the manufacture method of the light polarizing film of the PVA film blank of the present invention to describe.The manufacture of light polarizing film
Operation can regulate containing moisture, dye, stretch, the operation of colourity regulation etc..Now, the wet tensile of film is preferably carried out.Separately
Outward, as required, it is also possible to the then operation of wet tensile, stretch by gained stretched film and then in boric acid aqueous solution.Enter one
Step ground, as required, such as, can carry out colourity regulation in the aqueous solution containing boric acid and potassium iodide, and be dried, system
Make light polarizing film.
The moisture regulation of PVA film is preferably immersed in pure water or distilled water and carries out.Temperature now is preferably 20～40
DEG C, more preferably 25～35 DEG C, and then preferably 27～33 DEG C.If temperature is less than 20 DEG C, then there is the moisture content step-down of film blank,
During stretching afterwards, the tension force of film uprises, the possibility that the polarizing properties of the light polarizing film obtained reduces.If it addition, temperature is more than 40
DEG C, then the water absorption that there is film blank uprises, and in operation later, film is prone to produce fold or butt curl, becomes stretching
Time fracture the possibility of reason.On the other hand, as the time of impregnated membranes blank, probably in the range of 30～120 seconds.
The dyeing of PVA film is such as carried out in IKI aqueous solution.Now the concentration of preferred iodine is 0.01～0.1 matter
Amount %, the concentration of potassium iodide be 1～10 mass %, more preferably iodine concentration be 0.02～0.08 mass %, potassium iodide concentration be 2～8 matter
Amount %, so preferably iodine concentration be 0.03～0.06 mass %, potassium iodide concentration be 3～6 mass %.The temperature of aqueous solution does not has spy
Do not limit, preferably 25～40 DEG C.
The wet tensile of PVA film blank can also be carried out as the operation mutually independent with the regulation of above-mentioned moisture or dyeing,
But effectively preferably carry out in the water of above-mentioned moisture regulation or in the aqueous solution of dyeing, more preferably at the water of dyeing
Solution, i.e. IKI aqueous solution are carried out.PVA film blank, when wet tensile, represents with the length ratio of the film before and after stretching
Stretching ratio be preferably 2.0～2.9 times, more preferably 2.2～2.8 times, and then preferably 2.4～2.8 times.
From the point of view of the light polarizing film that available polarizing properties is the most excellent, PVA film is carried out temperature during wet tensile
Degree is preferably 20～40 DEG C, more preferably 25～40 DEG C, and then preferably 25～35 DEG C, particularly preferred 27～33 DEG C.
As mentioned above, it is also possible to then PVA film is carried out the operation of wet tensile, by the stretched film that obtains further at boron
Aqueous acid stretches.Stretching ratio now is preferably less than 3 times, more preferably 1.2～3 times, so preferably 1.3～
2.9 times, most preferably 1.4～2.8 times.
The boric acid concentration in aqueous solution now is preferably 2～6 mass %, more preferably 2～5 mass %, and then preferably 2～4
Quality %.When the concentration of boric acid is less than 2 mass %, it is possible in the light polarizing film obtained, mottle becomes many.It addition, work as the dense of boric acid
When degree is more than 6 mass %, there is the crosslinking excess of the PVA caused by boric acid, it is difficult to film is carried out with high magnification the possibility stretched.
It addition, in order to make the form and aspect of light polarizing film close to neutral gray, further preferably add potassium iodide in boric acid aqueous solution.
The concentration of potassium iodide is preferably 3～10 mass %, more preferably 4～8 mass %.When the concentration of potassium iodide is less than 3 mass %, gained
The green of light polarizing film likely becomes strong.On the other hand, when the concentration of potassium iodide is more than 10 mass %, the redness of gained light polarizing film
Likely become strong.Boric acid aqueous solution can also contain the metallic compound composition as other of such as ferrum, zirconium etc..
