CN103442871A - Polyvinyl alcohol polymer film and process for producing same - Google Patents

Polyvinyl alcohol polymer film and process for producing same Download PDF

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Publication number
CN103442871A
CN103442871A CN2012800158476A CN201280015847A CN103442871A CN 103442871 A CN103442871 A CN 103442871A CN 2012800158476 A CN2012800158476 A CN 2012800158476A CN 201280015847 A CN201280015847 A CN 201280015847A CN 103442871 A CN103442871 A CN 103442871A
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film
polymer film
pva
dryer roll
ave
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CN103442871B (en
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森保二郎
风藤修
日笠慎太郎
胜野良治
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Kuraray Co Ltd
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Kuraray Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/04—PVOH, i.e. polyvinyl alcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0034—Polarising
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

A PVA film that satisfies expressions (I) and (II), which has satisfactory stretchability and from which a polarizing film can be efficiently produced; and a process for film production which comprises (a) ejecting a PVA-containing film formation dope in a film form onto the first drying roll of a film formation device equipped with a plurality of drying rolls, partly drying the web, and then successively drying the web with the subsequent drying rolls to produce a film, wherein (b) the ratio of the peripheral speed (ST) of the drying roll on which the volatile content of the PVA film has fallen to 13 mass% to the peripheral speed (S1) of the first drying roll, ST/S1, is regulated to 0.990-1.050, (c) the ratio of the peripheral speed (SL) of the last drying roll to the peripheral speed ST, SL/ST, is regulated to 0.960-0.980, and (d) the SL/S1 ratio is regulated to 0.970-1.010. [delta]n(MD)Ave-0.1*10<-3><=[delta]n(TD)Ave<=[delta]n(MD)Ave+0.25*10<-3> (I) [delta]n(TD)Ave<=2.5*10<-3> (II) [In the expressions, [delta]n(MD)Ave indicates the value obtained by averaging the machine-direction birefringence values of the PVA film with respect to the film thickness direction, and [delta]n(TD)Ave indicates the value obtained by averaging the transverse-direction birefringence values of the PVA film with respect to the film thickness direction.]

Description

Polymer film of polyvinyl alcohol and manufacture method thereof
Technical field
The polarizing coating that the present invention relates to polymer film of polyvinyl alcohol (Off ィ Le system) and manufacture method thereof and made by this film.In more detail, though the present invention relates to have the high limit stretching ratio with the high magnification stretched film also not easy fracture, can not follow the fracture of film and the interruption of the operation that stretches etc., the polarizing coating that can manufacture the polymer film of polyvinyl alcohol of stretched film of the excellent in optical properties such as polarization property and manufacture method thereof and be made by this film with high finished product rate, good productivity ratio.
Background technology
Having the polarizer of optical transmission and function of shielding and the liquid crystal of the switching function with light etc. is all the important inscape of liquid crystal indicator (LCD).The vast scopes such as metrical instrument that the miniature instruments such as the calculator of the application of this liquid crystal indicator during also from initial stage of development and wrist-watch expand notebook computer, LCDs, color liquid crystal projecting apparatus, LCD TV, onboard navigation system, mobile phone to, use in doors, particularly in LCDs, LCD TV etc., the large positive development of pictureization.
The general manufacture as described below of polarizer: the method etc. that simultaneously is fixed processing in dyeing by the method processing dyeing with iodine, dichroic dye after the polymer film of polyvinyl alcohol uniaxial tension, by after polymer film of polyvinyl alcohol dyeing uniaxial tension, being fixed the method for processing with boron compound, in above-mentioned any method is manufactured polarizing coating, at diaphragms such as the one or both sides laminating tri cellulose acetate membrane of the polarizing coating obtained thus, cellulose acetate butyrate (CAB) films.
In recent years, along with expansion of the purposes of liquid crystal indicator etc., except display quality advanced, also require the further reduction of cost and the further raising of treatability.From the aspect reduced costs, need to improve the speed of production while manufacturing polarizing coating, and the tension failure in the time of need to preventing from polymer film of polyvinyl alcohol is stretched (fracture), reduce the fracture loss, improve yield rate, and prevent from following the fracture of film and the stretching operation produced, the interruption of stretching-dyeing operation etc.
A kind of method of the raising of the productivity ratio during as the manufacture polarizing coating, the shortening of drying time while requiring to manufacture polarizing coating, from this viewpoint, the former film of using as polarizing coating (former anti-Off ィ Le system), the polymer film of polyvinyl alcohol that general used thickness is 75 μ m left and right in the past, but the polymer film of polyvinyl alcohol of required thickness, further filming thinner than 70 μ m in recent years.
Yet, the problem of easier fracture when having a polymer film of polyvinyl alcohol more Bao Ze stretching with high magnification, from this viewpoint, though require to have the ultimate elongation multiplying power high very thin also can in the situation that not fracture can stretch thereby can have and the polymer film of polyvinyl alcohol of the polarizing coating of the equal above polarization property of the product that have now with good operability, high finished product rate, low cost, good productivity ratio manufacture with high magnification.
In the past, for purposes such as the draftability that improves polymer film of polyvinyl alcohol, the homogeneity while improving stretching, the polarization property that improves the polarizing coating that polymer film of polyvinyl alcohol is stretched and obtain and durability, the stoste that contains vinol series polymer in use is on one side during dry masking on one side, the adjustment of the moisture ratio of the vinol series polymer film while being filmed adjustment, the masking of draw ratio (ratio of the transporting velocity of the vinol series polymer film between the roller used of masking) etc.
As such prior art, known (1) has carried out the stretched film of molecularly oriented when the uniaxial tension fully in order to obtain, adopt the masking draw ratio below 1, ad infinitum reduce masking tension force and carry out the method (patent documentation 1, particularly its paragraph [0008]～[0009], embodiment etc.) for the manufacture of the masking operation of polymer film of polyvinyl alcohol; (2) in order to obtain carrying out the polymer film of polyvinyl alcohol of powerful stretching, when with the drum-type film-making machine, manufacturing polymer film of polyvinyl alcohol, make [coiling speed of the polymer film of polyvinyl alcohol of gained]/method (patent documentation 2) that [being positioned at the speed of drum of the upstream of the supply system pleurodiaphragmatic in terspace material] is 0.8～1.3; (3) in order to obtain carrying out the polymer film of polyvinyl alcohol of powerful stretching, in drying process when with the drum-type film-making machine, manufacturing polymer film of polyvinyl alcohol, make the volatile ingredient ratio of film reach the operation speed Rc of 10 % by weight when following and the method (patent documentation 3) that finally velocity ratio (Rf/Rc) of coiling speed Rf is 0.9～1.1 etc.
In addition, known (4) are even also have the polyvinyl alcohol mesentery of polarizing coating of wide cut of the optical property of homogeneous in order to obtain manufacturing large tracts of land, the volatile ingredient that will be positioned at polyvinyl alcohol film reaches the speed (Rc) of the dryer roll of the operation below 10% and the velocity ratio (Rf/Rc) of coiling speed (Rf) is controlled at 0.9～1.1, the temperature that reduces drying process is unequal, thereby manufactures the tensile elongation (S of MD direction m) and the tensile elongation (S of TD direction t) ratio (S m/ S t) be the method (patent documentation 4) of 0.7～1.3 polyvinyl alcohol mesentery; (5) even also there is the polyvinyl alcohol mesentery of polarizing coating of wide cut of the optical property of homogeneous in order to obtain manufacturing large tracts of land, reach the moment of 10～50 % by weight at the volatile ingredient of polyvinyl alcohol film, from the drum that is positioned at upstream side, polyvinyl alcohol film is peeled off, and made to be positioned at the method (patent documentation 5) that the speed of speed V2 of drum that the speed V1 of drum of upstream side and the volatile ingredient that is positioned at polyvinyl alcohol film just started to be less than the operation of 10 % by weight is 1.0～1.3 than V2/V1.
Also known (6) are in order to obtain providing the uniaxial tension that can carry out homogeneous, there is no fine crackle and the stretched film in space during stretching, the polymer film of polyvinyl alcohol that comprises specific skin/core/cortex, the stoste that is 50～90 quality % to the volatile ingredient ratio that contains vinol series polymer with the first dryer roll heating, and under defined terms, the vinol series polymer face do not contacted with the first dryer roll is sprayed to hot blast simultaneously, the moment that reaches 15～30 quality % in the volatile ingredient ratio peels off the vinol series polymer film from the first dryer roll, make it with the second dryer roll, contact to carry out drying, now, make the peripheral speed (S of the first dryer roll 1) and the peripheral speed (S of the second dryer roll 2) ratio (S 2/ S 1) be method (patent documentation 6) of 1.000～1.100 etc.
Yet, in above-mentioned patent documentation 1～6, and make the not scheme of fracture of film while being not disclosed in the polymer film of polyvinyl alcohol of the thin thickness of polymer film of polyvinyl alcohol, particularly film with the high magnification uniaxial tension, particularly further improve the scheme of the ultimate elongation multiplying power of film.
The prior art document
Patent documentation
Patent documentation 1: Japanese patent laid-open 6-136151 communique
Patent documentation 2: Japanese Patent Laid-Open 2001-315141 communique
Patent documentation 3: Japanese Patent Laid-Open 2001-315146 communique
Patent documentation 4: Japanese Patent Laid-Open 2002-30164 communique
Patent documentation 5: Japanese Patent Laid-Open 2002-79531 communique
Patent documentation 6: Japanese Patent Laid-Open 2005-324355 communique
Non-patent literature
Non-patent literature 1: " the high molecular smooth physical property of polymer science One Point 10 ", the 3rd printing of first edition, stand altogether and publish Co., Ltd., on December 15th, 2007, p.19-21.
Summary of the invention
Invent problem to be solved
The purpose of this invention is to provide a kind of ultimate elongation multiplying power high, can in the situation that not fracture stretch with high magnification thereby can have and the polymer film of polyvinyl alcohol of the stretched film such as polarizing coating of the equal above optical property of the product that have now with good operability, high finished product rate, low cost, good productivity ratio manufacture.
