CN103992606A - Polyvinyl alcohol film - Google Patents
Polyvinyl alcohol film Download PDFInfo
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- CN103992606A CN103992606A CN201410262444.2A CN201410262444A CN103992606A CN 103992606 A CN103992606 A CN 103992606A CN 201410262444 A CN201410262444 A CN 201410262444A CN 103992606 A CN103992606 A CN 103992606A
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
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Abstract
Provided is a film comprising a polyvinyl alcohol having a high polymerization degree which is useful as a material for producing a polarizing film having a good polarizing performance. A polyvinyl alcohol film which comprises a polyvinyl alcohol having a polymerization degree of 5100 to 10000, characterized by having a swelling degree of 200 to 240% and a retardation at the center in the width direction of 10 to 40 nm. In this polyvinyl alcohol film, the saponification degree of the polyvinyl alcohol is preferably 98 mol% or more. The thickness of the polyvinyl alcohol film is preferably 10 to 120 [mu]m.
Description
Technical field
The present invention relates to can be used as the polyvinyl alcohol film that the raw material of the light polarizing film that polarizing properties is good uses.
Background technology
Liquid crystal indicator (LCD) is at its initial stage of development, be used in the miniature instrument of desk top computer and wrist-watch etc., but in recent years, start to use it for the broad range of notebook computer, liquid-crystal display, color liquid crystal projector, LCD TV, vehicle mounted navigationsystem, portable phone, the spendable measuring instrument of indoor and outdoor etc.On the other hand, especially, in the purposes of LCD TV etc., people require all the more the raising of display quality, the raising of for example contrast gradient, even for the Polarizer as one of LCD member, and the also raising of strong request polarizing properties.
The current Polarizer generally using has the formation at the protective membranes such as single or double laminating three cellulose acetate membrane or cellulose acetate butyrate film of light polarizing film, and described light polarizing film is the light polarizing film obtaining for dyeing processing, the fixing processing of employing boron compound etc. of the base film enforcement uniaxial extension, employing iodine or the dichroic dye that comprise polyvinyl alcohol (being sometimes referred to as below PVA).As the method for polarizing properties that improves this Polarizer, proposed the whole bag of tricks such as the methods of creating conditions of the method improveing as the structure of the PVA of raw material, the method for controlling the physical property of PVA film, research Polarizer, it contributes to the raising of LCD contrast gradient.
For example, in patent documentation 1, record and comprised that the polymerization degree is more than 2500, preferably the light polarizing film of 6000～10000 PVA has excellent optical characteristics.Use the high PVA of the polymerization degree, this is favourable method for improving polarizing properties, but is difficult in industrial enforcement.
In addition, as other method that improves polarizing properties, for example in patent documentation 2, record the manufacture method of light polarizing film, it uses PVA mesentery as base film, and the consolute temperature (X) of described PVA mesentery in hot water is the scope shown in following formula with the pass of equilibrium swelling degree (Y).
Y?＞-0.0667X+6.73 (I)
X?≥?65 (II)
But the polymerization degree of the PVA using in foregoing invention is preferably 3500～5000 scope, shown in comparative example described as follows, even this manufacture method is directly applied to high-polymerization degree PVA, find that the polarizing properties of the light polarizing film obtaining is also insufficient.,, for the light polarizing film of the PVA that comprises high-polymerization degree in industrial manufacture, need the comprehensive knowledge relevant with structure, the physical property of PVA film etc. of PVA to find the condition of best raw material.
Patent documentation 1: Japanese kokai publication hei 1-105204 communique
Patent documentation 2: Japanese kokai publication hei 7-120616 communique.
Summary of the invention
Therefore, the object of the present invention is to provide can be used as for the manufacture of have high polarity can the raw material of light polarizing film and the film of the PVA that comprises high-polymerization degree.