In above-mentioned stretching, the temperature of aqueous solution is not particularly limited, preferably 50～60 DEG C, more preferably 55～60
DEG C, and then preferably 57～60 DEG C.If draft temperature is less than 50 DEG C, then has and can not sufficiently stretch, gained light polarizing film
The possibility that degree of polarization declines.If it addition, draft temperature is more than 60 DEG C, then there is the possibility that the transmitance of gained light polarizing film reduces.
Be preferably 4.5～7.0 times by the stretching ratio of whole operations, more preferably 4.7～6.5 times, and then preferably 5.0～
6.0 again.If stretching ratio is less than 4.5 times, then there is the possibility that the polarizing properties of gained light polarizing film reduces.If it addition, stretching
More than 7.0 times, then there is the fracture of fecund filming in stretching, it is difficult to stably manufacture the possibility of light polarizing film in multiplying power.
Colourity regulation after stretching is preferably carried out in the aqueous solution containing boric acid and potassium iodide.At this time it is also possible at water
Solution adds the metallic compound of zinc chloride, zinc iodide etc..In order to prevent the decline of polarizing properties, the temperature of aqueous solution is preferred
Lower than draft temperature, the most preferably 20～50 DEG C, more preferably 30～40 DEG C.The time of colourity regulation limits the most especially
Fixed.
Being dried of gained light polarizing film can use various drying machine, utilizes and contacts on batch (-type), the most swing, continuous rolling
The method of formula etc. is carried out.In order to prevent iodine from being distilled by light polarizing film, and suppress to react with the disengaging of the boric acid of PVA crosslinking, excellent
Being selected in baking temperature is to carry out at 40～80 DEG C, more preferably 45～70 DEG C, and then preferably 50～60 DEG C.Drying time is the most especially
Ground limits, and it is different, such as in the range of 3～6 minutes according to device, baking temperature.
Embodiment
Hereinafter, specifically describe the present invention by embodiment etc., but the present invention is not limited in any way the following examples.?
In embodiment etc., the viscometric degree of polymerization P of PVA, the swellbility of PVA film, degree of delay Re of PVA film, absorbance Y of light polarizing film and partially
Degree of shaking V is evaluated by following method.
(1) that PVA0.28g, distilled water 70g and stirrer are joined 100mL is common for the mensuration of the viscometric degree of polymerization P of PVA
In ground connection (common The り closes わ せ) conical flask.In the temperature chamber of 95 DEG C, dipping covers the above-mentioned triangle of stopper and burns
Bottle, with stirrer stirring while being dissolved by PVA, makes 0.4%PVA aqueous solution.By this PVA aqueous solution buchner funnel shape
Glass filter 3G filters, and cools down in the thermostatic water bath of 30 DEG C, makes polymerization degree measurement sample.As control sample,
In another 100mL common ground connection conical flask, add 70g distilled water and cover stopper, being immersed in the thermostatic water bath of 30 DEG C
In.
The evaporating dish heated 1 hour with the drying machine of 105 DEG C is cooled down 30 minutes in exsiccator, measures the matter of evaporating dish
Amount a (g).Utilize the full pipet that holds to transfer in this evaporating dish by polymerization degree measurement sample 10mL, use 105 DEG C dry
After machine is dried 16 hours, cool down 30 minutes in exsiccator, quality measurement b (g).The concentration c (g/L) of polymerization degree measurement sample
Following formula is utilized to calculate.
c = 1000×(b-a)/10
In オ ス ト ワ Le De viscometer, entirely hold pipet with 10mL add polymerization degree measurement sample or distilled water,
The thermostatic water bath of 30 DEG C stabilizes it 15 minutes.Measure add polymerization degree measurement sample fall number of seconds t1(s) and steaming
Distilled water fall number of seconds t0S (), utilizes following formula to calculate viscometric degree of polymerization P.
ηr = t1/t0
[η] = 2.303×Log(ηr/c)
Log(P) = 1.613×Log([η]×104/8.29)
(2) PVA film is cut into the size of 5cm × 5cm by the mensuration of the swellbility of PVA film, in the distilled water 1L of 30 DEG C
Impregnate 4 hours.This PVA film is taken out from distilled water, clamp the water droplet of sorbent surface with 2 filter paper after, quality measurement D.