Even purpose of the present invention particularly provide than the polymer film of polyvinyl alcohol in the past used in the manufacture of polarizing coating thinlyyer also there is the high limit stretching ratio, in the situation that can carry out swimmingly uniaxial tension at fracture not while stretching with high magnification, can make than in the past thinner stretched film and further shorten drying time while manufacturing polarizing coating, can manufacture with better productivity ratio the polymer film of polyvinyl alcohol of polarizing coating.
Purpose of the present invention also is to provide and can manufactures continuously swimmingly the method for the polymer film of polyvinyl alcohol of the characteristic with above-mentioned excellence with high production rate.
In addition, the purpose of this invention is to provide the polarizing coating of being made by above-mentioned polymer film of polyvinyl alcohol.
For solving the means of problem
The inventor has carried out conscientiously research in order to achieve the above object and repeatedly, found that, if the birefringence of the mechanical flow direction (length direction) of polymer film of polyvinyl alcohol on the thickness direction of film equalization and value and the birefringence of width on the thickness direction of film equalization and value meet specific relation, and the birefringence of the width of polymer film of polyvinyl alcohol on the thickness direction of film equalization and value in specific number range, the ultimate elongation multiplying power of film raises, even stretch and also be difficult for occurring the fracture of film with high magnification, can be in the situation that do not interrupt stretching operation with high finished product rate, with low cost, manufacture the stretched film such as polarizing coating of the excellent in optical properties such as polarization property with good productivity ratio.Also find in addition, if the birefringence of the mechanical flow direction of polymer film of polyvinyl alcohol on the thickness direction of film equalization and value in specific number range, the ultimate elongation multiplying power of film further improves.
Particularly find, the birefringence of the mechanical flow direction of polymer film of polyvinyl alcohol on the thickness direction of film equalization and value and the birefringence of width on the thickness direction of film equalization and value meet specific relation, and the birefringence of width on the thickness direction of film equalization and the above-mentioned polymer film of polyvinyl alcohol of value in specific scope in, even the Thickness Ratio of this film in the past in the manufacture of polarizing coating the thickness of polymer film of polyvinyl alcohol commonly used thinner, be the thickness of 30～65 μ m left and right, also there is the high limit stretching ratio, therefore can in the situation that not fracture carry out swimmingly uniaxial tension with high magnification, thereby the further filming can realize manufacturing polarizing coating the time, can further shorten the drying time while manufacturing polarizing coating.
In addition, the discoveries such as the inventor, above-mentioned polymer film of polyvinyl alcohol with high limit stretching ratio can be by the following method manufactured swimmingly continuously with high production rate: the masking stoste that will contain vinol series polymer spues to after on the first dryer roll of the film forming apparatus that possesses many dryer rolls, with these many dryer rolls drying successively, be filmed, now, the peripheral speed of the dryer roll while making the volatile ingredient ratio of vinol series polymer film reach 13 quality % with respect to the ratio of the peripheral speed of the first dryer roll in specific number range, the ratio of the peripheral speed of the dryer roll when peripheral speed that makes final dryer roll reaches 13 quality % with respect to the volatile ingredient ratio of vinol series polymer film is in specific number range, the peripheral speed that makes final dryer roll with respect to the ratio of the peripheral speed of the first dryer roll in specific number range.
In addition, the discoveries such as the inventor, when the polymer film of polyvinyl alcohol high by said method manufacturing limit stretching ratio, the volatile ingredient ratio of the vinol series polymer film while preferably making to peel off from the first dryer roll is in specific number range, preferably the roll surface temperature of each dryer roll is more than 65 ℃, also have, if the volatile ingredient ratio of the masking stoste that contains vinol series polymer is 60～75 quality %, and the roll surface temperature of the first dryer roll is 80～120 ℃, even the peripheral speed of the first dryer roll reaches the high speed more than 8m/ minute, the birefringence of mechanical flow direction of also can be swimmingly with good productivity ratio, manufacturing polymer film of polyvinyl alcohol on the thickness direction of film equalization and value and the birefringence of width on the thickness direction of film equalization and value meet specific relation, and the birefringence of width on the thickness direction of film equalization and value the regulation number range in, the polymer film of polyvinyl alcohol that the ultimate elongation multiplying power is high, based on these discoveries, further repeatedly studied, thereby completed the present invention.
That is, the present invention is:
(1) polymer film of polyvinyl alcohol, is characterized in that, meets following formula (I) and (II).
Δn(MD) Ave—0.1×10 -3≤Δn(TD) Ave≤Δn(MD) Ave+0.25×10 -3 (I)
Δn(TD) Ave≤2.5×10 -3 (II)
[in above formula, Δ n (MD) avethe birefringence of mechanical flow direction that means polymer film of polyvinyl alcohol on the thickness direction of this film equalization and value, Δ n (TD) avethe birefringence of width that means polymer film of polyvinyl alcohol on the thickness direction of this film equalization and value].
In addition, the present invention is:
(2) polymer film of polyvinyl alcohol of above-mentioned (1), it meets following formula (III);
1.3 * 10 -3≤ Δ n (MD) ave≤ 2.0 * 10 -3(III); And
(3) polymer film of polyvinyl alcohol of above-mentioned (1) or (2), its thickness is in the scope of 30～65 μ m.
The present invention is still:
(4) manufacture method of polymer film of polyvinyl alcohol, is characterized in that,
(a) use the film forming apparatus possess the many dryer rolls that rotating shaft is parallel to each other, the masking stoste that will contain vinol series polymer spues to the first dryer roll of this film forming apparatus and, after carrying out the part drying, further carries out drying with follow-up dryer roll and carry out masking with membranaceous; Now,
(b) peripheral speed (S of the dryer roll when volatile ingredient ratio of vinol series polymer film reaches 13 quality % t) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S t/ S 1) be 0.990～1.050;
(c) peripheral speed (S of final dryer roll l) peripheral speed (S of dryer roll while with respect to the volatile ingredient ratio of vinol series polymer film, reaching 13 quality % t) ratio (S l/ S t) be 0.960～0.980;
(d) peripheral speed (S of final dryer roll l) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S l/ S 1) be 0.970～1.010.
In addition, the present invention is:
(5) manufacture method of above-mentioned (4), wherein, the volatile ingredient ratio of the vinol series polymer film while peeling off from the first dryer roll is 17～30 quality %;
(6) manufacture method of above-mentioned (4) or (5), wherein, the roll surface temperature of each dryer roll is more than 65 ℃; And
(7) manufacture method of any one in above-mentioned (4)～(6), wherein, the volatile ingredient ratio of the masking stoste that contains vinol series polymer is 60～75 quality %, and the roll surface temperature of the first dryer roll is 80～120 ℃, the peripheral speed (S of the first dryer roll 1) be 8～25m/ minute.
In addition, the present invention is:
(8) polarizing coating, the polymer film of polyvinyl alcohol of its any one in above-mentioned (1)～(3) is made.
The effect of invention
Polymer film of polyvinyl alcohol of the present invention has the high limit stretching ratio, therefore when manufacturing stretched film, even the fracture of film also be difficult for to occur with the high magnification uniaxial tension, thus can in the situation that the operation of not interrupting stretching with high finished product rate, with the stretched film such as polarizing coating low-cost, manufacture the excellent in optical properties such as polarization property with good productivity ratio.
Even particularly the Thickness Ratio of polymer film of polyvinyl alcohol film of the present invention in the past in order to manufacture polarizing coating etc. the thickness of polymer film of polyvinyl alcohol commonly used thinner, be the thickness of 30～65 μ m left and right, also there is the high limit stretching ratio, therefore can in the situation that not fracture carry out swimmingly uniaxial tension with high magnification, thereby the further filming can realize manufacturing stretched film the time, can further shorten the drying time while manufacturing polarizing coating etc., and can boost productivity by this.
In addition, in recent years, the former film of using as polarizing coating, also use length to surpass the polymer film of polyvinyl alcohol of 1000m, and polymer film of polyvinyl alcohol of the present invention has the high limit stretching ratio, therefore can stretch with the multiplying power than in the past higher, thereby the amount of obtaining of the polarizing coating of being made by polymer film of polyvinyl alcohol is more than ever before.
By adopting manufacture method of the present invention, can manufacture continuously swimmingly the polymer film of polyvinyl alcohol of the present invention of the characteristic with above-mentioned excellence with high production rate.
The accompanying drawing explanation
[Fig. 1] Fig. 1 means the Δ n (MD) that measures polymer film of polyvinyl alcohol avethe time the schematic diagram of acquisition method of sample.
[Fig. 2] Fig. 2 means the Δ n (TD) that measures polymer film of polyvinyl alcohol avethe time the schematic diagram of acquisition method of sample.
The specific embodiment
Below, the present invention is described in detail.
In general, in the transparent film made from transparent polymer such as vinol series polymers, polymer chain under the effect of the plastic deformation caused by shear stress and strain etc. along flow direction (the mechanical flow direction: length direction) orientation, the polarised direction of the atomic group of formation polymer is consistent on microcosmic, thereby produces the distinctive birefringence of polymer (non-patent literature 1).
The birefringence of the mechanical flow direction of polymer film of polyvinyl alcohol [Δ n (MD)] is tried to achieve by following formula [i], and in addition, the birefringence of width [Δ n (TD)] is tried to achieve by following formula [ii].
Δn(MD)=nMD-nz [i]
Δn(TD)=nTD-nz [ii]
[in formula, nMD means the refractive index of the mechanical flow direction (length direction) of film, and nTD means the refractive index of the width of film, and nz means the refractive index of the thickness direction of film].
As record in non-patent literature 1, in the film made from transparent polymer such as vinol series polymers, the polymer chain that forms film easily is orientated along mechanical flow direction (length direction), comprise in the polymer film of polyvinyl alcohol of the polymer film of polyvinyl alcohol of record in above-mentioned patent documentation 1～6, generally be " birefringence of mechanical flow direction [Δ n (MD)] ">relation of " birefringence of width [Δ n (TD)] ", that is, the birefringence of mechanical flow direction [Δ n (MD)] is easily larger than the birefringence of width [Δ n (TD)].