Contrivers etc. bring into play to greatest extent about the knowledge of the physical property of the structure of PVA and PVA film and are studied.Found that following PVA film realized above-mentioned purpose, thereby completed the present invention, described PVA film is characterised in that, comprises the polymerization degree and be 5100～10000 PVA, and swelling capacity is 200～240%, and the delay degree of the central part of width is 10～40nm.
In this situation, the saponification deg of preferred above-mentioned PVA is more than 98 % by mole.
In addition, preferably the thickness of PVA film is 10～120 μ m.
The present invention also comprises the manufacture method of above-mentioned PVA film, and it is that 5100～10000 PVA and the film forming stoste of water are carried out film forming as raw material using containing the polymerization degree.
The present invention further also comprises the light polarizing film that above-mentioned PVA film is dyeed, stretched and obtains.
The raw material that PVA film of the present invention can be used as the light polarizing film that polarizing properties is good uses.The light polarizing film obtaining can be effective to the making of Polarizer, and described Polarizer is the component parts of the liquid crystal indicator of desk top computer, wrist-watch, notebook computer, liquid-crystal display, color liquid crystal projector, LCD TV, vehicle mounted navigationsystem, portable phone, the spendable measuring instrument of indoor and outdoor etc.
Embodiment
Below explain the present invention.
In order to tackle the good polarizing properties as the light polarizing film of the object of the invention, the polymerization degree of the PVA using in the present invention need to be 5100～10000, is preferably 5200～9500, more preferably 5400～9200.If the polymerization degree of PVA is less than 5100,, in the time manufacturing light polarizing film, be difficult to show high polarity energy.On the other hand, if the polymerization degree of PVA exceedes 10000, the productivity of PVA reduces.Should illustrate, in the present invention, the polymerization degree of so-called PVA refers to the polymerization degree (viscometric degree of polymerization) of measuring according to the method for recording in following embodiment.
In addition, the saponification deg of PVA is preferably more than 98 % by mole, more preferably more than 99 % by mole, and then is preferably more than 99.5 % by mole, most preferably is more than 99.8 % by mole.If the saponification deg of PVA is less than 98 % by mole,, in the manufacturing process of light polarizing film, there is PVA to be easy to stripping, the PVA of stripping is attached on film and makes the possibility of the degradation of light polarizing film.
The PVA using in the present invention can manufacture by polyvinylesters based polymer is carried out to saponification, and described polyvinylesters based polymer is by obtaining vinyl ester polymerization.Vinyl ester can be enumerated vinyl acetate, vinyl formate, propionate, vinyl butyrate, trimethylacetic acid vinyl acetate, vinyl neodecanoate (バ ー サ テ ィ ッ Network acid PVC ニ Le), vinyl laurate, stearic acid vinyl ester, vinyl benzoate etc., can be one kind or two or more from wherein selecting.Wherein, from obtaining easiness, the consideration of cost equal angles of easiness, PVA manufacture, preferably use vinyl acetate.Polymerization temperature is not particularly limited, and in the time using methyl alcohol as polymer solvent, preferable polymerization temperature is near the i.e. 60 DEG C of left and right of boiling point of methyl alcohol preferably.
Only otherwise damage effect of the present invention, PVA is not limited to homopolymer saponified of vinyl ester.Can be also for example that to be less than the ratio of 5 % by mole, by unsaturated carboxylic acid or derivatives thereof, unsaturated sulfonic acid or derivatives thereof, carbonatoms, alpha-olefin as 2～30 etc. carries out the modified PVA that graft copolymerization forms on PVA; By vinyl ester, carry out the saponified of modified polyvinyl ester that copolymerization forms with unsaturated carboxylic acid or derivatives thereof, unsaturated sulfonic acid or derivatives thereof, the carbonatoms alpha-olefin that is 2～30 etc. to be less than the ratio of 15 % by mole; With aldehydes such as formalin, butyraldehyde, phenyl aldehydes by the polyvinyl acetal based polymer forming that an is crosslinked part for the hydroxyl of PVA etc.