Further, this PVA film is dried 16 hours with the drying machine of 105 DEG C, after cooling down 30 minutes in exsiccator, quality measurement E,
Following formula is utilized to calculate the swellbility of PVA film.
A = 100×D/E(%)
(3) central part from PVA film that measures of degree of delay Re of PVA film takes width 5cm × flow direction
The Rectangular samples of 10cm, uses the optical material of big electronics society to check device RETS-1100, to measuring wavelength is
Degree of delay Re at 550nm is measured.
(4) mensuration of absorbance Y of light polarizing film
From the central part of the width of light polarizing film, take on 2 4cm(draw directions) on × 4cm(width)
Foursquare sample, use the spectrophotometer U-4100 (with integrating sphere) of Hitachi, according to JIS Z 8722
(assay method of object color), carries out the visibility correction of the visible region in illuminant-C, 2 ° of visuals field, for 1 light polarizing film sample
Product, the absorbance of light when measuring the absorbance of light when tilting 45 ° relative to tensile axis direction and inclination-45 °, and try to achieve it
Meansigma methods Y1 (%).For another 1 light polarizing film sample, when the transmitance of light during same mensuration inclination 45 ° and inclination-45 °
The transmitance of light, try to achieve their meansigma methods Y2 (%).Utilize following formula Y1 and Y2 is average, as absorbance Y of light polarizing film
(%)。
Y = (Y1+Y2)/2
(5) mensuration of the degree of polarization V of light polarizing film
In the same manner as the situation of the absorbance described in (4), measure 2 light polarizing film taking in above-mentioned (4) with it
Absorbance Y of light during the parallel mode overlap of draw direction | | (%) and light during overlap in the way of draw direction is orthogonal
Absorbance Y ⊥ (%), utilizes following formula to try to achieve degree of polarization V (%).
V = {(Y||-Y⊥)/(Y||+Y⊥)}1/2×100
[embodiment 1]
Using be 5800 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 40 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film does not shrinks, carry out 3 at 120 DEG C
Minute heat treatment.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is 230%.Separately
Outward, utilizing the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 29nm.
Then, above-mentioned PVA film is cut into the size of flow direction 11cm × width 10cm, make with flow direction
For draw direction, it is arranged on the stretching clamp that jaw separation is 4cm, it is impregnated 1 minute in the pure water of 30 DEG C, then exists
Containing 0.03 mass % iodine, 3 mass % potassium iodide dyeing liquor (temperature 30 DEG C) in dipping, with the speed tensile of 0.13m/min extremely
2.6 times, iodine is made to adsorb.
Then, this stretched film is immersed in containing 4 mass % boric acid, the stretching liquid (temperature 57.5 DEG C) of 6 mass % potassium iodide
In, with the speed tensile of 0.13m/min to after 2.3 times, draw direction is fixed, is dried 4 minutes at 50 DEG C, obtains polarisation
Film.The method described in above-mentioned (4) and (5) is utilized to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%,
99.99%, the light polarizing film that polarizing properties is good can be obtained.
[embodiment 2]
Using be 5800 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 40 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film does not shrinks, carry out at 115 DEG C
The heat treatment of 3 minutes.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is 240%.
It addition, utilize the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 26nm.
Then, similarly to Example 1, stretch above-mentioned PVA film and make iodine adsorb, carry out further stretching and
Obtain light polarizing film.Utilizing the method described in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively
It is 44.0%, 99.96%, the light polarizing film that polarizing properties is good can be obtained.
[embodiment 3]
Using be 9100 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 20 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film does not shrinks, enter at 110 DEG C
The row heat treatment of 3 minutes.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is
230%.It addition, utilize the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 39nm.
Then, in addition to making stretching ratio be 2.5 times, similarly to Example 1, above-mentioned PVA film one is stretched
While make iodine adsorb, stretch further, obtain light polarizing film.The method described in above-mentioned (4) and (5) is utilized to measure this light polarizing film
Transmitance and degree of polarization, result is respectively 44.0%, 99.95%, can obtain the light polarizing film that polarizing properties is good.