In contrast, polymer film of polyvinyl alcohol of the present invention meets following formula (I) and (II), different from existing polymer film of polyvinyl alcohol in this.
Δn(MD) Ave—0.1×10 -3≤Δn(TD) Ave≤Δn(MD) Ave+0.25×10 -3 (I)
Δn(TD) Ave≤2.5×10 -3 (II)
[in above formula, Δ n (MD) avethe birefringence of mechanical flow direction that means polymer film of polyvinyl alcohol on the thickness direction of this film equalization and value, Δ n (TD) avethe birefringence of width that means polymer film of polyvinyl alcohol on the thickness direction of this film equalization and value].
; from above formula (I); in polymer film of polyvinyl alcohol of the present invention (following sometimes " polyvinyl alcohol " is called to " PVA "), the birefringence of the mechanical flow direction of PVA series polymer film (the streamline direction while manufacturing continuously the PVA series polymer film) [below be sometimes referred to as " length direction (MD) "] on the thickness direction of this film equalization and value " Δ n (MD) ave" with the birefringence of the width (with the rectangular direction of length direction) of PVA series polymer film [below be sometimes referred to as " width (TD) "] on the thickness direction of this film equalization and value " Δ n (TD) ave" equal or smaller, even or over " Δ n (TD) ave", it is measured also seldom.
PVA series polymer film of the present invention, except this formula (I), also has the feature that meets above formula (II).
PVA series polymer film of the present invention meets above formula (I) and (II), even thereby in the situation that the Thickness Ratio of film is in the past thinner, also there is the high limit stretching ratio, even thereby also be difficult for occurring the fracture of film with the high magnification uniaxial tension when the stretched film such as manufacture polarizing coating, can not cause because of the fracture of film the interruption of stretching operation, can be with high finished product rate, manufacture the stretched film of the filming of the excellent in optical properties such as polarization property with good productivity ratio.
If do not meet above formula (I), the ultimate elongation multiplying power of PVA series polymer film reduces, and the fracture, particularly easy fracture when the thin thickness of film of film easily occur during with the high magnification uniaxial tension.
PVA series polymer film of the present invention preferably meets following formula (I '), more preferably meets following formula (I ' '), further preferably meets following formula (I ' ' ').
Δn(MD) Ave-0.05×10 -3≤Δn(TD) Ave≤Δn(MD) Ave+0.23×10 -3 (I’)
Δn(MD) Ave≤Δn(TD) Ave≤Δn(MD) Ave+0.2×10 -3 (I’’)
Δn(MD) Ave+0.05×10 -3≤Δn(TD) Ave≤Δn(MD) Ave+0.18×10 -3 (I’’’)
In addition, if the Δ n (TD) of PVA series polymer film avebe greater than 2.5 * 10 -3, outside the scope of above-mentioned formula (II), the ultimate elongation multiplying power of PVA series polymer film reduces, and is difficult to make the PVA series polymer film to stretch with high magnification at length direction (MD), is difficult to obtain the stretched film of excellent in optical properties.
In order exceedingly to reduce Δ n (TD) ave, need to when manufacturing the PVA series polymer film, allow the drying of width to shrink, the tendency of the effective width yield reduction of PVA series polymer film is arranged, therefore the Δ n (TD) of PVA series polymer film of the present invention avepreferably 1.5 * 10 -3～2.2 * 10 -3scope in, more preferably 1.6 * 10 -3～2.0 * 10 -3scope in.
PVA series polymer film of the present invention, except above formula (I) with (II), preferably also meets following formula (III).
1.3×10 -3≤Δn(MD) Ave≤2.0×10 -3 (III)
Δ n (MD) by the PVA series polymer film ave2.0 * 10 -3below, the ultimate elongation multiplying power of PVA series polymer film further improves, and easily the PVA series polymer film is stretched with high magnification at length direction (MD), more easily obtains the stretched film of excellent in optical properties.On the other hand, in order to make the Δ n (MD) of PVA series polymer film avebe less than 1.3 * 10 -3, need to greatly reduce the peripheral speed ratio of dryer roll, so have PVA based polymer film when masking that lax tendency easily occurs between dryer roll.
The Δ n (MD) of PVA series polymer film of the present invention avemore preferably 1.4 * 10 -3～1.95 * 10 -3scope in, further preferably 1.5 * 10 -3～1.9 * 10 -3scope in.
In addition, in the PVA series polymer film, at the upper Δ n (MD) of the width (TD) of film aveand/or Δ n (TD) avevalue often can change, particularly at the both ends of width, Δ n (MD) aveeasily raise, but, as long as at least at the central portion of the width (TD) of PVA series polymer film, meet formula (I) and (II), preferably meet formula (I)～(III), preferably in the whole zone of the part more than 8 one-tenth of the width centered by the central part of the width by the PVA series polymer film (TD) (TD), meet formula (I) and (II), preferably meet formula (I)～(III).(deburring) can removed by alongst (MD) stretching cutting before of PVA series polymer film in the both ends that do not meet the width (TD) of formula (I) and PVA series polymer film (II).
" the Δ n (MD) of PVA series polymer film ave" [birefringence of the length direction of PVA series polymer film (MD) on the thickness direction of this film equalization and value] and " Δ n (TD) ave" [birefringence of the width of PVA series polymer film (TD) on the thickness direction of this film equalization and value] can measure by the following method.
" 1 " Δ n (MD) avedetermination method:
(that exemplify here is the Δ n (MD) of central portion of the width (TD) of PVA series polymer film avedetermination method.)
(i) on the optional position of the length direction (MD) of PVA series polymer film, cut out the shred of the size of MD * TD=2mm * 10mm from the central portion of the width (TD) of film as shown in Fig. 1 (a), this shred is clamped from both sides with the PET film of thick 100 μ m, again it is clipped in wooden frame, is installed on the slicer device.
(ii) then, the length direction (MD) of the shred that gathers as mentioned above (PET film and wooden frame are not shown) and shred as shown in Fig. 1 (b), abreast with the cut-space of 10 μ m, is manufactured to the section (MD * TD=2mm * 10 μ m) of the observation use shown in 10 Fig. 1 (c).From this section, select 5 tangent planes level and smooth and there is no the section of slice thickness inequality, they are put respectively on slide, with microscope (Keyemce company system), measure slice thickness.In addition, in the visual field of 10 times, eyepiece, object lens 20 times (amounting to 200 times), observed.
(iii) then, in order to observe tangent plane, to cut into slices and fall as described in Fig. 1 (d), cut side up is put on slide, with cover glass and silicone oil (refractive index 1.04) sealing, measure the delay of 5 sections by two-dimentional photoelastic evaluation system " PA-micro " (the Photonic Lattice of Co., Ltd. system).
(iv) under the state on the delay by each section distributes the mensuration picture that is presented at " PA-micro ", mark the line α of the Surface Vertical come with pleurodiaphragmatic in terspace in the mode across section, in the enterprising line linearity analysis of this line segment α, obtain the delay distributed data of the thickness direction of film.In addition, in the visual field of 10 times, eyepiece, object lens 20 times (amounting to 200 times), observed.In addition, the error for the variation suppressed because of the position passed through of line segment α in section causes, be made as 300 pixels by live width, gets the mean value of delay.
(v) value that the delay of the thickness direction of the film that will obtain as mentioned above distributes is divided by the thickness recorded with microscope, the birefringence Δ n (MD) that obtains the thickness direction of film distributes, and gets the mean value that the birefringence Δ n (MD) of the thickness direction of this film distributes.The mean value that the birefringence Δ n (MD) of the thickness direction of the film that will try to achieve respectively for 5 sections distributes is further average, as " Δ n (MD) ave".
" 2 " Δ n (TD) avedetermination method:
(that exemplify here is the Δ n (TD) of central portion of the width (TD) of PVA series polymer film avedetermination method.)
(i) on the optional position of the length direction (MD) of PVA series polymer film, cut out the shred of the size of MD * TD=10mm * 2mm from the central portion of the width (TD) of film as shown in Fig. 2 (a), this shred is clamped from both sides with the PET film of thick 100 μ m, again it is clipped in wooden frame, is installed on the slicer device.
(ii) then, the width (TD) of the shred that gathers as mentioned above (PET film and wooden frame are not shown) and shred as shown in Fig. 2 (b), abreast with the cut-space of 10 μ m, is manufactured to the section (MD * TD=10 μ m * 2mm) of the observation use shown in 10 Fig. 2 (c).From this section, select 5 tangent planes level and smooth and there is no the section of slice thickness inequality, they are put respectively on slide, with microscope (Keyemce company system), measure slice thickness.In addition, in the visual field of 10 times, eyepiece, object lens 20 times (amounting to 200 times), observed.
(iii) then, in order to observe tangent plane, to cut into slices and fall as described in Fig. 2 (d), cut side up is put on slide, with cover glass and silicone oil (refractive index 1.04) sealing, measure the delay of 5 sections by two-dimentional photoelastic evaluation system " PA-micro " (the Photonic Lattice of Co., Ltd. system).
(iv) under the state on the delay by each section distributes the mensuration picture that is presented at " PA-micro ", mark the line β of the Surface Vertical come with pleurodiaphragmatic in terspace in the mode across section, in the enterprising line linearity analysis of this line segment β, obtain the delay distributed data of the thickness direction of film.In addition, in the visual field of 10 times, eyepiece, object lens 20 times (amounting to 200 times), observed.In addition, the error for the variation suppressed because of the position passed through of line segment β in section causes, be made as 300 pixels by live width, gets the mean value of delay.
(v) value that the delay of the thickness direction of the film that will obtain as mentioned above distributes is divided by the thickness recorded with microscope, the birefringence Δ n (TD) that obtains the thickness direction of film distributes, and gets the mean value that the birefringence Δ n (TD) of the thickness direction of this film distributes.The mean value that the birefringence Δ n (TD) of the thickness direction of the film that will try to achieve respectively for 5 sections distributes is further average, as " Δ n (TD) ave".