By by above-mentioned PVA film forming, can obtain PVA film of the present invention.Film is except the method that moisture PVA is melt extruded, the method that can also adopt casting filming therapy, wet type to become embrane method (discharging), gel to become embrane method (by after temporary transient PVA aqueous solution cooling gel, extraction except desolventizing), be cast into embrane method (キ ャ ス ト System embrane method) (make the PVA aqueous solution flow, dry) and these Combination of Methods are formed in poor solvent on substrate etc.Wherein, consider from the angle that can obtain good PVA film, preferred molten is extruded into embrane method and casting filming therapy.The solvent using when film forming preferably makes water.
Mainly comprise the volatile matter rate (Play development point rate of the film forming stoste of PVA and solvent) change according to the molecular weight of film or PVA and to some extent, but be preferably 50～95 quality %, more preferably 60～95 quality %, and then preferred 70～95 quality %.If volatile matter rate is less than 50 quality %, exist the viscosity of film forming stoste too high, filtration when modulation or froth breaking become difficulty, are difficult to the possibility of the PVA film that obtains inclusion-free or defect.In addition, if volatile matter rate exceedes 95 quality %, exist the viscosity of film forming stoste too low, be difficult to manufacture the possibility of the PVA film with target thickness or high thickness and precision.
In the time manufacturing PVA film of the present invention, also can use softening agent.Softening agent can be enumerated glycerine, Glycerol dimer, ethylene glycol etc., but is not limited to this.The usage quantity of softening agent is not particularly limited, and is in the scope of 10～15 mass parts conventionally with respect to PVA100 mass parts.
As the drying means of the PVA film after film forming, for example, can enumerate and adopt the contact drying that is dried, uses hot-rolling of hot blast or adopt being dried of infrared heater etc.Can use separately a kind in these methods, also two or more can be used in combination.Drying temperature is not particularly limited, preferably in the scope of 50～70 DEG C.In addition, although also depend on concentration or the filming condition of film forming stoste time of drying now, it is probably 45～75 minutes.
By dry PVA film damping and regulate after moisture rate (water ratio), only the both sides of the parallel both sides of film, preferable width direction are fixed, in the scope of 100～140 DEG C, heat-treat, utilize thus the stress of following moisture to reduce and to produce, can apply stable stretching to film.Thus, can stably give film following low-level delay degree.Now the moisture rate of film is preferably 1～15 quality %, more preferably 1～10 quality %, and then preferred 2～6 quality %.The heat treated time is not particularly limited, and it is according to thermal treatment temp and different, but is roughly in 5 minutes.
The thickness of the PVA film of the present invention obtaining is like this preferably 10～120 μ m, more preferably 12～80 μ m, and then preferably 15～75 μ m, most preferably 20～60 μ m.If thickness is less than 10 μ m,, in following stretching process, there is the possibility that is easy to the fracture that film occurs.In addition, if thickness exceedes 120 μ m, exist film upper stress in the time stretching to become large, be difficult to carry out the possibility of stretching fully.
The swelling capacity of PVA film of the present invention need to be 200～240%, preferably 205～235%, more preferably 210～230%.If swelling capacity is less than 200%, the overtension while stretching, is difficult to stretch fully.In addition, if swelling capacity exceedes 240%, water-absorbent is high, and therefore, in the manufacturing process of following light polarizing film, film is easy to produce fold or end is curling, becomes the reason of fracture while stretching.For swelling capacity being controlled to predetermined scope, for example, temperature when the PVA film to after film forming can be heat-treated or Timing are to above-mentioned scope.The swelling capacity of PVA film can utilize the following method in embodiment project to measure.
In PVA film of the present invention, the delay degree of the central part of width need to be 10～40nm, more preferably 13～37nm, and then preferably 17～33nm, most preferably 20～30nm.If delay degree is less than 10nm, the dyeing kinetics while manufacturing light polarizing film is slack-off, is therefore easy to produce dyeing inequality.In addition, if delay degree exceedes 40nm, even low stretching ratio, the fracture that also can produce film.The delay degree of PVA film can utilize the following method in the project of embodiment to measure.