[embodiment 4]
Using be 5200 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 40 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film does not shrinks, enter at 135 DEG C
The row heat treatment of 3 minutes.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is
205%.It addition, utilize the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 29nm.
Then, similarly to Example 3, stretch above-mentioned PVA film and make iodine adsorb, stretch further,
Obtain light polarizing film.Utilizing the method described in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively
It is 44.0%, 99.95%, the light polarizing film that polarizing properties is good can be obtained.
[embodiment 5]
Using be 5500 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 30 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film does not shrinks, carry out at 130 DEG C
The heat treatment of 3 minutes.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is 215%.
It addition, utilize the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 29nm.
Then, similarly to Example 1, stretch above-mentioned PVA film and make iodine adsorb, stretch further,
Obtain light polarizing film.Utilizing the method described in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively
It is 44.0%, 99.99%, the light polarizing film that polarizing properties is good can be obtained.
[comparative example 1]
Using be 4800 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
6.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 40 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film shrinks the most in the width direction, at 120 DEG C, carry out 3
Minute heat treatment.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is 220%.Separately
Outward, utilizing the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 28nm.
Then, in addition to making stretching ratio be 2.7 times, similarly to Example 1, above-mentioned PVA film one is stretched
While make iodine adsorb, stretch further, obtain light polarizing film.The method described in above-mentioned (4) and (5) is utilized to measure this light polarizing film
Transmitance and degree of polarization, result is respectively 44.0%, 99.92%, and the degree of polarization of light polarizing film is the most not enough.
[comparative example 2]
Using be 5800 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 40 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film does not shrinks, carry out at 140 DEG C
The heat treatment of 3 minutes.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is 195%.
It addition, utilize the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 29nm.
Then, similarly to Example 1, stretch above-mentioned PVA film and make iodine adsorb, stretch further,
Obtain light polarizing film.Utilizing the method described in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively
Being 44.0%, 99.92%, the degree of polarization of light polarizing film is the most not enough.
[comparative example 3]
Using be 5800 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 40 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film does not shrinks, carry out at 110 DEG C
The heat treatment of 3 minutes.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is 250%.
It addition, utilize the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 28nm.
Then, similarly to Example 1, stretch above-mentioned PVA film and make iodine adsorb, stretch further,
Obtain light polarizing film.Utilizing the method described in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively
Being 44.0%, 99.87%, the degree of polarization of light polarizing film is the most not enough.
[comparative example 4]
Using be 5800 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 40 μm.By this film 26 DEG C, damping 16 hours under conditions of 20%RH, make moisture content regulation to after 3 mass %, fixing
In whole four limits of metal frame, at 120 DEG C, carry out the heat treatment of 3 minutes.The method described in above-mentioned (2) is utilized to measure at heat
The swellbility of the PVA film after reason, result is 230%.It addition, utilize the method described in above-mentioned (3) to measure the degree of delay of PVA film,
Result is 5nm.
Then, similarly to Example 1, stretch above-mentioned PVA film and make iodine adsorb, carry out further stretching and
Obtain light polarizing film.Utilizing the method described in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively
Being 44.0%, 99.97%, polarizing properties is good, if but so that the state that light polarizing film is orthogonal is observed, then find big dye
Color is uneven.
[comparative example 5]
Using be 5800 containing the degree of polymerization, saponification degree be PVA 100 mass parts of 99.8 moles of % and as the glycerol of plasticizer
5.5 mass %PVA aqueous solutions of 12 mass parts, in the metallic roll of 60 DEG C be cast, carry out 60 minutes be dried, obtaining thickness is
The PVA film of 40 μm.By this film 26 DEG C, damping 16 hours under conditions of 65%RH, make moisture content regulation to after 8 mass %, by film
The two ends of width be fixed on the parallel both sides of metal frame so that film does not shrinks, carry out at 120 DEG C
The heat treatment of 3 minutes.Utilizing the swellbility of the PVA film after the method mensuration heat treatment described in above-mentioned (2), result is 230%.