The thickness of PVA series polymer film of the present invention can, in the scope of 5～150 μ m, in the former film situation of using as polarizing coating etc., be preferably 30～65 μ m.PVA series polymer film of the present invention has the high limit stretching ratio, even therefore Film Thickness Ratio in the past the multiplex polarizing coating of doing with the thickness of former film, be that PVA series polymer film about 75 μ m is thinner, be in the situation of 30～65 μ m as mentioned above, also can be in the situation that the fracture of film do not occur stretch with high magnification, thereby can have with good productivity ratio manufacture swimmingly and have the product stretched film of the above optical characteristics such as polarization property on an equal basis now with high finished product rate, and by being that the PVA series polymer film of 30～65 μ m stretches with high magnification by thickness, the Thickness Ratio of the film after making to stretch is in the past thinner, and can shorten the drying time while manufacturing polarizing coating, can improve the manufacturing speed of polarizing coating.
If the thickness of PVA series polymer film is blocked up, when manufacturing polarizing coating, be difficult to promptly carry out drying, on the other hand, if the thickness of PVA series polymer film is excessively thin, the fracture of film easily occurs when the uniaxial tension for the manufacture of polarizing coating.
The width of PVA series polymer film of the present invention is not particularly limited, but in recent years, because the large picture of LCD TV, display screen, so in order effectively to use therein, more than width is preferably 2m, more preferably more than 3m, more preferably more than 4m.In addition, in fact with the production machine, manufacture in the situation of polarizer, if the width of film is excessive, be difficult to carry out the uniaxial tension of homogeneous, so the width of PVA series polymer film is preferably below 8m.
Its quality swellbility of PVA series polymer film of the present invention is preferably 180～250%, and more preferably 185～240%, more preferably 190～230%.If the quality swellbility of PVA series polymer film is too low, be difficult to stretch, the tendency of the stretched film that is difficult to manufacture excellent in optical properties is arranged, on the other hand, if the quality swellbility is too high, the operation trafficability characteristic variation while stretching, can't obtain the polarizing coating of high-durability sometimes.
Here said quality swellbility refer to after quality when the PVA series polymer film is flooded to 30 minutes in the distilled water of 30 ℃ is divided by above-mentioned dipping the quality after dry 16 hours under 105 ℃ and the percentage of value, particularly can measure by the method for putting down in writing in following examples.
As the PVA based polymer that forms PVA series polymer film of the present invention, can exemplify such as making the vinyl esters polymerization the polyvinylesters saponification and PVA, make comonomer graft copolymerization on the main chain of PVA and the modified PVA based polymer, will make vinyl esters and comonomer copolymerization and the saponification of modified polyvinyl ester and the modified PVA based polymer made, by the part of the hydroxyl of unmodified PVA or modified PVA based polymer by crosslinked so-called polyvinyl acetal resins that obtain of aldehydes such as formaldehyde, butyraldehyde, benzaldehydes etc.
In the situation that the PVA based polymer that forms PVA series polymer film of the present invention is the modified PVA based polymer, the modification amount of PVA based polymer is preferably below 15 % by mole, more preferably below 5 % by mole.
The above-mentioned vinyl esters used in manufacture as the PVA based polymer, can exemplify such as vinyl acetate, vinyl formate, vinyl laurate, propionate, vinyl butyrate, new vinyl acetate acid, tertiary ethylene carbonate, stearic acid vinyl ester, vinyl benzoate etc.These vinyl esters can be used alone or in combination.In these vinyl esters, from the preferred vinyl acetate of the viewpoint of productivity ratio.
In addition, as above-mentioned copolymer, can exemplify the olefines (alpha-olefin etc.) of carbon numbers 2～30 such as ethene, propylene, 1-butylene, isobutene; Acrylic acid or its salt; The esters of acrylic acids (for example acrylic acid carbon number 1～18 Arrcostab) such as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid-2-ethyl caproite, dodecylacrylate, acrylic acid stearyl; Methacrylic acid or its salt; The methyl acrylic esters (for example carbon number 1～18 Arrcostab of methacrylic acid) such as methyl methacrylate, EMA, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, methacrylic acid-2-Octyl Nitrite, lauryl methacrylate, methacrylic acid stearyl; Acrylamide, N methacrylamide, N-ethyl acrylamide, N,N-DMAA, DAAM, acrylamido propane sulfonic acid or its salt, acrylamido diemethylamine or the acrylamide derivatives such as its salt, N hydroxymethyl acrylamide or derivatives thereof; Methacrylamide, N-methyl acrylamide, N-ethyl-methyl acrylamide, methacryl amido propane sulfonic acid or the methacrylamide derivatives such as its salt, methacryl amido diemethylamine or its salt, N-methylol methacrylamide or derivatives thereof; The N-vinylamide classes such as N-vinyl formamide, N-vinyl acetamide, NVP; The vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether, IVE, tert-Butyl vinyl ether, dodecyl vinyl, stearyl vinyl ethers; The nitrile such as acrylonitrile, methacrylonitrile; The vinyl halides base class such as vinyl chloride, vinylidene chloride, PVF, vinylidene; The allyl compound such as allyl acetate, chloropropene; The derivatives such as the unsaturated dicarboxylic such as maleic acid, itaconic acid, its salt or its ester; The vinyl silanes based compounds such as vinyltrimethoxy silane; Methylvinyl acetate; Unsaturated sulfonic acid or derivatives thereof etc.Wherein preferably alpha-olefin, particularly preferably ethene.
From the viewpoint of the polarization property of the polarizing coating of gained and durability etc., the average degree of polymerization that forms the PVA based polymer of PVA series polymer film of the present invention is preferably more than 1000, more preferably more than 1500, more preferably more than 2000.On the other hand, from the viewpoint of the easiness of the manufacture of the PVA series polymer film of homogeneous, draftability etc., the upper limit of the average degree of polymerization of PVA based polymer is preferably below 8000, is particularly preferably below 6000.
Here, " average degree of polymerization " of the PVA based polymer in this specification refers to take the average degree of polymerization that JIS K6726-1994 records as benchmark, according to the inherent viscosity by recording in the water of 30 ℃ after the saponification again of PVA based polymer, purifying, tries to achieve.
Viewpoint from the polarization property of the polarizing coating of gained and durability etc., the saponification degree that forms the PVA based polymer of PVA series polymer film of the present invention is preferably more than 95.0 % by mole, more preferably more than 98.0 % by mole, more preferably, more than 99.0 % by mole, most preferably be more than 99.3 % by mole.
Here, " saponification degree " of the PVA based polymer in this specification refer to respect to can by saponification change into the shared ratio of the molal quantity of total mole number, this vinyl alcohol units of the construction unit (being typically vinyl ester units) of vinyl alcohol units and vinyl alcohol units (% by mole).The saponification degree of PVA based polymer is measured with the benchmark that is recited as of JIS K6726-1994.
The method for making of PVA series polymer film of the present invention is not particularly limited, so long as can manufacture the method that meets above formula (I) and PVA series polymer film (II), can manufacture by any method, and PVA series polymer film of the present invention can be manufactured with high production rate swimmingly continuously by manufacture method of the present invention, this manufacture method comprises the steps:
(a) use the film forming apparatus possess the many dryer rolls that rotating shaft is parallel to each other, the masking stoste that will contain the PVA based polymer spues to the first dryer roll of this film forming apparatus and, after carrying out the part drying, further carries out drying with follow-up dryer roll and carry out masking with membranaceous; Now,
(b) peripheral speed (S of the dryer roll when volatile ingredient ratio of PVA based polymer film reaches 13 quality % t) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S t/ S 1) be 0.990～1.050;
(c) peripheral speed (S of final dryer roll l) peripheral speed (S of dryer roll while with respect to the volatile ingredient ratio of PVA based polymer film, reaching 13 quality % t) ratio (S l/ S t) be 0.960～0.980;
(d) peripheral speed (S of final dryer roll l) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S l/ S 1) be 0.970～1.010.
Below the manufacture method of the PVA series polymer film of the invention described above is carried out to more specific description.
Can prepare by the PVA based polymer being mixed with liquid medium make solution or make fused solution by the meltings such as PVA based polymer particle that will contain liquid medium etc. by the masking stoste that contains the PVA based polymer.
The dissolving of PVA based polymer in liquid medium, the melting of PVA based polymer particle that contains liquid medium etc. can be carried out with stirring-type mixing arrangement, melt extruder etc.
As liquid medium now used, can exemplify such as water, methyl-sulfoxide, dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, ethylenediamine, diethylenetriamines etc., these liquid mediums can a kind of independent uses or are used in combination.Wherein preferably make water, methyl-sulfoxide or both mixtures, particularly preferably make water.
The viewpoint of the draftability of operation trafficability characteristic when dissolving, melting, the raising film from promotion PVA based polymer liquid medium manufactured, the PVA series polymer film of raising gained etc. is preferably added plasticizer in masking stoste.
As plasticizer, preferably use polyalcohol, can exemplify such as ethylene glycol, glycerine, diglycerol, propane diols, diethylene glycol, triethylene glycol, TEG, trimethylolpropane etc., these plasticizer can a kind of independent uses or are used in combination.From the viewpoint of the raising effect excellence of draftability, wherein preferably use one or more in glycerine, diglycerol and ethylene glycol.
The addition of plasticizer is preferably 0～30 mass parts with respect to PVA based polymer 100 mass parts, and more preferably 3～25 mass parts, be particularly preferably 5～20 mass parts.If the addition of plasticizer is with respect to PVA based polymer 100 mass parts more than 30 mass parts, the PVA series polymer film of gained is too soft sometimes, and treatability reduces.
The viewpoint of the treatability of the fissility the dryer roll during from raising from manufacture PVA series polymer film, the PVA series polymer film of gained etc. is preferably added surfactant in masking stoste.Kind as surfactant, be not particularly limited, and preferably uses anionic surfactant or nonionic surfactant.
As the anionic surfactant, preference is as the anionic surfactant of the sulfonic acid types such as the sulfuric acid ester types such as the carboxylic acid types such as potassium laurate, sulfuric acid monooctyl ester, dodecyl benzene sulfonate.