For the delay degree of PVA film is controlled to predetermined scope, except the above-mentioned method of known method stretching PVA film of utilizing carrying out heat-treating methods after the damping of PVA film, can also enumerating, but be not limited to these methods.Wherein, from angle fixing the delay degree producing is considered, preferably after damping, carry out heat-treating methods.Now, it is important only the both sides of the parallel both sides of PVA film, preferable width direction being fixed and heat-treated.If do not fix film, or surrounding is fixedly heat-treated, the stress of film is isotropic, and therefore degree of delay not, can not realize object.
Then, narrate for the manufacture method of the light polarizing film that uses PVA film blank of the present invention.The operation of moisture adjusting, dyeing, stretching, colourity adjusting etc. can be contained in the manufacturing process of light polarizing film.Now, preferably carry out the wet type stretching of film.In addition, as required, also can follow the operation that wet type stretches, by gained stretched film and then stretch in boric acid aqueous solution.Further, as required, for example, can in the aqueous solution that contains boric acid and potassiumiodide, carry out colourity adjusting, and be dried, manufacture light polarizing film.
The moisture of PVA film regulates to be preferably immersed in pure water or distilled water and carries out.Preferably 20～40 DEG C of temperature now, more preferably 25～35 DEG C, and then preferably 27～33 DEG C.If temperature is less than 20 DEG C, there is the water ratio step-down of film blank, when stretching afterwards, the tension force of film uprises, the possibility that the polarizing properties of the light polarizing film obtaining reduces.In addition, if temperature exceedes 40 DEG C, exist the water-absorbent of film blank to uprise, after operation in, film is easy to produce fold or end is curling, becomes the possibility of the reason of the time fracture of stretching.On the other hand, as the time of impregnated membranes blank, general in the scope of 30～120 seconds.
The dyeing of PVA film is for example carried out in the IKI aqueous solution.Now the concentration of preferred iodine is that the concentration of 0.01～0.1 quality %, potassiumiodide is 1～10 quality %, more preferably iodine concentration is that 0.02～0.08 quality %, potassiumiodide concentration are 2～8 quality %, and then preferably iodine concentration is that 0.03～0.06 quality %, potassiumiodide concentration are 3～6 quality %.The temperature of the aqueous solution is not particularly limited, and is preferably 25～40 DEG C.
The wet type of PVA film blank stretch also can be used as regulate with above-mentioned moisture or dyeing mutually independently operation carry out, but preferably effectively regulate in the water of use or in the aqueous solution of dyeing use and carry out at above-mentioned moisture, more preferably at the aqueous solution of dyeing use, carry out in the IKI aqueous solution.PVA film blank is in the time that wet type stretches, and the stretching ratio representing with the Length Ratio of the film before and after stretching is preferably 2.0～2.9 times, and more preferably 2.2～2.8 times, and then preferably 2.4～2.8 times.
Consider from the angle that can obtain the more excellent light polarizing film of polarizing properties, temperature when PVA film is carried out to wet type stretching is preferably 20～40 DEG C, and more preferably 25～40 DEG C, and then preferably 25～35 DEG C, particularly preferably 27～33 DEG C.
As mentioned above, also can then PVA film be carried out to the operation of wet type stretching, the stretched film obtaining is further stretched in boric acid aqueous solution.Stretching ratio is now preferably below 3 times, and more preferably 1.2～3 times, and then be preferably 1.3～2.9 times, most preferably be 1.4～2.8 times.
Boric acid concentration in the aqueous solution is now preferably 2～6 quality %, more preferably 2～5 quality %, and then preferred 2～4 quality %.In the time that the concentration of boric acid is less than 2 quality %, likely in the light polarizing film obtaining, color spot becomes many.In addition, in the time that the concentration of boric acid exceedes 6 quality %, have the crosslinked excessive of the PVA that caused by boric acid, what be difficult to film to stretch with high magnification may.