It addition, utilize the method described in above-mentioned (3) to measure the degree of delay of PVA film, result is 70nm.
Then, similarly to Example 1, stretch above-mentioned PVA film and make iodine adsorb, and then except making stretching times
Rate is beyond 1.8 times, similarly to Example 1, stretches, obtains light polarizing film.Utilize the side described in above-mentioned (4) and (5)
Method measures transmitance and the degree of polarization of this light polarizing film, and result is respectively 44.0%, 99.20%, and the degree of polarization of light polarizing film is the most not enough.
Therefore, in order to improve degree of polarization, the desired value of stretching ratio is changed into 2.3 times from 1.8 times, result generation tension failure, no
Light polarizing film can be obtained.
Collect the above results and be shown in table 1.
[table 1]
Industrial applicability
The light polarizing film obtained by the PVA film of the present invention can be effective to the making of Polarizer, and described Polarizer is desk-top
Electronic computer, wrist-watch, notebook computer, liquid crystal display, color liquid crystal projector, LCD TV, vehicle-mounted navigation system,
The component parts of the liquid crystal indicator of portable phone, the spendable metrical instrument of indoor and outdoor etc..
Claims (8)
1. polyvinyl alcohol film, it is used as the polyvinyl alcohol film of raw material of the light polarizing film that degree of polarization is more than 99.95%, wherein,
Comprising the polyvinyl alcohol that the degree of polymerization is 5100～10000, swellbility is 200～240%, the delay of the central part of width
Degree is 10～40nm, and the saponification degree of above-mentioned polyvinyl alcohol is 98 moles of more than %, and described swellbility measures as follows:
Polyvinyl alcohol film is cut into the size of 5cm × 5cm, impregnates 4 hours in the distilled water 1L of 30 DEG C, by this polyvinyl alcohol
Film takes out from distilled water, and clamp the water droplet of sorbent surface with 2 filter paper after, quality measurement D, further, by this poly-second
Enol film is dried 16 hours with the drying machine of 105 DEG C, after cooling down 30 minutes in exsiccator, and quality measurement E, utilize following formula to calculate
The swellbility of polyvinyl alcohol film,
A=100 × D/E (%).
2. the polyvinyl alcohol film described in claim 1, its thickness is 10～120 μm.
3. the manufacture method of polyvinyl alcohol film, its be comprise polyvinyl alcohol that the degree of polymerization is 5100～10000, swellbility is 200
～240%, the manufacture method of the polyvinyl alcohol film that degree of delay is 10～40nm of the central part of width, wherein, will contain
The film forming stock solution of the polyethylene alcohol and water having the degree of polymerization to be 5100～10000 carries out film forming as raw material, is then dried, only by film
Parallel both sides fix, carry out heat treatment, wherein, the saponification degree of above-mentioned polyvinyl alcohol is 98 moles of more than %, described swellbility
Following mensuration:
Polyvinyl alcohol film is cut into the size of 5cm × 5cm, impregnates 4 hours in the distilled water 1L of 30 DEG C, by this polyvinyl alcohol
Film takes out from distilled water, and clamp the water droplet of sorbent surface with 2 filter paper after, quality measurement D, further, by this poly-second
Enol film is dried 16 hours with the drying machine of 105 DEG C, after cooling down 30 minutes in exsiccator, and quality measurement E, utilize following formula to calculate
The swellbility of polyvinyl alcohol film,
A=100 × D/E (%).
4. the manufacture method described in claim 3, wherein, in the range of 50～70 DEG C at a temperature of be dried.
5. the manufacture method described in claim 3 or 4, wherein, carries out heat treatment in the range of 100～140 DEG C.
6. the manufacture method described in claim 3 or 4, it is used as the manufacture method of polyvinyl alcohol film of raw material of light polarizing film.
7. the manufacture method described in claim 3 or 4, it is used as the raw material of light polarizing film that degree of polarization is more than 99.95%
The manufacture method of polyvinyl alcohol film.