In addition, as nonionic surfactant, preference is as the nonionic surfactant of the allyl phenyl ether types such as the alkanolamide types such as polypropylene glycol ether type, the oleic acid diethyl amides such as alkylamide type, the polyoxyethylene poly-oxygen propylene aethers such as the alkylamine types such as the Arrcostab types such as alkyl phenyl ether type, the polyoxyethylene laurates such as the alkyl ether types such as polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene lauryl amino ethers, polyoxyethylene lauramide, polyoxyalkylene allyl phenyl ether.These surfactants can a kind of independent uses or are used in combination.
The addition of surfactant is preferably 0.01～1 mass parts with respect to PVA based polymer 100 mass parts, and more preferably 0.02～0.5 mass parts, be particularly preferably 0.05～0.3 mass parts.If be less than 0.01 mass parts, sometimes be difficult to embody the raising effect of masking, fissility, on the other hand, if more than 1 mass parts, surfactant, in film surface stripping, becomes the reason of adhesion sometimes, and treatability reduces.
Masking stoste can contain in the scope of the characteristic that does not hinder PVA series polymer film of the present invention various additives, such as stabilizing agent (such as antioxidant, ultra-violet absorber, heat stabilizer etc.), bulking agent (dissolving mutually drug), anti-blocking agent, fire retardant, antistatic agent, lubricant, dispersant, fluidizing reagent, antiseptic etc.These additives can a kind of independent uses or are used in combination.
The volatile ingredient ratio of the masking stoste of using in the manufacture of PVA series polymer film is preferably 60～75 quality %, more preferably 65～70 quality %.If the volatile ingredient ratio of masking stoste is less than 60 quality %, the viscosity of masking stoste raises, and is difficult to be filtered and deaeration, and in addition masking itself is all very difficult sometimes.On the other hand, if the volatile ingredient ratio of masking stoste is greater than 75 quality %, viscosity is too low sometimes, and the homogeneity of the thickness of PVA series polymer film is impaired.
Here, said in this specification " the volatile ingredient ratio of masking stoste " refers to the volatile ingredient ratio of trying to achieve by following formula [iii].
The volatile ingredient ratio (quality %) of masking stoste={ (Wa-Wb)/Wa} * 100 [iii]
[in formula, Wa means the quality (g) of masking stoste, and Wb means the masking stoste of Wa (g) quality (g) after dry 16 hours in the electric air drier of 105 ℃.]
In the film forming apparatus that possesses the many dryer rolls that rotating shaft is parallel to each other used in the manufacture of PVA series polymer film, the quantity of dryer roll is preferably more than 3, more preferably more than 4, and more preferably 5～30.
Many dryer rolls are such as preferably being formed by metals such as nickel, chromium, copper, iron, stainless steels, and the metal material that particularly preferably by the roller surface, is difficult for burn into and has a bright luster forms.In addition, in order to improve the durability of dryer roll, more preferably use plating that the dryer roll of the nickel dam, chromium layer, nickel/chromium alloy layer etc. of individual layer or two-layer above combination is arranged.
The roll surface temperature of each dryer roll in many dryer rolls is preferably more than 65 ℃, more preferably more than 75 ℃.In addition, roll surface temperature as each dryer roll, roll surface temperature at final operation or the dryer roll that can use as Heat treating roll in close operation with it is preferably more than 100 ℃, and more preferably 100～120 ℃, the roll surface temperature of dryer roll in addition is preferably below 100 ℃.
The film forming apparatus used in the present invention can have hot-air drying device, annealing device, humidity control device of hot-blast stove formula etc. as required after many dryer rolls.
The masking stoste that will contain the PVA based polymer spues on the first dryer roll of film forming apparatus the time with membranaceous, such as using the known membranaceous device for discharging fixed (membranaceous casting device) such as T-shaped slit die, hopper plate (hopper plate), I-mould, lip coating machine mould, the masking stoste that will contain the PVA based polymer with membranaceous spuing (curtain coating) to the first dryer roll.
Dry on the first dryer roll with the membranaceous liquid that contains the PVA based polymer spued on the first dryer roll, the volatile ingredient ratio of PVA based polymer film reach be preferably 17～30 quality %, more preferably 17～29 quality %, more preferably the moment of 18～28 quality % peels off from the first dryer roll.
If the volatile ingredient ratio of the PVA based polymer film while peeling off from the first dryer roll is less than 17 quality %, Δ n (MD) is arranged avevalue with respect to Δ n (TD) aveincrease and do not meet the tendency of formula (I), on the other hand, if the volatile ingredient ratio of the PVA based polymer film while peeling off from the first dryer roll more than 30 quality %, have be difficult to from the first dryer roll peel off, fracture or easily produce uneven tendency sometimes.
Here, " the volatile ingredient ratio of PVA based polymer film or PVA series polymer film " in this specification refers to the volatile ingredient ratio of trying to achieve by following formula [iv].
A (quality %)={ (Wc-Wd)/Wc} * 100 [iv]
[in formula, A means the volatile ingredient ratio (quality %) of PVA based polymer film or PVA series polymer film, Wc means the quality (g) of the sample that gathers from PVA based polymer film or PVA series polymer film, and Wd means above-mentioned sample Wc (g) is put into to temperature 50 C, the following quality (g) of vacuum drier in the time of dry 4 hours of pressure 0.1kPa].
By using the PVA based polymer, the polyalcohols such as glycerine (plasticizer), in PVA based polymer film or PVA series polymer film that masking stoste prepared by surfactant and water forms, at above-mentioned " temperature 50 C, below pressure 0.1kPa, 4 hours " condition under when dry, mainly only has the water volatilization, other composition beyond water volatilizees hardly, remain in PVA based polymer film or PVA series polymer film, therefore the volatile ingredient ratio of PVA based polymer film or PVA series polymer film can be tried to achieve by measuring contained amount of moisture (moisture ratio) in PVA based polymer film or PVA series polymer film.
When dry with the first dryer roll, from the viewpoint of homogeneous drying property, rate of drying etc., the roll surface temperature of the first dryer roll is preferably 80～120 ℃, and more preferably 85～105 ℃, more preferably 93～99 ℃.If the surface temperature of the first dryer roll is higher than 120 ℃, film easily foams, and on the other hand, during lower than 80 ℃, the drying on the first dryer roll is insufficient, becomes and peels off bad reason.
From the viewpoint of productivity ratio of homogeneous drying property, rate of drying and PVA series polymer film etc., the peripheral speed (S of the first dryer roll 1) be preferably 8～25m/ minute, more preferably 11～23m/ minute, more preferably 14～22m/ minute.If the peripheral speed (S of the first dryer roll 1) be less than 8m/ minute, productivity ratio reduces, and birefringence easily increases, not preferred.On the other hand, if the peripheral speed (S of the first dryer roll 1) be greater than 25m/ minute, the drying on the first dryer roll is easily insufficient, not preferred.
With the membranaceous part drying of the masking stoste that contains the PVA based polymer on the first dryer roll spued, can only be used to carry out from the heat of the first dryer roll, but the viewpoint from homogeneous drying property, rate of drying etc., preferably when being heated with the first dryer roll, the face that do not contact with the first dryer roll (below be sometimes referred to as " the first dryer roll noncontact face ") is sprayed to hot blast, apply heat from the two sides of PVA based polymer film and carry out drying.
When the first dryer roll noncontact face that is positioned at the PVA based polymer film on the first dryer roll is sprayed to hot blast, preferably to the hot blast of whole area spray wind speed 1～10m/ second of the first dryer roll noncontact face, more preferably spray wind speed 2～8m/ hot blast of second, further preferably spray wind speed 3～8m/ hot blast of second.
If the wind speed of the hot blast that the first dryer roll noncontact face is sprayed is too small, be difficult to obtain the PVA series polymer film high as the ultimate elongation multiplying power of target of the present invention, and the dewfall of steam etc. occurs when dry on the first dryer roll, this water droplet drops onto on PVA based polymer film, easily produces defect in the PVA series polymer film finally obtained.On the other hand, if the wind speed of the hot blast that the first dryer roll noncontact face is sprayed is excessive, be difficult to obtain the PVA series polymer film high as the ultimate elongation multiplying power of target of the present invention, and the PVA series polymer film finally obtained produces uneven thickness, the uneven problems such as generation of dyeing easily occur thereupon.
From the viewpoint of drying efficiency, dry homogeneity etc., the temperature of the hot blast that the first dryer roll noncontact face of PVA based polymer film is sprayed is preferably 50～150 ℃, and more preferably 70～120 ℃, more preferably 80～95 ℃.The dew-point temperature of the hot blast in addition, the first dryer roll noncontact face of PVA based polymer film sprayed is preferably 10～15 ℃.If the temperature of the hot blast that the first dryer roll noncontact face of PVA based polymer film is sprayed is too low, drying efficiency, homogeneous drying property etc. easily reduce, and on the other hand, if too high, easily foam.
The mode of spraying hot blast for the first dryer roll noncontact face to PVA based polymer film is not particularly limited, can adopt can be to the first dryer roll noncontact face of PVA based polymer film, preferably its integral body is sprayed any mode of the hot blast of wind speed homogeneous and temperature homogeneous equably, wherein preferably adopts nozzle mode, cowling panel mode or their combination etc.The injection direction of the hot blast on the first dryer roll noncontact face of PVA based polymer film can be both the direction relative with the first dryer roll noncontact face, can be also roughly along the direction of the circumferential shapes of the first dryer roll noncontact face of the PVA based polymer film direction of the circumference on the roller surface of the first dryer roll (roughly along), or can be also direction in addition.
In addition, during the PVA based polymer film on the first dryer roll dry, the volatile ingredient that preferably will be produced by PVA based polymer film by drying and spray after hot blast carry out exhaust.The method of exhaust is not particularly limited, and preferred employing can not produce the method for exhausting of and temperature inequality uneven to the wind speed of the hot blast of the first dryer roll noncontact face injection of PVA based polymer film.