In addition, in order to make the form and aspect of light polarizing film close to neutral gray, also preferably in boric acid aqueous solution, add potassiumiodide.The concentration of potassiumiodide is preferably 3～10 quality %, more preferably 4～8 quality %.In the time that the concentration of potassiumiodide is less than 3 quality %, likely grow of the green of gained light polarizing film.On the other hand, in the time that the concentration of potassiumiodide exceedes 10 quality %, likely grow of the redness of gained light polarizing film.Boric acid aqueous solution also can contain the metallic compound of such as iron, zirconium etc. as other composition.
In above-mentioned stretching, the temperature of the aqueous solution is not particularly limited, and is preferably 50～60 DEG C, and more preferably 55～60 DEG C, and then preferably 57～60 DEG C.If draft temperature is less than 50 DEG C, has and can not stretch fully, the possibility that the degree of polarization of gained light polarizing film declines.In addition, if draft temperature exceedes 60 DEG C, the possibility that has the transmitance of gained light polarizing film to reduce.
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 times.If stretching ratio is less than 4.5 times, the possibility that has the polarizing properties of gained light polarizing film to reduce.In addition, if stretching ratio exceedes 7.0 times, there is the fracture of the raw film of fecund in stretching, be difficult to stably manufacture the possibility of light polarizing film.
Colourity after stretching regulates preferably carries out in the aqueous solution that contains boric acid and potassiumiodide.Now, also can in the aqueous solution, add the metallic compound of zinc chloride, zinc iodide etc.In order to prevent the decline of polarizing properties, the temperature of the aqueous solution is preferably low than draft temperature, is preferably specifically 20～50 DEG C, more preferably 30～40 DEG C.The time that colourity regulates is not particularly limited.
The dry of gained light polarizing film can use various drying machines, utilizes intermittent type, the method for contact etc. is carried out on swing, continuous rolling continuously.In order to prevent that iodine from being distilled by light polarizing film, and the disengaging of the inhibition boric acid crosslinked with PVA reacts, and is preferably to carry out at 40～80 DEG C at drying temperature, and more preferably 45～70 DEG C, and then preferably 50～60 DEG C.Be not particularly limited time of drying, and it for example, according to device, drying temperature and different, in the scope of 3～6 minutes.
Embodiment
Below, wait and specifically describe the present invention by embodiment, but the present invention is not limited in any way the following examples.In embodiment etc., the delay degree Re of the viscometric degree of polymerization P of PVA, the swelling capacity of PVA film, PVA film, the transmissivity Y of light polarizing film and degree of polarization V evaluate by following method.
(1) mensuration of the viscometric degree of polymerization P of PVA joins PVA0.28g, distilled water 70g and stirrer in the common ground joint of 100mL (common The り closes わ せ) Erlenmeyer flask.In the thermostatic bath of 95 DEG C, dipping covers the above-mentioned Erlenmeyer flask of stopper, stirs on one side PVA is dissolved on one side with stirrer, makes the 0.4%PVA aqueous solution.This PVA aqueous solution is filtered with Büchner funnel shape glass filter 3G, and cooling in the Water Tank with Temp.-controlled of 30 DEG C, make polymerization degree measurement sample.Sample in contrast adds 70g distilled water and covers stopper in the common ground joint Erlenmeyer flask of another 100mL, is immersed in the Water Tank with Temp.-controlled of 30 DEG C.
By the furnace pot of 1 hour of the drying machine heating with 105 DEG C in moisture eliminator cooling 30 minutes, measure the quality a (g) of furnace pot.Utilize the full transfer pipet that holds that polymerization degree measurement is transferred in this furnace pot with sample 10mL, used the drying machine of 105 DEG C to be dried after 16 hours, in moisture eliminator cooling 30 minutes, quality measurement b (g).Polymerization degree measurement utilizes following formula to calculate by the concentration c (g/L) of sample.
c?=?1000×(b-a)/10
In オ ス ト ワ Le De viscometer, entirely hold transfer pipet with 10mL and add polymerization degree measurement sample or distilled water, in the Water Tank with Temp.-controlled of 30 DEG C, make it stablize 15 minutes.The polymerization degree measurement that mensuration adds falls number of seconds t with sample
1(s) and distilled water fall number of seconds t
0(s), utilize following formula to calculate viscometric degree of polymerization P.