8. light polarizing film, the polyvinyl alcohol film according to any one of claim 1～2 is carried out dyeing, stretch and obtaining by it.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-321801 | 2008-12-18 | ||
| JP2008321801 | 2008-12-18 | ||
| CN200980151021.0A CN102257044B (en) | 2008-12-18 | 2009-12-14 | Polyvinyl alcohol film |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980151021.0A Division CN102257044B (en) | 2008-12-18 | 2009-12-14 | Polyvinyl alcohol film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103992606A CN103992606A (en) | 2014-08-20 |
| CN103992606B true CN103992606B (en) | 2016-08-24 |
Family
ID=42268764
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410262444.2A Active CN103992606B (en) | 2008-12-18 | 2009-12-14 | Polyvinyl alcohol film |
| CN200980151021.0A Active CN102257044B (en) | 2008-12-18 | 2009-12-14 | Polyvinyl alcohol film |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200980151021.0A Active CN102257044B (en) | 2008-12-18 | 2009-12-14 | Polyvinyl alcohol film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5628025B2 (en) |
| KR (2) | KR101910668B1 (en) |
| CN (2) | CN103992606B (en) |
| TW (1) | TWI468454B (en) |
| WO (1) | WO2010071094A1 (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013023598A (en) * | 2011-07-21 | 2013-02-04 | Kuraray Co Ltd | Acrylic thermoplastic resin composition |
| JP5667533B2 (en) * | 2011-07-21 | 2015-02-12 | 株式会社クラレ | Acrylic thermoplastic resin composition |
| CN103765255B (en) * | 2011-09-09 | 2018-01-30 | 日本化药株式会社 | Polarizer and polarizer |
| JP5812483B2 (en) * | 2011-09-09 | 2015-11-11 | 日本化薬株式会社 | Polarizing element and polarizing plate |
| JP5651089B2 (en) * | 2011-09-09 | 2015-01-07 | 日本化薬株式会社 | Polarizing element and polarizing plate |
| WO2013146459A1 (en) * | 2012-03-30 | 2013-10-03 | 株式会社クラレ | Polyvinyl alcohol-based polymer film |
| KR102059228B1 (en) * | 2012-08-06 | 2019-12-24 | 주식회사 쿠라레 | Layered object, polarizing film, and process for producing polarizing film |
| KR101624072B1 (en) * | 2012-09-26 | 2016-05-24 | 주식회사 쿠라레 | Polyvinyl alcohol film and polarizing film |
| WO2015076169A1 (en) * | 2013-11-21 | 2015-05-28 | 株式会社クラレ | Polyvinyl alcohol film |
| KR102232980B1 (en) * | 2014-01-28 | 2021-03-26 | 주식회사 쿠라레 | Master film for producing optical film |
| JP6215864B2 (en) | 2014-04-25 | 2017-10-18 | 日東電工株式会社 | Polarizer, polarizing plate and image display device |
| JP6214594B2 (en) | 2014-04-25 | 2017-10-18 | 日東電工株式会社 | Polarizer, polarizing plate and image display device |
| JP6215261B2 (en) | 2014-06-27 | 2017-10-18 | 日東電工株式会社 | Long polarizer, long polarizing plate and image display device |
| KR101577911B1 (en) * | 2014-10-23 | 2015-12-16 | 경북대학교 산학협력단 | A method for preparing polyvinyl alcohol films by the heterogeneous surface saponification of polyvinyl acetate films |
| CN104459864B (en) * | 2014-12-12 | 2016-12-07 | 云南云天化股份有限公司 | Polymer film of polyvinyl alcohol and manufacture method thereof |
| US10472481B2 (en) | 2015-02-27 | 2019-11-12 | Kyungpook National University Industry-Academic Cooperation Foundation | Method for preparing functional extract-containing polyvinyl alcohol film by heterogeneous saponification of polyvinyl acetate film |
| KR102461860B1 (en) * | 2015-03-17 | 2022-11-01 | 미쯔비시 케미컬 주식회사 | Polyvinyl alcohol film, method for producing polyvinyl alcohol film, polarizing film, and polarizing plate |