To on the first dryer roll, preferably be dried to the PVA based polymer film that the volatile ingredient ratio reaches 17～30 quality % peels off from the first dryer roll, this time, preferably make the first dryer roll noncontact face of PVA based polymer film relative with the second dryer roll, with the second dryer roll, carry out drying
Peripheral speed (the S of the second dryer roll 2) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S 2/ S 1) be preferably 1.005～1.090, more preferably 1.010～1.080.If ratio (S 2/ S 1) be less than 1.005, the pick-up point of PVA based polymer film from the first dryer roll the heterogeneity that easily becomes, the birefringence of width is uneven to be increased, and sometimes can't be used as the former film of optical film.In addition, if ratio (S 2/ S 1) be greater than 1.090, be difficult to obtain having the PVA series polymer film of the present invention of high limit stretching ratio.
When dry with the second dryer roll, from the viewpoint of homogeneous drying property, rate of drying etc., the roll surface temperature of the second dryer roll is preferably 65～100 ℃, and more preferably 65～98 ℃, more preferably 75～96 ℃.
To from the second dryer roll, peel off with the dried PVA based polymer of the second dryer roll film, according to quantity of the dryer roll arranged in film forming apparatus etc., with the 3rd dryer roll, the 4th dryer roll, the 5th dryer roll ... carry out successively drying etc. many dryer rolls.
Now, in the present invention, while regulate the tension force that puts on PVA based polymer film, carry out drying, so that the peripheral speed (S of the dryer roll of the volatile ingredient ratio of PVA based polymer film while reaching 13 quality % t) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S t/ S 1) be 0.990～1.050.Here, as " dryer roll when volatile ingredient ratio of PVA based polymer film reaches 13 quality % ", the volatile ingredient ratio of PVA based polymer film is in the situation that reach 13 quality % on dryer roll, refer to this dryer roll, the volatile ingredient ratio is in the situation that reach 13 quality % between two dryer rolls, refers to the dryer roll after position in these two dryer rolls is leaned on.By making ratio (S t/ S 1) in above-mentioned scope, the problems such as lax, circumvolution of film can not occur in the drying process till the volatile ingredient ratio of PVA based polymer film reaches 13 quality %, swimmingly the birefringence of factory length direction (MD) on the thickness direction of film equalization and value [Δ n (MD) ave] and the birefringence of width (TD) on the thickness direction of film equalization and value [Δ n (TD) ave] meet above formula (I) and (II) and then also meet the PVA series polymer film of the present invention of above formula (III).
Above-mentioned ratio (S while manufacturing the PVA series polymer film t/ S 1) be preferably 1.000～1.045.
In the present invention, the PVA based polymer film that the volatile ingredient ratio is reached to 13 quality % is further dry with follow-up dryer roll, makes PVA based polymer film.Now, in the present invention, Yi Bian make the peripheral speed (S of final dryer roll l) peripheral speed (S of dryer roll while with respect to the volatile ingredient ratio of PVA series polymer film, reaching 13 quality % t) ratio (S l/ S t) in 0.960～0.980 scope, Yi Bian carry out drying.By making ratio (S l/ S t) in above-mentioned scope, the problems such as lax, circumvolution of film can not occur in the drying process till obtaining final PVA series polymer film, swimmingly the birefringence of factory length direction (MD) on the thickness direction of film equalization and value [Δ n (MD) ave] and the birefringence of width (TD) on the thickness direction of film equalization and value [Δ n (TD) ave] meet above formula (I) and (II) and then also meet the PVA series polymer film of the present invention of above formula (III).
Above-mentioned ratio (S while manufacturing the PVA series polymer film l/ S t) be preferably 0.963～0.976.
In addition, while by said method, manufacturing the PVA series polymer film, the birefringence of the length direction of PVA series polymer film (MD) on the thickness direction of film equalization and value [Δ n (MD) ave] and the birefringence of width (TD) on the thickness direction of film equalization and value [Δ n (TD) ave] according to the peripheral speed (S of the first dryer roll 1) and the peripheral speed (S of final dryer roll l) ratio (S l/ S 1) and change.In order to manufacture swimmingly the PVA series polymer film of the present invention that meets above formula (I) and (II) and then also meet above formula (III), need to make the peripheral speed (S of final dryer roll l) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S l/ S 1) in 0.970～1.010 scope, preferably in 0.972～1.008 scope, more preferably in 0.975～1.006 scope.By this, while can suppress fold and the PVA series polymer film that meets above formula (I) and (II) and then also meet above formula (III) is manufactured in lax generation swimmingly.
In the manufacture method of the invention described above, final dryer roll or close to final dryer roll with final dryer roll can improve its surface temperature and as Heat treating roll.By dryer roll, as in the situation of Heat treating roll, roll surface temperature is preferably 90～140 ℃, more preferably 100～130 ℃.
In addition, also can divide the annealing device that is arranged with dryer roll.
Heating direction when the process from the first dryer roll to final dryer roll, that PVA based polymer film is dry is not particularly limited, because can be more equably by PVA based polymer film drying, so the mode preferably alternately contacted with each dryer roll from the first dryer roll to final dryer roll with the front and back of the arbitrary portion of PVA based polymer film is carried out drying.
Carried out that the above-mentioned dry PVA series polymer film of processing can be heat-treated as required, damping processing etc., finally the length with regulation coils into the roller shape, thereby obtains PVA series polymer film of the present invention.
The volatile ingredient ratio of the PVA series polymer film finally obtained by above-mentioned a succession of processing is preferably in the scope of 1～5 quality %, more preferably in the scope of 2～4 quality %.
While by PVA series polymer film of the present invention, manufacturing polarizing coating, for example can be dyeed to the PVA series polymer film, uniaxial tension, fixingly process, the dry processing and heat treatment as required.The order of dyeing and uniaxial tension is not particularly limited, and the processing of both can having dyeed before uniaxial tension is processed, also can process the processing of simultaneously dyeing with uniaxial tension, or the processing of also can dyeing after uniaxial tension is processed.In addition, the operation such as uniaxial tension, dyeing can be repeatedly.
The dyestuff used in dyeing as the PVA series polymer film, can be used iodine or dichroism organic dyestuff (for example directly to deceive (DirectBlack) 17,19,154; Direct brown (DirectBrown) 44,106,195,210,223; Direct red (DirectRed) 2,23,28,31,37,39,79,81,240,242,247; Directly blue (DirectBlue) 1,15,22,78,90,98,151,168,202,236,249,270; Directly purple (DirectViolet) 9,12,51,98; Direct green (DirectGreen) 1,85; Directly yellow (DirectYellow) 8,12,44,86,87; The dichroic dyes such as direct orange (DirectOrange) 26,39,106,107) etc.These fuel can a kind of independent uses or are used in combination.Dyeing usually can be by carrying out in the solution that the PVA series polymer film is immersed in contain above-mentioned dyestuff, and its treatment conditions and processing method are not particularly limited.
The PVA series polymer film uniaxial tension that alongst (MD) stretches can be undertaken by any method in wet type pulling method or xeothermic pulling method.By the wet type pulling method, undertaken in the situation of uniaxial tension, both can in borated warm water, carry out uniaxial tension, also can in containing the solution of above-mentioned dyestuff or in following fixedly processing bath, carry out uniaxial tension, also can carry out uniaxial tension in air with the PVA series polymer film after water suction, can also carry out uniaxial tension by other method.Draft temperature when uniaxial tension is processed is not particularly limited, by the PVA series polymer film in the situation that stretch in warm water (wet type stretching), employing is preferably 30～90 ℃, more preferably 40～70 ℃, the temperature of 45～65 ℃ more preferably, in the situation of xeothermic stretching, adopt the temperature that is preferably 50～180 ℃.In addition, the stretching ratio of processing as uniaxial tension (carry out in the situation of uniaxial tension is total stretching ratio with multistep), from the viewpoint of polarization property preferably until film facing fracture, stretch as much as possible, particularly be preferably more than 4 times, more preferably more than 5 times, more preferably more than 5.5 times.The upper limit of stretching ratio, as long as film does not rupture and just is not particularly limited, in order to carry out the stretching of homogeneous, is preferably below 8.0 times.
The thickness of the film after stretching (polarizing coating) is preferably 5～35 μ m, is particularly preferably 20～30 μ m.
While manufacturing polarizing coating, in order to make the absorption on the film of dyestuff after uniaxial tension firm, mostly be fixed processing.The general extensive employing of fixing processing is the method in the processing that is added with boric acid and/or boron compound is bathed by film immersion.Now, can add iodine compound as required in processing bath.
Then, preferably to having carried out, uniaxial tension is processed or uniaxial tension is processed and the fixing film of processing carries out drying processing (heat treatment).The dry temperature of processing (heat treatment) is preferably 30～150 ℃, is particularly preferably 50～140 ℃.Dry process (heat treatment) if temperature too low, the dimensional stability of the polarizing coating of gained easily reduces, and on the other hand, if too high, easily follow the decomposition etc. of dyestuff and the reduction of polarization property occurs.
Can be on the two sides of the polarizing coating obtained as mentioned above or one side laminating transparent and diaphragm with mechanical strength optically, thus polarizer made.As diaphragm now, use cellulose triacetate (TAC) film, cellulose acetate butyrate (CAB) (CAB) film, acrylic acid mesentery, polyester mesentery etc.In addition, as the bonding agent for the diaphragm of fitting, generally using PVA is bonding agent and urethane adhesive etc., and wherein preferably using PVA is bonding agent.
The polarizer obtained as mentioned above can fit in glass substrate after the bonding agents such as coating acrylic acid series, as the parts use of LCD device.When polarizer is fitted in to glass substrate, the phase retardation film of can simultaneously fitting, viewing-angle increasing film, brightness improve film etc.
Embodiment
By the following examples the present invention is specifically described, but the present invention is not limited in any way the following examples.
In following examples and comparative example, the volatile ingredient ratio of the volatile ingredient ratio of masking stoste, PVA film or PVA film (moisture ratio), each physical property of PVA film and the optical property of polarizing coating are measured by the following method.
(1) the volatile ingredient ratio of masking stoste:
By above formula [iii], try to achieve according to the method described above.
(2) the volatile ingredient ratio of PVA film or PVA film (moisture ratio):
By above formula [iv], try to achieve according to the method described above.
In addition, the use of the mensuration of the volatile ingredient ratio of PVA film or PVA film (moisture ratio) is carried out from the sample of width (TD) the central portion collection of the PVA film by the dryer roll taking-up or PVA film.