η
r?=?t
1/t
0
[η]?=?2.303×Log(η
r/c)
Log(P)?=?1.613×Log([η]×10
4/8.29)
(2) mensuration of the swelling capacity of PVA film is cut into PVA film the size of 5cm × 5cm, in the distilled water 1L of 30 DEG C, floods 4 hours.This PVA film is taken out from distilled water, clamp after the water droplet of absorbing surface quality measurement D with 2 filter paper.Further, this PVA film is dried to 16 hours with the drying machine of 105 DEG C, in moisture eliminator, after cooling 30 minutes, quality measurement E, utilizes following formula to calculate the swelling capacity of PVA film.
A?=?100×D/E(%)
(3) mensuration of the delay degree Re of PVA film is taked the rectangle sample of width 5cm × flow direction 10cm from the central part of PVA film, the optical material inspection units RETS-1100 of Shi Yong great mound electronics society system, the delay degree Re that is 550nm place to mensuration wavelength measures.
(4) mensuration of the transmissivity 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's system, according to JIS Z 8722 (measuring method of object color), carry out the visibility meter correction of the visible region in illuminant-C, 2 ° of visuals field, for 1 light polarizing film sample, measure the optical transmission rate while tilting optical transmission rate 45 ° time and inclination-45 ° with respect to tensile axis direction, and try to achieve their mean value Y1 (%).For another 1 light polarizing film sample, the transmitance of the light when transmitance of same light while measuring 45 ° and inclination-45 °, tries to achieve their mean value Y2 (%).Utilize following formula by average to Y1 and Y2, as the transmissivity Y (%) of light polarizing film.
Y?=?(Y1+Y2)/2
(5) mensuration of the degree of polarization V of light polarizing film
With (4) in record transmissivity situation similarly, measure optical transmission rate Y|| (%) when 2 light polarizing film taking in above-mentioned (4) are overlapping in the parallel mode of its draw direction and the optical transmission rate Y ⊥ (%) when overlapping in the orthogonal mode of draw direction, utilize following formula to try to achieve degree of polarization V (%).
V?=?{(Y||-Y⊥)/(Y||+Y⊥)}
1/2×100
[embodiment 1]
To contain that the polymerization degree is 5800, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 40 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, the two ends of the width of film are fixed on to the parallel both sides of metal frame, so that film does not shrink on width, carry out the thermal treatment of 3 minutes at 120 DEG C.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 230%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 29nm.
Then, above-mentioned PVA film is cut into the size of flow direction 11cm × width 10cm, using flow direction as draw direction, be arranged on the stretching clamp that chuck spacing is 4cm, it is flooded 1 minute in the pure water of 30 DEG C, then dipping in the staining fluid that contains 0.03 quality % iodine, 3 quality % potassiumiodides (30 DEG C of temperature), is stretched to 2.6 times with the speed of 0.13m/min, makes iodine absorption.
Then, this stretched film is immersed in the stretching liquid (57.5 DEG C of temperature) that contains 4 quality % boric acid, 6 quality % potassiumiodides, is stretched to after 2.3 times with the speed of 0.13m/min, draw direction is fixed, at 50 DEG C, be dried 4 minutes, obtain light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.99%, can obtain the light polarizing film that polarizing properties is good.
[embodiment 2]
To contain that the polymerization degree is 5800, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 40 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, the two ends of the width of film are fixed on to the parallel both sides of metal frame, so that film does not shrink on width, at 115 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 240%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 26nm.