| JP6592509B2 (en) * | 2015-04-13 | 2019-10-16 | 株式会社クラレ | Polyvinyl alcohol film |
| JP6668338B2 (en) * | 2015-05-13 | 2020-03-18 | 株式会社クラレ | Polyvinyl alcohol film |
| JP7163000B2 (en) | 2015-06-25 | 2022-10-31 | 日東電工株式会社 | Polarizer with non-polarizing portion |
| JP6743502B2 (en) * | 2015-08-12 | 2020-08-19 | 三菱ケミカル株式会社 | Method for producing polyvinyl alcohol film |
| JP6812795B2 (en) * | 2015-08-26 | 2021-01-13 | 三菱ケミカル株式会社 | Polyvinyl alcohol-based resin for manufacturing polarizing film and its manufacturing method, polyvinyl alcohol-based film and its manufacturing method, polarizing film, polyvinyl alcohol-based resin |
| TWI772409B (en) * | 2017-04-26 | 2022-08-01 | 日商三菱化學股份有限公司 | Production method of polyvinyl alcohol-based film, polarizing film, polarizing plate, and polyvinyl alcohol-based film |
| WO2018199139A1 (en) * | 2017-04-26 | 2018-11-01 | 日本合成化学工業株式会社 | Polyvinyl alcohol film, polarizing film and polarizing plate, and polyvinyl alcohol film production method |
| TWI789390B (en) * | 2017-04-26 | 2023-01-11 | 日商三菱化學股份有限公司 | Polyvinyl alcohol-based film, polarizing film, polarizing plate, and method for producing polyvinyl alcohol-based film |
| WO2018199140A1 (en) * | 2017-04-26 | 2018-11-01 | 日本合成化学工業株式会社 | Polyvinyl alcohol film, polarizing film and polarizing plate, and polyvinyl alcohol film production method |
| CN107167860A (en) * | 2017-05-27 | 2017-09-15 | 中国石油化工集团公司 | Polyvinyl alcohol film and its method of testing |
| JP2021059612A (en) * | 2018-01-30 | 2021-04-15 | 株式会社クラレ | Polyvinyl alcohol film and manufacturing method therefor |
| CN111732749B (en) * | 2020-08-10 | 2022-11-11 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl alcohol optical film |
| KR20230116249A (en) * | 2022-01-28 | 2023-08-04 | 경북대학교 산학협력단 | Method of fabricating pva-containing functional polymer structure and pva-containing functional polymer structure fabricated thereby |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321704A (en) * | 2000-05-01 | 2001-11-14 | 可乐丽股份有限公司 | Polyvinyl alcohol polymer film and polarized light film |
| CN1715968A (en) * | 2004-06-29 | 2006-01-04 | 日东电工株式会社 | Polarizer and method of producing the same, polarizing plate, optical film, and image display |
| CN1973219A (en) * | 2004-06-22 | 2007-05-30 | 富士胶片株式会社 | Polarizing plate and liquid crystal display |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2543748B2 (en) | 1987-07-03 | 1996-10-16 | 株式会社クラレ | Polarizing film and manufacturing method thereof |
| JP3273627B2 (en) * | 1992-02-25 | 2002-04-08 | 株式会社クラレ | Polarizing film |
| JP3283564B2 (en) * | 1992-03-04 | 2002-05-20 | 株式会社クラレ | Method for producing polyvinyl alcohol-based film |
| JP3327423B2 (en) | 1993-10-21 | 2002-09-24 | 日本合成化学工業株式会社 | Manufacturing method of polarizing film |
| JPH0815524A (en) * | 1994-06-28 | 1996-01-19 | Sumitomo Bakelite Co Ltd | Production of heat resistant optical film and heat resistant optical film and liquid crystal display panel using the same |
| JP3719761B2 (en) * | 1995-12-22 | 2005-11-24 | 住友ベークライト株式会社 | Optical compensation film manufacturing method, optical compensation film, and liquid crystal display device using the same |
| JP4104916B2 (en) * | 2002-06-12 | 2008-06-18 | 株式会社クラレ | Optical polyvinyl alcohol film and method for producing the same |