(3) the Δ n (MD) of PVA film ave:
By " " 1 " Δ n (MD) avedetermination method " in project hereinbefore described method obtain the Δ n (MD) of central portion of the width (TD) of PVA film ave, using its Δ as PVA film n (MD) ave.
(4) the Δ n (TD) of PVA film ave:
By " " 2 " Δ n (TD) avedetermination method " in project hereinbefore described method obtain the Δ n (TD) of central portion of the width (TD) of PVA film ave, using its Δ as PVA film n (TD) ave.
(5) the quality swellbility of PVA film:
The PVA film is cut into to 1.5g, and in the distilled water 1000g of 30 ℃, dipping is 30 minutes, floods after 30 minutes the PVA film is taken out, and after sucking surperficial water with filter paper, measures its quality (W e).Then, this PVA film after dry 16 hours, is measured to its quality (W with the drying machine of 105 ℃ f).Quality W by gained eand W fobtain the quality swellbility of PVA film by following formula [v].
Quality swellbility (%)=(W e/ W f) * 100 [v].
(6) the ultimate elongation multiplying power of PVA film:
The test film of the central portion acquisition length direction (MD) of the width (TD) of the PVA film before the stretching obtained from following examples or comparative example * width (TD)=10cm * 5cm, stretching clamp is fixed in in the two ends of the length direction of this test film, so that stretched portion is of a size of length direction (MD) * width (TD)=5cm * 5cm, in the water of 30 ℃, flooded for 38 seconds, in this process with the draw speed of 12cm/ minute alongst (MD) uniaxial tension (first step stretching) to 2.2 times of raw footage, contain iodine in the concentration with 0.03 quality %, 90 seconds of dipping in iodine/potassium iodide aqueous solution that the temperature that contains KI with the concentration of 3 quality % is 30 ℃, in this process with the draw speed of 12cm/ minute alongst (MD) uniaxial tension (second step stretching) to 3.3 times of raw footage, then, contain boric acid in the concentration with 3 quality %, dipping about 20 seconds in boric acid/potassium iodide aqueous solution that the temperature that contains KI with the concentration of 3 quality % is 30 ℃, in this process with the draw speed of 12cm/ minute alongst (MD) uniaxial tension (the 3rd step stretches) to 3.6 times of raw footage, then, contain boric acid in the concentration with 4 quality % on one side, with temperature that approximately concentration of 5 quality % contains KI, approximately in the boric acid/potassium iodide aqueous solution of 60 ℃, flood, on one side with the draw speed of 12cm/ minute alongst (MD) uniaxial tension to test film rupture, stretching ratio (length during fracture is with respect to the ratio of raw footage) while reading the test film fracture.
For same PVA film, carry out 5 above-mentioned tension tests, get the ultimate elongation multiplying power (doubly) of its mean value as the PVA film.
(7) optical property of polarizing coating:
(i) transmissivity:
The central portion of the width of the polarizing coating obtained from following examples or comparative example and the differently-oriented directivity of polarizing coating gather the foursquare sample of 2 1.5cm * 1.5cm abreast, take JIS Z8722 (assay method of object color) with the spectrophotometer V-7100 of Hitachi's system (subsidiary integrating sphere) respectively for each sample and carry out illuminant-C as benchmark, the brightness correction of the visible region in the 2 degree visuals field, for 1 polarizing coating sample, optical transmission rate when optical transmission rate when mensuration is spent with respect to tensile axis direction inclination 45 and inclination-45 are spent, obtain their mean value (Y 1).
For another piece polarizing coating sample, the optical transmission rate while also spending with above-mentioned similarly measure 45 optical transmission rates while spending and inclination-45, obtain their mean value (Y 2).
By the Y tried to achieve as mentioned above 1and Y 2on average, as the transmissivity (Y) of polarizing coating (%).
(ii) degree of polarization:
For 2 polarizing coating samples that gather in above-mentioned (i), with the assay method with above-mentioned transmissivity, same method is measured the optical transmission rate (Y ∥) of the mode parallel with its differently-oriented directivity when overlapping and the optical transmission rate (Y ⊥) when overlapping in the mode of differently-oriented directivity quadrature, by following formula [vi], obtains degree of polarization (V) (%).
Degree of polarization (V) (%)={ (Y ∥-Y ⊥)/(Y ∥+Y ⊥) } 1/2* 100 [vi].
(iii) degree of polarization during transmissivity 44.25%:
As put down in writing in following embodiment and comparative example, in each embodiment or comparative example, dip time in iodine/potassium iodide aqueous solution while changing the second step stretching, make 5 polarizing coatings, for each polarizing coating, obtain transmissivity (Y) and degree of polarization (V) with said method respectively, for each embodiment or comparative example, the transmissivity (Y) of take respectively becomes figure by 5 point-renderings as the longitudinal axis as transverse axis, the degree of polarization (V) of take, obtain curve of approximation, the value of the degree of polarization (V) when by this curve of approximation, obtaining transmissivity (Y) and be 44.25%.
" embodiment 1 "
(1) manufacture of PVA film:
(i) the masking stoste that the volatile ingredient ratio that will be comprised of the PVA by the polyvinyl acetate saponification is obtained (99.9 % by mole of saponification degrees, the degree of polymerization 2400) 100 mass parts, glycerine 12 mass parts, lauric acid diethyl amide 0.1 mass parts and water is 66 quality % spues to the first dryer roll (93 ℃ of surface temperatures, peripheral speed (S with membranaceous from T-shaped mould 1) 16.7m/ minute) on, on one side on the first dryer roll, whole the first dryer roll noncontact face is sprayed to the hot blast of 90 ℃ with the wind speed of 5m/ second, being dried to the moisture ratio reaches 18 quality % on one side, then, from the first dryer roll, peel off, approximately under the condition of 85 ℃, carry out the later drying of the second dryer roll at roll surface temperature, so that the surface of the arbitrary portion of PVA film alternately contacts with each dryer roll with the back side, finally, after heat-treating with the final dryer roll (Heat treating roll) of 108 ℃ of surface temperatures, batched, obtain PVA film (thick 60 μ m, wide 3m, volatile ingredient ratio 3 quality %).In this embodiment 1, the dryer roll when volatile ingredient ratio reaches 13 quality % is the 7th dryer roll.
In this embodiment 1, the peripheral speed (S of dryer roll when (α) the volatile ingredient ratio reaches 13 quality % (the 7th dryer roll) t) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S t/ S 1) be 1.000; (β) peripheral speed (S of final dryer roll l) peripheral speed (S of dryer roll (the 7th dryer roll) while with respect to the volatile ingredient ratio, reaching 13 quality % t) ratio (S l/ S t) be 0.974; (γ) peripheral speed (S of the second dryer roll 2) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S 2/ S 1) be 1.030; (δ) peripheral speed (S of next dryer roll (the 8th dryer roll) t+1) peripheral speed (S of dryer roll (the 7th dryer roll) while with respect to the volatile ingredient ratio, reaching 13 quality % t) ratio (S t/ S t+1) be 0.998; (ε) peripheral speed (S of final dryer roll l) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S l/ S 1) be 0.975, make the PVA film.
(ii) measure the Δ n (MD) of the PVA film obtained in above-mentioned (i) with said method ave, Δ n (TD) ave, quality swellbility and ultimate elongation multiplying power, result is as shown in table 1 below.
(2) manufacture of polarizing coating:
(i) test film of the central portion acquisition length direction (MD) of the width (TD) of the PVA film obtained from above-mentioned (1) * width (TD)=10cm * 5cm, stretching clamp is fixed in in the two ends of the length direction of this test film, so that stretched portion is of a size of length direction (MD) * width (TD)=5cm * 5cm, in the water of 30 ℃, flooded for 38 seconds, in this process with the draw speed of 12cm/ minute alongst (MD) uniaxial tension (first step stretching) to 2.2 times of raw footage, contain iodine in the concentration with 0.03 quality %, 60 seconds of dipping in iodine/potassium iodide aqueous solution that the temperature that contains KI with the concentration of 3 quality % is 30 ℃, in this process with the draw speed of 12cm/ minute alongst (MD) uniaxial tension (second step stretching) to 3.3 times of raw footage, then, contain boric acid in the concentration with 3 quality %, dipping about 20 seconds in boric acid/potassium iodide aqueous solution that the temperature that contains KI with the concentration of 3 quality % is 30 ℃, in this process with the draw speed of 12cm/ minute alongst (MD) uniaxial tension (the 3rd step stretches) to 3.6 times of raw footage, then, contain boric acid in the concentration with 4 quality % on one side, with temperature that approximately concentration of 5 quality % contains KI, approximately in the boric acid/potassium iodide aqueous solution of 60 ℃, flood, on one side with the draw speed of 12cm/ minute alongst (MD) uniaxial tension (the 4th step stretches) to the stretching ratio faced before the ultimate elongation multiplying power that reaches the PVA film of measuring as mentioned above, in the potassium iodide aqueous solution that contains KI in the concentration with 3 quality %, flooded for 10 seconds, carry out iodide ion impregnation processing, then use dry 4 minutes of the drying machine of 60 ℃, make polarizing coating (thick approximately 21 μ m).
Obtain transmissivity (Y) and the degree of polarization (V) of the polarizing coating obtained thus with said method, this point-rendering take to transmissivity (Y) in the figure that transverse axis, the degree of polarization (V) of take are the longitudinal axis.
(ii) in above-mentioned (i), dip time when second step is stretched in the iodine/potassium iodide aqueous solution of 30 ℃ of temperature changed for 75 seconds into from 60 seconds, carry out the operation same with above-mentioned (i), make the polarizing coating (thick approximately 21 μ m) of [draw speed of each draw stage all is similarly 12cm/ minute with above-mentioned (i)].
Obtain transmissivity (Y) and the degree of polarization (V) of the polarizing coating obtained thus with said method, by this point-rendering in the figure of above-mentioned (i).
(iii) in above-mentioned (i), dip time when second step is stretched in the iodine/potassium iodide aqueous solution of 30 ℃ of temperature changed for 90 seconds into from 60 seconds, carry out the operation same with above-mentioned (i), make the polarizing coating (thick approximately 21 μ m) of [draw speed of each draw stage all is similarly 12cm/ minute with above-mentioned (i)].
Obtain transmissivity (Y) and the degree of polarization (V) of the polarizing coating obtained thus with said method, by this point-rendering in the figure of above-mentioned (i).
(iv) in above-mentioned (i), dip time when second step is stretched in the iodine/potassium iodide aqueous solution of 30 ℃ of temperature changed for 105 seconds into from 60 seconds, carry out the operation same with above-mentioned (i), make the polarizing coating (thick approximately 21 μ m) of [draw speed of each draw stage all is similarly 12cm/ minute with above-mentioned (i)].
Obtain transmissivity (Y) and the degree of polarization (V) of the polarizing coating obtained thus with said method, by this point-rendering in the figure of above-mentioned (i).
(v) in above-mentioned (i), dip time when second step is stretched in the iodine/potassium iodide aqueous solution of 30 ℃ of temperature changed for 120 seconds into from 60 seconds, carry out the operation same with above-mentioned (i), make the polarizing coating (thick approximately 21 μ m) of [draw speed of each draw stage all is similarly 12cm/ minute with above-mentioned (i)].
Obtain transmissivity (Y) and the degree of polarization (V) of the polarizing coating obtained thus with said method, by this point-rendering in the figure of above-mentioned (i).
(vi) draw in above-mentioned (i)～(v) curve of approximation of drawing 5 points in the drawings on figure, the value of the degree of polarization (V) when by this curve of approximation, obtaining transmissivity (Y) and be 44.25%, result is as shown in table 1 below is 99.98.
" embodiment 2～5 "
(1), in embodiment 1, the film forming condition while as record in following table 1, changing manufacture PVA film, similarly manufacture the PVA film with embodiment 1 (1).But, in embodiment 2, as masking stoste, the masking stoste that the volatile ingredient ratio that use is comprised of the PVA by the polyvinyl acetate saponification is obtained (99.9 % by mole of saponification degrees, the degree of polymerization 2400) 100 mass parts, glycerine 12 mass parts, lauric acid diethyl amide 0.1 mass parts and water is 73 quality %.
Measure the Δ n (MD) of each PVA film obtained thus with said method ave, Δ n (TD) ave, quality swellbility and ultimate elongation multiplying power, result is as shown in table 1 below.
(2) test film of the length direction (MD) that the central portion of the width (TD) of each PVA film that use obtains from above-mentioned (1) gathers * width (TD)=10cm * 5cm, carry out the operation same with embodiment 1 (2), manufacture respectively 5 kinds of polarizing coatings for each embodiment, obtain transmissivity (Y) and the degree of polarization (V) of each polarizing coating, by this point-rendering, take transmissivity (Y), be transverse axis, in the figure that the degree of polarization (V) of take is the longitudinal axis, draw the curve of approximation of drafting 5 points in the drawings on figure, the value of the degree of polarization (V) when by this curve of approximation, obtaining transmissivity (Y) and be 44.25%, result is as shown in table 1 below.
" comparative example 1～5 "
(1), in embodiment 1, the film forming condition while as record in following table 2, changing manufacture PVA film, similarly manufacture the PVA film with embodiment 1 (1).
Measure the Δ n (MD) of each PVA film obtained thus with said method ave, Δ n (TD) ave, quality swellbility and ultimate elongation multiplying power, result is as shown in table 2 below.
(2) test film of the length direction (MD) that the central portion of the width (TD) of each PVA film that use obtains from above-mentioned (1) gathers * width (TD)=10cm * 5cm, carry out the operation same with embodiment 1 (2), manufacture respectively 5 kinds of polarizing coatings for each comparative example, obtain transmissivity (Y) and the degree of polarization (V) of each polarizing coating, by this point-rendering, take transmissivity (Y), be transverse axis, in the figure that the degree of polarization (V) of take is the longitudinal axis, draw the curve of approximation of drafting 5 points in the drawings on figure, the value of the degree of polarization (V) when by this curve of approximation, obtaining transmissivity (Y) and be 44.25%, result is as shown in table 2 below.
[table 1]
Figure 393765DEST_PATH_IMAGE001
[table 2]
Figure 310905DEST_PATH_IMAGE002
From above-mentioned table 1 and table 2, the Δ n (MD) of the PVA film of embodiment 1～5 ave[birefringence of the length direction of PVA film (MD) on the thickness direction of film equalization and value] and Δ n (TD) ave[birefringence of the width of PVA film (TD) on the thickness direction of film equalization and value] meet formula (I) and (II), thereby there are 6.72～6.94 such high limit stretching ratios, and there is the polarization property with the equal above excellence of existing polarizing coating by the polarizing coating that the PVA film of embodiment 1～5 obtains.
In contrast, the PVA film of comparative example 1～4 does not meet formula (I), and the PVA film of comparative example 4 and 5 do not meet formula (II), therefore with the PVA film of embodiment 1～5, compares, and the ultimate elongation multiplying power is all low.
While by the PVA series polymer film, manufacturing polarizing coating, usually the fracture of the film when stretching and carry out uniaxial tension with the stretching ratio more lower slightly than ultimate elongation multiplying power, but because the ultimate elongation multiplying power of the PVA film of embodiment 1～5 is all up to more than 6.72, so while under the condition of this embodiment, manufacturing polarizing coating, the PVA film of embodiment 1～5 can carry out uniaxial tension with the high stretching ratio more than 6 times, even carry out uniaxial tension with the high stretching ratio more than 6.5 times, the fracture of film also can not occur, can be stretched swimmingly.
In contrast, in the PVA film of comparative example 1～5, because the ultimate elongation multiplying power of the PVA film of comparative example 4 is less than 6, so while under the condition of this comparative example, manufacturing polarizing coating, can not carry out uniaxial tension with the stretching ratio more than 6 times, when stretching, film easily ruptures, in addition, comparative example 1～3 and 5 PVA film are when the stretching ratio uniaxial tension with more than 6 times, troubling on the fracture this point of film.
In addition, the length that 1 volume is also arranged in the former film that polarizing coating is used is the above former film of 1000m, for example, in the PVA series polymer film of total length 1000m, its ultimate elongation multiplying power rising 0.1 point (0.1 times), uniaxial tension and the length of stretched film increase 100m (1000m * 0.1 times=100m), can obtain more polarizing coating by the former film of equal length.
About this point, from embodiment 1～5, the PVA film of embodiment 1～5 is compared with the PVA film of comparative example 1～5, the ultimate elongation multiplying power is up to 0.10～0.98 point (doubly), for example, if the length of PVA film is 1000m, with the PVA film itself in the situation that manufacture polarizing coating under the condition of above-described embodiment, the length of polarizing coating is compared and will be grown 100～980m with the situation of the PVA film that uses comparative example 1～5, can obtain more polarizing coating.
Industrial usability
Even PVA series polymer film of the present invention is at the thinner thickness of film, be in the situation of 30～65 μ m left and right, also there is the high limit stretching ratio, even when manufacturing polarizing coating etc. with the high magnification uniaxial tension, also be difficult for occurring the fracture of film, therefore can be in the situation that do not interrupt stretching operation with high finished product rate, and with the drying time than in the past shorter, manufacture the stretched film such as polarizing coating of the excellent in optical properties such as polarization property with good productivity ratio, so extremely useful as the former film for the manufacture of stretched film such as polarizing coatings, and, manufacture method of the present invention is useful as the method for manufacturing continuously swimmingly this PVA series polymer film of the present invention with high production rate.

Claims (8)

1. polymer film of polyvinyl alcohol, is characterized in that, meets following formula (I) and (II);
Δn(MD) Ave—0.1×10 -3≤Δn(TD) Ave≤Δn(MD) Ave+0.25×10 -3 (I)
Δn(TD) Ave≤2.5×10 -3 (II)
In above formula, Δ n (MD) avethe birefringence of mechanical flow direction that means polymer film of polyvinyl alcohol on the thickness direction of this film equalization and value, Δ n (TD) avethe birefringence of width that means polymer film of polyvinyl alcohol on the thickness direction of this film equalization and value.
2. polymer film of polyvinyl alcohol according to claim 1, it meets following formula (III);
1.3×10 -3≤Δn(MD) Ave≤2.0×10 -3 (III)。
3. polymer film of polyvinyl alcohol according to claim 1 and 2, its thickness is in the scope of 30～65 μ m.
4. the manufacture method of polymer film of polyvinyl alcohol, it is the manufacture method of polymer film of polyvinyl alcohol, it is characterized in that,
(a) use the film forming apparatus possess the many dryer rolls that rotating shaft is parallel to each other, the masking stoste that will contain vinol series polymer spues to the first dryer roll of this film forming apparatus and, after carrying out the part drying, further carries out drying with follow-up dryer roll and carry out masking with membranaceous; Now,
(b) peripheral speed (S of the dryer roll when volatile ingredient ratio of vinol series polymer film reaches 13 quality % t) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S t/ S 1) be 0.990～1.050;
(c) peripheral speed (S of final dryer roll l) peripheral speed (S of dryer roll while with respect to the volatile ingredient ratio of vinol series polymer film, reaching 13 quality % t) ratio (S l/ S t) be 0.960～0.980;
(d) peripheral speed (S of final dryer roll l) with respect to the peripheral speed (S of the first dryer roll 1) ratio (S l/ S 1) be 0.970～1.010.
5. manufacture method according to claim 4, wherein, the volatile ingredient ratio of the vinol series polymer film while peeling off from the first dryer roll is 17～30 quality %.
6. according to the described manufacture method of claim 4 or 5, wherein, the roll surface temperature of each dryer roll is more than 65 ℃.
7. according to the described manufacture method of any one in claim 4～6, wherein, the volatile ingredient ratio of the masking stoste that contains vinol series polymer is 60～75 quality %, and the roll surface temperature of the first dryer roll is 80～120 ℃, the peripheral speed (S of the first dryer roll 1) be 8～25m/ minute.
8. polarizing coating, it is made by the described polymer film of polyvinyl alcohol of any one in claim 1～3.
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