Then, similarly to Example 1, the PVA film that stretches above-mentioned while make iodine absorption, further stretches and obtains light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.96%, can obtain the light polarizing film that polarizing properties is good.
[embodiment 3]
To contain that the polymerization degree is 9100, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 20 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, the two ends of the width of film are fixed on the parallel both sides of metal frame, so that film does not shrink on width, at 110 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 230%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 39nm.
Then,, except making stretching ratio is 2.5 times, similarly to Example 1, the PVA film that stretches above-mentioned while make iodine absorption, further stretches, and obtains light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.95%, can obtain the light polarizing film that polarizing properties is good.
[embodiment 4]
To contain that the polymerization degree is 5200, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 40 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, the two ends of the width of film are fixed on the parallel both sides of metal frame, so that film does not shrink on width, at 135 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 205%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 29nm.
Then, similarly to Example 3, the PVA film that stretches above-mentioned while make iodine absorption, further stretches, and obtains light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.95%, can obtain the light polarizing film that polarizing properties is good.
[embodiment 5]
To contain that the polymerization degree is 5500, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 30 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, the two ends of the width of film are fixed on to the parallel both sides of metal frame, so that film does not shrink on width, at 130 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 215%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 29nm.
Then, similarly to Example 1, the PVA film that stretches above-mentioned while make iodine absorption, further stretches, and obtains light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.99%, can obtain the light polarizing film that polarizing properties is good.
[comparative example 1]
To contain that the polymerization degree is 4800, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 6.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 40 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, the two ends of the width of film are fixed on to the parallel both sides of metal frame so that film not broad ways shrink, at 120 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 220%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 28nm.
Then,, except making stretching ratio is 2.7 times, similarly to Example 1, the PVA film that stretches above-mentioned while make iodine absorption, further stretches, and obtains light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.92%, and the degree of polarization of light polarizing film is not enough a little.
[comparative example 2]
To contain that the polymerization degree is 5800, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 40 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, the two ends of the width of film are fixed on to the parallel both sides of metal frame, so that film does not shrink on width, at 140 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 195%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 29nm.
Then, similarly to Example 1, the PVA film that stretches above-mentioned while make iodine absorption, further stretches, and obtains light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.92%, and the degree of polarization of light polarizing film is not enough a little.
[comparative example 3]
To contain that the polymerization degree is 5800, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 40 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, the two ends of the width of film are fixed on to the parallel both sides of metal frame, so that film does not shrink on width, at 110 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 250%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 28nm.
Then, similarly to Example 1, the PVA film that stretches above-mentioned while make iodine absorption, further stretches, and obtains light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.87%, and the degree of polarization of light polarizing film is not enough a little.
[comparative example 4]
To contain that the polymerization degree is 5800, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 40 μ m.By the damping 16 hours under 26 DEG C, the condition of 20%RH of this film, water ratio is adjusted to after 3 quality %, be fixed on whole four limits of metal frame, at 120 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 230%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 5nm.
Then, similarly to Example 1, the PVA film that stretches above-mentioned while make iodine absorption, further stretches and obtains light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.97%, polarizing properties is good, if but so that light polarizing film is orthogonal state observes, find large dyeing inequality.
[comparative example 5]
To contain that the polymerization degree is 5800, saponification deg is PVA 100 mass parts of 99.8 % by mole and as the 5.5 quality %PVA aqueous solution of glycerine 12 mass parts of softening agent, curtain coating in the metallic roll of 60 DEG C, carry out 60 minutes dry, obtaining thickness is the PVA film of 40 μ m.By the damping 16 hours under 26 DEG C, the condition of 65%RH of this film, water ratio is adjusted to after 8 quality %, the two ends of the width of film are fixed on to the parallel both sides of metal frame, so that film does not shrink on width, at 120 DEG C, carry out the thermal treatment of 3 minutes.Utilize the method for recording in above-mentioned (2) to measure the swelling capacity of the PVA film after thermal treatment, result is 230%.In addition, utilize the method for recording in above-mentioned (3) to measure the delay degree of PVA film, result is 70nm.
Then, similarly to Example 1, the PVA film that stretches above-mentioned while make iodine absorption, and then, similarly to Example 1, stretch stretching ratio is 1.8 times except making, obtain light polarizing film.Utilize the method for recording in above-mentioned (4) and (5) to measure transmitance and the degree of polarization of this light polarizing film, result is respectively 44.0%, 99.20%, and the degree of polarization of light polarizing film is not enough a little.Therefore, in order to improve degree of polarization, the target value of stretching ratio is changed into 2.3 times from 1.8 times, result generation tension fracture, can not obtain light polarizing film.
Gather the above results and be shown in table 1.
[table 1]
industrial applicability
The light polarizing film being obtained by PVA film of the present invention can be effective to the making of Polarizer, and described Polarizer is the component parts of the liquid crystal indicator of desk top computer, wrist-watch, notebook computer, liquid-crystal display, color liquid crystal projector, LCD TV, vehicle mounted navigationsystem, portable phone, the spendable measuring instrument of indoor and outdoor etc.
Claims (9)
1. polyvinyl alcohol film, it is to be the polyvinyl alcohol film of the raw material of more than 99.95% light polarizing film as degree of polarization, wherein, comprises the polymerization degree and be 5100～10000 polyvinyl alcohol, swelling capacity is 200～240%, and the delay degree of the central part of width is 10～40nm.
2. polyvinyl alcohol film claimed in claim 1, wherein, the saponification deg of above-mentioned polyvinyl alcohol is more than 98 % by mole.
3. the polyvinyl alcohol film described in claim 1 or 2, its thickness is 10～120 μ m.
4. the manufacture method of polyvinyl alcohol film, it is to comprise the manufacture method that the polymerization degree is the polyvinyl alcohol film that 5100～10000 polyvinyl alcohol, swelling capacity are 200～240%, the delay degree of the central part of width is 10～40nm, wherein, be that the film forming stoste of 5100～10000 polyethylene alcohol and water is carried out film forming as raw material using containing the polymerization degree, then dry, only the parallel both sides of film are fixed, heat-treated.
5. manufacture method claimed in claim 4, wherein, is dried at the temperature in the scope of 50～70 DEG C.
6. the manufacture method described in claim 4 or 5 wherein, is heat-treated in the scope of 100～140 DEG C.
7. the manufacture method described in claim 4 or 5, it is the manufacture method as the polyvinyl alcohol film of the raw material of light polarizing film.
8. the manufacture method described in claim 4 or 5, it is to be the manufacture method of the polyvinyl alcohol film of the raw material of more than 99.95% light polarizing film as degree of polarization.
9. light polarizing film, it dyes the polyvinyl alcohol film described in any one in claim 1～3, stretch and obtains.
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| JP2008321801 | 2008-12-18 | ||
| JP2008-321801 | 2008-12-18 | ||
| CN200980151021.0A CN102257044B (en) | 2008-12-18 | 2009-12-14 | Polyvinyl alcohol film |
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| CN201410262444.2A Active CN103992606B (en) | 2008-12-18 | 2009-12-14 | Polyvinyl alcohol film |
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| JP (1) | JP5628025B2 (en) |
| KR (2) | KR101910668B1 (en) |
| CN (2) | CN102257044B (en) |
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Also Published As
| Publication number | Publication date |
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| CN103992606B (en) | 2016-08-24 |
| KR20110105803A (en) | 2011-09-27 |
| WO2010071094A1 (en) | 2010-06-24 |
| JPWO2010071094A1 (en) | 2012-05-31 |
| CN102257044B (en) | 2015-12-02 |
| CN102257044A (en) | 2011-11-23 |
| KR20160120356A (en) | 2016-10-17 |
| TW201033273A (en) | 2010-09-16 |
| JP5628025B2 (en) | 2014-11-19 |
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| KR101910668B1 (en) | 2018-10-22 |
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