| CN101091127B (en) * | 2004-12-28 | 2010-09-08 | 日本合成化学工业株式会社 | Polyvinyl alcohol film, and polarizing film and polarizing plate using the same |
| JP4581690B2 (en) * | 2005-01-05 | 2010-11-17 | 住友化学株式会社 | Manufacturing method of polarizing film |
-
2009
- 2009-12-14 CN CN201410262444.2A patent/CN103992606B/en active Active
- 2009-12-14 KR KR1020117016313A patent/KR101910668B1/en active IP Right Grant
- 2009-12-14 CN CN200980151021.0A patent/CN102257044B/en active Active
- 2009-12-14 KR KR1020167027669A patent/KR20160120356A/en not_active Application Discontinuation
- 2009-12-14 WO PCT/JP2009/070800 patent/WO2010071094A1/en active Application Filing
- 2009-12-14 JP JP2010509605A patent/JP5628025B2/en active Active
- 2009-12-17 TW TW98143272A patent/TWI468454B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321704A (en) * | 2000-05-01 | 2001-11-14 | 可乐丽股份有限公司 | Polyvinyl alcohol polymer film and polarized light film |
| CN1973219A (en) * | 2004-06-22 | 2007-05-30 | 富士胶片株式会社 | Polarizing plate and liquid crystal display |
| CN1715968A (en) * | 2004-06-29 | 2006-01-04 | 日东电工株式会社 | Polarizer and method of producing the same, polarizing plate, optical film, and image display |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2010071094A1 (en) | 2012-05-31 |
| JP5628025B2 (en) | 2014-11-19 |
| KR20110105803A (en) | 2011-09-27 |
| KR101910668B1 (en) | 2018-10-22 |
| KR20160120356A (en) | 2016-10-17 |
| CN102257044B (en) | 2015-12-02 |
| CN102257044A (en) | 2011-11-23 |
| TW201033273A (en) | 2010-09-16 |
| TWI468454B (en) | 2015-01-11 |
| CN103992606A (en) | 2014-08-20 |
| WO2010071094A1 (en) | 2010-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103992606B (en) | Polyvinyl alcohol film | |
| CN102257413B (en) | Method for producing polarizing film | |
| CN104640912B (en) | Polyvinyl alcohol film and polarizing coating | |
| JP5446871B2 (en) | Optical compensation film, and polarizing plate and liquid crystal display device using the same | |
| JP6788673B2 (en) | Polarizing film and its manufacturing method | |
| JP3021494B2 (en) | Polarizing film and manufacturing method thereof | |
| JP4764658B2 (en) | Method for producing polyvinyl alcohol film | |
| KR20160089349A (en) | Polyvinyl alcohol film | |
| JP5931125B2 (en) | Manufacturing method of polarizing film | |
| JP4592147B2 (en) | Polyvinyl alcohol film and polarizing film | |
| JP5493285B2 (en) | Optical film | |
| JPH06118231A (en) | Optical film | |
| JP4664087B2 (en) | Polyvinyl alcohol film and method for producing the same | |
| JP5724705B2 (en) | Optical film, polarizing plate and liquid crystal display device using the same | |
| JP2021059612A (en) | Polyvinyl alcohol film and manufacturing method therefor | |
| JP4302393B2 (en) | Polarized film | |
| JP6776129B2 (en) | the film | |
| CN105683786B (en) | Polarizer and polarizing film with uniform transmissivity under each wavelength | |
| JP3145747B2 (en) | Polarizing film | |
| JPWO2013125419A1 (en) | Optical film, polarizing plate and liquid crystal display device | |
| JP2011048145A (en) | Polarizing film and method of manufacturing the same | |
| JP3657419B2 (en) | Polarized film | |
| JPH06313809A (en) | Manufacture of polarizing film | |
| JPH08190017A (en) | Production of polarizing film | |
| TWI688579B (en) | Film and method for manufacturing optical film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |