WO2015129538A1 - ポリビニルアルコールフィルムおよびその製造方法 - Google Patents

ポリビニルアルコールフィルムおよびその製造方法 Download PDF

Info

Publication number
WO2015129538A1
WO2015129538A1 PCT/JP2015/054560 JP2015054560W WO2015129538A1 WO 2015129538 A1 WO2015129538 A1 WO 2015129538A1 JP 2015054560 W JP2015054560 W JP 2015054560W WO 2015129538 A1 WO2015129538 A1 WO 2015129538A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
pva
polyvinyl alcohol
orientation axis
polarizing
Prior art date
Application number
PCT/JP2015/054560
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
絵美 藤井
修 風藤
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Priority to CN201580010788.7A priority Critical patent/CN106029755B/zh
Priority to JP2016505162A priority patent/JP6556693B2/ja
Priority to KR1020167022570A priority patent/KR102387498B1/ko
Publication of WO2015129538A1 publication Critical patent/WO2015129538A1/ja

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • 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
    • B29C41/28—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 an endless belt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a polyvinyl alcohol film, a method for producing the same, and an optical film such as a polarizing film produced from the film. More specifically, the present invention relates to polyvinyl alcohol that provides an optical film such as a polarizing film that has a narrow color spot and is less noticeable as a spot even when the light transmittance is high or the light intensity of the backlight is high.
  • the present invention relates to a film, a manufacturing method thereof, and an optical film such as a polarizing film manufactured from the film.
  • a polarizing plate having a light transmission and shielding function is a basic component of a liquid crystal display (LCD) together with a liquid crystal that changes a polarization state of light.
  • LCD liquid crystal display
  • Many polarizing plates have a structure in which a protective film such as a cellulose triacetate (TAC) film is bonded to the surface of a polarizing film.
  • TAC cellulose triacetate
  • Such a polarizing film is obtained by uniaxially stretching a polyvinyl alcohol film containing a dichroic dye in advance, adsorbing a dichroic dye simultaneously with uniaxial stretching of the polyvinyl alcohol film, or uniaxially stretching the polyvinyl alcohol film. Manufactured by adsorbing dichroic dyes.
  • LCDs are used in a wide range of applications, including small devices such as calculators and wristwatches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measuring devices used indoors and outdoors. .
  • small devices such as calculators and wristwatches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measuring devices used indoors and outdoors.
  • reduction of power consumption is particularly strongly demanded, it has become important for LCDs to maintain high screen brightness even when the light intensity of the backlight is low.
  • a high-polarizing plate is more prominent in color spots than a polarizing plate having a low light transmittance.
  • Patent Document 1 As a polyvinyl alcohol film for reducing color spots of a polarizing film, a polyvinyl alcohol film (see Patent Document 1) in which birefringence spots and thickness spots are reduced, between two points separated by 1 cm in the width direction of the film A polyvinyl alcohol film having a retardation difference in a specific range (see Patent Document 2), a polyvinyl alcohol film having a thickness variation per mm in the width direction of the film in a specific range (see Patent Document 3), and the like are known. .
  • the inclination of the optical axis over the entire film width direction of the film can be reduced with respect to the longitudinal direction of the film, as it can reduce the generation of wrinkles when the polyvinyl alcohol film swells and streak-like stained spots existing in the longitudinal direction of the polarizing film.
  • a polyvinyl alcohol film having an angle of 45 to 135 ° is known (see Patent Document 4).
  • the above-mentioned conventional polyvinyl alcohol film has a relatively wide color spot even if the color difference of the color spot can be reduced, for example, when the polarizing film is used for manufacturing a polarizing plate. It has been found that there is a problem that it is easily noticeable as spots.
  • An object of the present invention is to provide a polyvinyl alcohol film that can easily produce an optical film such as a polarizing film that has a narrow color spot and is less noticeable as a spot, and a method for producing the same. Furthermore, this invention aims at providing optical films, such as a polarizing film manufactured using the said polyvinyl alcohol film.
  • an optical film such as Furthermore, when manufacturing the film using the film-forming stock solution containing polyvinyl alcohol, the inventors of the present invention use the film-forming stock solution on a support such as a roll or a belt from a discharge port of a discharge device. It has been found that smooth production can be achieved by blowing a specific wind speed to the discharged film within a specific time after discharging into a film. The present inventors have further studied based on these findings and completed the present invention.
  • the present invention [1] In the distribution of orientation axis angles obtained by measuring the orientation axis angle in the plane of the film at a pitch of 0.8 mm in the width direction of the film, the maximum distance between adjacent peaks is 6 cm or less. It is the characteristic polyvinyl alcohol film. And this invention, [2] In the distribution of the orientation axis angles obtained by measuring the orientation axis angles in the plane of the film at a pitch of 0.8 mm in the width direction of the film, the maximum difference between the orientation axis angles in adjacent peaks is 10 ° or less.
  • the present invention provides [4] A method for producing a polyvinyl alcohol film by discharging a film-forming stock solution containing polyvinyl alcohol in the form of a film from a discharge port of a discharge device onto a support, and producing a polyvinyl alcohol film within 10 seconds after discharge.
  • a method for producing a polyvinyl alcohol film comprising a step of spraying a film of 3 to 5 m / sec.
  • the present invention also provides: [5] An optical film produced using the polyvinyl alcohol film of any one of [1] to [3]; [6] The optical film according to [5], which is a polarizing film; It is.
  • the polyvinyl alcohol film of the present invention As a raw material, even if the light transmittance is high or a backlight having a higher light intensity is used, the polarizing film has a narrow color spot and is hardly noticeable as a spot. An optical film such as can be obtained.
  • the polyvinyl alcohol film of the present invention having the above-described excellent characteristics can be produced smoothly.
  • FIG. 1 is a diagram schematically showing an orientation axis angle in a film plane of a polyvinyl alcohol film.
  • FIG. 2 is a schematic view showing an example of measurement points when measuring the orientation axis angle in the film plane of the polyvinyl alcohol film.
  • the present invention is described in detail below.
  • the polyvinyl alcohol film of the present invention (hereinafter, polyvinyl alcohol may be referred to as “PVA”) has an orientation axis angle obtained by measuring the orientation axis angle in the plane of the film at a pitch of 0.8 mm in the width direction of the film. In the distribution, the maximum distance between adjacent peaks is 6 cm or less.
  • the PVA film of the present invention since the said distance is large, in the polarizing film manufactured using it, and a polarizing plate, there existed a problem that the width
  • the PVA film of the present invention has a maximum distance of 6 cm or less, which is different from conventional PVA films.
  • the orientation axis angle in the plane of the film in the present invention refers to the angle ⁇ between the longitudinal direction (MD) and the orientation axis (slow axis) in the plane of the film, and the orientation axis angle. It depends on the orientation state of the PVA molecules at the measurement position.
  • the orientation axis angle can be measured based on light (for example, light having a wavelength of 543 nm) traveling in a direction perpendicular to the film surface (film thickness direction) using a birefringence measurement device, a cell gap measurement device, or the like. Specifically, it can be measured by the method described later in the examples.
  • a virtual straight line A1-A2 in the width direction orthogonal to the length direction of the PVA film is defined at an arbitrary position in the length direction (MD) of the PVA film, and the virtual straight line A1-A2 is The orientation axis angle is measured by light traveling in a direction perpendicular to the film surface (thickness direction of the film) at a pitch of 0.8 mm over the entire width of the virtual straight line A1-A2 (full width of the film).
  • the measurement position for measuring the orientation axis angle is not particularly limited.
  • an arbitrary point (for example, the center) on the imaginary straight line connecting A1 and A2 is A3, and a pitch of 0.8 mm from A3 toward A1.
  • a method of measuring the orientation axis angle at a pitch of 0.8 mm from A3 to A2 and the like can be adopted.
  • the width direction of the film is a direction (TD) in the plane of the film orthogonal to the length direction (MD) of the film.
  • the length direction (MD) of the film coincides with the direction in which the PVA film should be uniaxially stretched when producing an optical film such as a polarizing film, and the direction in the plane of the film orthogonal to the length direction.
  • the width direction (TD) In the case of a non-long PVA film, the direction to be uniaxially stretched when manufacturing an optical film such as a polarizing film is the length direction (MD) of the film, and the direction in the plane of the film orthogonal thereto
  • the width direction (TD) may be used.
  • the long-period noise can be eliminated as follows. That is, for each measurement point, a total of 500 points of 250 points (250 pitches) continuous on one side of the film width direction (TD) and 250 points (250 pitches) continuous on the other side from the measurement points.
  • the average value of the orientation axis angles is obtained, and this average value is subtracted from the orientation axis angle value at the target measurement point.
  • data indicating the variation of the orientation axis angle from which long-period noise has been eliminated can be obtained.
  • the “distance between adjacent peaks” can be obtained by analyzing the data indicating the variation in the orientation axis angle from which long-period noise has been eliminated by the following method. In the case of eliminating the long-period noise, both end portions in the film width direction (TD) without data of orientation axis angles for 250 points continuous on one side in the film width direction (TD). (Each portion having a width of about 20 cm) is often not manufactured because it is usually slit in the optical film manufacturing process, and can therefore be excluded from the analysis of “distance between adjacent peaks”.
  • the peak detection of the orientation axis angle distribution is performed based on the data indicating the orientation axis angle fluctuation from which the long-period noise has been eliminated. Do. To detect the peak of the distribution of the orientation axis angle, set “constant (average)” as the baseline mode, and set “based on height (threshold height 30%)” as the peak fit filtering method. Peaks smaller than the threshold are excluded. Next, the position in the width direction at each peak is obtained, the distance in the width direction between adjacent peaks is calculated, and this is defined as “distance between adjacent peaks”. In the present invention, the peak in “distance between adjacent peaks” includes a positive peak and a negative peak.
  • the maximum distance between adjacent peaks obtained as described above is 6 cm or less, and the distance between adjacent peaks is all 6 cm or less.
  • the maximum value of the distance between adjacent peaks is larger than 6 cm, the width of the color spot becomes thick when the polarizing film and the polarizing plate are used, and the spot becomes easily noticeable as a spot.
  • the maximum distance between adjacent peaks in the PVA film is preferably 5.5 cm or less, more preferably 5 cm or less, and in some cases 4 cm or less, 2 cm or less, and further 1 cm or less. It may be.
  • the lower limit of the maximum distance between adjacent peaks is not particularly limited, but a PVA film having a very small maximum distance between adjacent peaks is difficult to produce with high productivity.
  • the value is preferably 0.1 cm or more, more preferably 0.2 cm or more, and further preferably 0.3 cm or more.
  • the maximum value of the difference in orientation axis angles at adjacent peaks is preferably 10 ° or less.
  • the maximum value of the difference in the orientation axis angle between adjacent peaks is 10 ° or less, the difference in color shading when the polarizing film and the polarizing plate are formed can be reduced.
  • the maximum value of the difference in the orientation axis angle in the adjacent peak is preferably 0.01 ° or more.
  • the orientation in the adjacent peak is
  • the maximum value of the difference in the shaft angle is more preferably 0.01 to 10 °, further preferably 0.02 to 8 °, and particularly preferably 0.05 to 5 °.
  • the difference in orientation axis angle between adjacent peaks can be determined from the value of the orientation axis angle at the peak detected in the above-mentioned “distance between adjacent peaks”.
  • the thickness of the PVA film of the present invention is not particularly limited, but if it is too thick, drying when producing an optical film such as a polarizing film is difficult to be performed quickly, while if too thin, it is difficult to produce an optical film.
  • the thickness of the PVA film is preferably in the range of 5 to 150 ⁇ m, more preferably in the range of 8 to 120 ⁇ m, since the film is likely to break during uniaxial stretching. More preferably, it is particularly preferably in the range of 12 to 50 ⁇ m.
  • the width of the PVA film of the present invention is not particularly limited, in recent years, liquid crystal televisions and monitors have become larger in screen, so that they can be effectively used for them, preferably 2 m or more. More preferably.
  • an optical film such as a polarizing film is manufactured with a realistic production machine, if the width of the film is too wide, uniform uniaxial stretching may be difficult, so the width of the PVA film is 8 m or less. It is preferable.
  • the length of the PVA film of the present invention is not particularly limited, but a more uniform PVA film can be continuously and smoothly manufactured, and is also used continuously when an optical film is manufactured using the PVA film. Therefore, it is preferably in the range of 5 to 50,000 m, more preferably in the range of 100 to 20,000 m.
  • Examples of PVA constituting the PVA film of the present invention include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, isopropenyl acetate, etc.
  • Those obtained by saponifying a polyvinyl ester obtained by polymerizing one or more of these vinyl esters can be used.
  • a compound having a vinyloxycarbonyl group (H 2 C ⁇ CH—O—CO—) in the molecule is preferable from the viewpoint of ease of production, availability, and cost of PVA, More preferred is vinyl acetate.
  • the polyvinyl ester is preferably obtained using only one or two or more vinyl esters as monomers, and more preferably obtained using only one vinyl ester as a monomer.
  • a copolymer of one or more vinyl esters and other monomers copolymerizable therewith may be used.
  • Examples of the other monomer copolymerizable with the vinyl ester include ⁇ -olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene; (meth) acrylic acid or a salt thereof; (Meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate i-propyl, (meth) acrylate n-butyl, (meth) acrylate i-butyl, ( (Meth) acrylic acid esters such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate and octadecyl (meth) acrylate; (meth) acrylamide; N-methyl ( (Meth) acrylamide, N-ethyl (meth) acrylamide, N, N
  • Vinyl ether vinyl cyanide such as (meth) acrylonitrile; halo such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride Allyl compounds such as allyl acetate, allyl chloride, etc .; maleic acid or its salt, ester or acid anhydride; itaconic acid or its salt, ester or acid anhydride; vinylsilyl compound such as vinyltrimethoxysilane; unsaturated sulfone An acid or its salt can be mentioned.
  • Said polyvinyl ester can have a structural unit derived from 1 type, or 2 or more types of an above described other monomer.
  • the proportion of structural units derived from the other monomers in the polyvinyl ester is preferably 15 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester, and is preferably 10 mol% or less. More preferably, it is 5 mol% or less.
  • those not graft-copolymerized can be preferably used, but PVA can be used for one or more kinds of graft copolymer as long as the effects of the present invention are not significantly impaired. It may be modified with a monomer.
  • the said graft copolymerization can be performed with respect to at least one of polyvinyl ester and PVA obtained by saponifying it.
  • the graft copolymerizable monomer include unsaturated carboxylic acids or derivatives thereof; unsaturated sulfonic acids or derivatives thereof; ⁇ -olefins having 2 to 30 carbon atoms, and the like.
  • the proportion of structural units derived from the graft copolymerizable monomer in the polyvinyl ester or PVA is preferably 5 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester or PVA.
  • the hydroxyl group may be cross-linked or may not be cross-linked.
  • the PVA may have a hydroxyl group partially reacted with an aldehyde compound such as acetaldehyde or butyraldehyde to form an acetal structure, or may not react with these compounds to form an acetal structure. Also good.
  • the polymerization degree of the above PVA is not particularly limited, but is preferably 1,000 or more.
  • the degree of polymerization of PVA is 1,000 or more, the polarizing performance of the polarizing film obtained from the PVA film can be further improved. If the polymerization degree of PVA is too high, it tends to lead to an increase in the production cost of PVA and poor processability during film formation. Therefore, the polymerization degree of PVA should be in the range of 1,000 to 10,000. Is more preferably in the range of 1,500 to 8,000, particularly preferably in the range of 2,000 to 5,000.
  • the degree of polymerization of PVA as used herein means the average degree of polymerization measured according to the description of JIS K6726-1994.
  • the degree of saponification of PVA is preferably 98 mol% or more, more preferably 99 mol% or more, since the heat and heat resistance of an optical film such as a polarizing film obtained from the PVA film is improved. More preferably, it is 8 mol% or more, and it is especially preferable that it is 99.9 mol% or more.
  • the degree of saponification of PVA refers to the vinyl alcohol relative to the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification of PVA. The ratio (mol%) occupied by the number of moles of units.
  • the degree of saponification can be measured according to the description of JIS K6726-1994.
  • the PVA film may contain a plasticizer together with the above PVA.
  • a plasticizer polyhydric alcohol is preferably used, and specific examples include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like.
  • PVA film Can contain one or more of these plasticizers. Among these, glycerin is preferable because the stretchability of the PVA film becomes better.
  • the content of the plasticizer in the PVA film is preferably 3 to 20 parts by mass, more preferably 5 to 17 parts by mass, and further preferably 7 to 14 parts by mass with respect to 100 parts by mass of PVA. .
  • the content of the plasticizer in the PVA film is 3 parts by mass or more with respect to 100 parts by mass of PVA, the stretchability of the PVA film is improved.
  • the content of the plasticizer in the PVA film is 20 parts by mass or less with respect to 100 parts by mass of PVA, the plasticizer bleeds out on the surface of the PVA film and the handling property of the PVA film is reduced. be able to.
  • surfactant that is blended in the film-forming stock solution for producing the PVA film, and thus the surfactant contained in the PVA film, but from the viewpoint of releasability from a metal roll or belt, an anion is used.
  • Surfactants or nonionic surfactants are preferred, and nonionic surfactants are particularly preferred.
  • anionic surfactant for example, a carboxylic acid type such as potassium laurate; a sulfate ester type such as octyl sulfate; a sulfonic acid type such as dodecylbenzene sulfonate and the like are suitable.
  • nonionic surfactants include alkyl ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl ester types such as polyoxyethylene laurate; polyoxyethylene Alkylamine types such as laurylamino ether; alkylamide types such as polyoxyethylene lauric acid amide; polypropylene glycol ether types such as polyoxyethylene polyoxypropylene ether; alkanolamide types such as lauric acid diethanolamide and oleic acid diethanolamide; An allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether is preferred. These surfactants can be used alone or in combination of two or more.
  • the content of the surfactant should be in the range of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of PVA contained in the film-forming stock solution. Preferably, it is in the range of 0.02 to 0.3 parts by mass.
  • the content of the surfactant is 0.01 parts by mass or more with respect to 100 parts by mass of PVA, the film forming property and the peelability can be improved.
  • the content of the surfactant is 0.5 parts by mass or less with respect to 100 parts by mass of PVA, the surfactant bleeds out on the surface of the PVA film, resulting in blocking, and handling properties are reduced. Can be suppressed.
  • the PVA film may be composed only of PVA, or may be composed only of PVA and the above-described plasticizer and / or surfactant. If necessary, an antioxidant, an antifreeze agent, a pH adjuster, You may further contain 1 type, or 2 or more types of other components, such as a masking agent, a coloring preventing agent, and an oil agent.
  • the PVA content in the PVA film is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and in the range of 85 to 100% by mass. Further preferred.
  • the manufacturing method in particular of the PVA film of this invention is not restrict
  • a production method including a step of blowing a wind of 0.3 to 5 m / sec on the discharged film is preferably employed since the PVA film of the present invention can be produced smoothly.
  • adopted suitably in this invention (henceforth "the manufacturing method of this invention" is demonstrated.
  • the film-forming stock solution examples include PVA and, if necessary, a plasticizer, a surfactant, a film-forming stock solution in which other components are dissolved in a liquid medium, PVA and, if necessary, a plasticizer and an interface.
  • examples include a film-forming stock solution containing an active agent, other components, and a liquid medium and in which PVA is melted.
  • the film-forming stock solution contains at least one of a plasticizer, a surfactant, and other components, it is preferable that these components are uniformly mixed.
  • liquid medium used for the preparation of the membrane forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. , Trimethylolpropane, ethylenediamine, diethylenetriamine and the like, and one or more of them can be used. Among these, water is preferable from the viewpoint of a small environmental load and recoverability.
  • the volatile fraction of the film-forming stock solution may vary depending on the film-forming method, the film-forming conditions, etc. It is preferably in the range of -95% by mass, more preferably in the range of 55-90% by mass, and still more preferably in the range of 60-85% by mass.
  • the volatile fraction of the film-forming stock solution is 50% by mass or more, the viscosity of the film-forming stock solution does not become too high, and filtration and defoaming are smoothly performed during preparation of the film-forming stock solution, and there are few foreign matters and defects. Film production is facilitated.
  • the temperature of the film forming stock solution is preferably 90 to 110 ° C.
  • Examples of the discharge device for discharging the film-forming stock solution into a film include a T-type slit die, an I-die, and a lip coater die.
  • the production method of the present invention includes a step of blowing wind at a wind speed of 0.3 to 5 m / second within 10 seconds after the film-forming stock solution is discharged into a film form from the discharge port. Since the PVA film of the present invention can be obtained more efficiently, the time when the wind is blown (the time when the wind is first blown to the discharged film) is preferably within 5 seconds after the discharge. It is more preferable that the time is within the range of 1 second to 1 second immediately after discharge. At that time, the length of time for blowing the wind is preferably 0.1 to 10 seconds, more preferably 0.5 to 5 seconds, and further preferably 0.8 to 2 seconds. .
  • the wind speed of the blown wind is 0.3 to 5 m / second, and the PVA film of the present invention can be obtained more efficiently. Therefore, the wind speed is preferably 0.4 m / second or more, and 0.5 m / second. It is more preferably at least 2 seconds, more preferably at least 0.7 m / second, particularly preferably at least 0.77 m / second, and the wind speed is preferably less than 3 m / second, preferably 1 m. Is more preferably less than 0.9 m / sec, and even more preferably less than 0.9 m / sec.
  • the temperature of the blowing air is preferably 20 to 100 ° C, more preferably 30 to 90 ° C, and further preferably 40 to 80 ° C. If the temperature of the blowing air is too low, the discharged PVA film tends to be insufficiently dried. On the other hand, if the temperature of the blowing air is too high, foaming tends to occur.
  • the method of blowing the wind is not particularly limited, but a structure that reduces wind speed spots of the blowing wind is preferable, and a nozzle method, a rectifying plate method, or a combination thereof is generally used.
  • a nozzle method, a rectifying plate method, or a combination thereof is generally used.
  • the film forming apparatus to be used only needs to have a support for discharging the film forming stock solution.
  • a drum type film forming apparatus or a belt type film forming apparatus can be used.
  • a drum-type film forming apparatus is preferable, and in particular, a drum-type film forming apparatus including a plurality of drying rolls whose rotation axes are parallel to each other is more preferably used.
  • volatile components are evaporated from one surface of the PVA film discharged onto the first roll, followed by drying.
  • the other surface of the discharged PVA film can be dried by passing over the peripheral surface of the heated second roll that rotates.
  • the volatile fraction when peeling the PVA film from the first roll is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and further preferably 20 to 30% by mass.
  • the volatile content rate at the time of peeling from the first roll is too small, the stretchability tends to deteriorate during the processing to the polarizing film.
  • the volatile content rate when peeling from the first roll is too large, peeling from the first roll tends to be difficult.
  • the film-forming stock solution is dried with the first roll, it is further dried on the peripheral surface of one or a plurality of rotating heated rolls arranged on the downstream side, or further dried by passing through a hot air drying apparatus. Thereafter, a method of winding around a winding device can be preferably employed industrially. Drying with a heated roll and drying with a hot air dryer may be performed in an appropriate combination.
  • a device for manufacturing the PVA film is provided with a heat treatment device; a humidity control device; a motor for driving each roll; a speed adjustment mechanism such as a transmission. It is preferable.
  • the drying temperature during the drying process in the production process of the PVA film is preferably in the range of 50 to 150 ° C., more preferably in the range of 60 to 120 ° C. From this point of view, when producing a PVA film using a drum-type film forming apparatus comprising a plurality of drying rolls whose rotation axes are parallel to each other, the surface temperature of the first roll and the subsequent roll is 50 to 150 ° C., particularly 60 ° C. It is preferable that the temperature be ⁇ 120 ° C. When a hot air dryer is further arranged downstream of the drying roll, it is preferable that the atmospheric temperature in the hot air dryer is 50 to 150 ° C., particularly 60 to 120 ° C.
  • the drying treatment may be performed until the volatile content of the PVA film is 10% by mass or less, further 5% by mass or less, particularly 2 to 4% by mass. It is preferable from the point.
  • the PVA film of the present invention is preferably used as a raw material for producing an optical film.
  • the optical film include a polarizing film and a retardation film. These optical films can be produced by a production method having a step of uniaxial stretching using the PVA film of the present invention.
  • dyeing, uniaxial stretching, fixing treatment, drying treatment and further heat treatment may be performed using the PVA film of the present invention.
  • the order of dyeing and uniaxial stretching is not particularly limited, and dyeing may be performed before uniaxial stretching, dyeing may be performed simultaneously with uniaxial stretching, or dyeing may be performed after uniaxial stretching. In addition, steps such as uniaxial stretching and dyeing may be repeated a plurality of times.
  • iodine or a dichroic organic dye for example, DirectBlack 17, 19, 154; DirectBrown 44, 106, 195, 210, 223; DirectRed 2, 23, 28, 31, 37, 39, 79, 81, 240, 242, 247; DirectBlue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; DirectViolet 9, 12, 51, 98; DirectGreen 1, 85; Direct Yellow 8, 12, 44, 86, 87; dichroic dyes such as Direct Orange 26, 39, 106, 107) can be used.
  • dichroic dyes may be used alone or in combination of two or more. Dyeing can usually be performed by immersing the PVA film in a solution containing the above-described dichroic dye, but the treatment conditions and treatment method are not particularly limited.
  • Uniaxial stretching of the PVA film may be performed by either a wet stretching method or a dry heat stretching method.
  • a wet stretching method When uniaxially stretching by a wet stretching method, it may be uniaxially stretched in warm water containing boric acid, or may be uniaxially stretched in a solution containing the above-described dichroic dye or in a fixing treatment bath described later.
  • the PVA film after water absorption may be uniaxially stretched in the air or may be uniaxially stretched by other methods.
  • the stretching temperature during the uniaxial stretching treatment is not particularly limited, but when the PVA film is stretched in warm water (wet stretching), it is preferably 30 to 90 ° C, more preferably 40 to 70 ° C, and still more preferably 45 to 65 ° C.
  • the stretching ratio of uniaxial stretching is preferably stretched as much as possible from the point of polarization performance until just before the film is cut, and specifically 4 times or more. It is preferably 5 times or more, more preferably 5.5 times or more.
  • the upper limit of the stretching ratio is not particularly limited as long as the film is not broken, but is preferably 8.0 times or less in order to perform uniform stretching.
  • the draw ratio in this specification is based on the length of the film before extending
  • the thickness of the stretched film (polarizing film) is preferably 3 to 35 ⁇ m, particularly 5 to 30 ⁇ m.
  • uniaxial stretching in the length direction can be adopted. Therefore, uniaxial stretching in the length direction is preferable. Uniaxial stretching in the length direction can be performed by changing the peripheral speed between the rolls using a stretching apparatus including a plurality of rolls parallel to each other. On the other hand, uniaxial stretching in the transverse direction can be performed using a tenter type stretching machine.
  • the fixing treatment In the production of the polarizing film, it is preferable to perform a fixing treatment in order to strengthen the adsorption of the dichroic dye to the uniaxially stretched film.
  • the fixing treatment include a method of immersing the film in a fixing treatment bath to which a boron compound such as boric acid or borax is added. In that case, you may add an iodine compound in a fixed treatment bath as needed.
  • the film subjected to uniaxial stretching or uniaxial stretching and fixing treatment is then subjected to a drying treatment (heat treatment).
  • the temperature of the drying treatment (heat treatment) is preferably in the range of 30 to 150 ° C., more preferably in the range of 50 to 140 ° C. If the temperature of the drying treatment (heat treatment) is too low, the dimensional stability of the obtained polarizing film tends to be lowered, while if too high, the polarization performance is likely to deteriorate due to decomposition of the dichroic dye.
  • the polarizing film obtained as described above can be made into a polarizing plate by attaching a protective film that is optically transparent and has mechanical strength to both sides or one side.
  • a protective film in this case, a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, a cycloolefin polymer (COP) film, or the like is used.
  • a PVA adhesive agent, a urethane adhesive agent, etc. are mentioned, Among these, a PVA adhesive agent is preferable.
  • the polarizing plate obtained as described above can be used as a component of a liquid crystal display device after being coated with a pressure-sensitive adhesive such as acrylic and then attached to a glass substrate.
  • a pressure-sensitive adhesive such as acrylic
  • a retardation film, a viewing angle improving film, a brightness improving film, or the like may be bonded.
  • the virtual straight line connecting A1 and A2 is defined as a central line so that the virtual straight line connecting A1 and A2 becomes the measurement site of the orientation axis angle, and 20 mm upstream of the virtual straight line.
  • the tape-shaped sample over the full width of the PVA film was taken so that it might become a total of 40 mm by 20 mm downstream.
  • the measurement positions are determined at a pitch of 0.8 mm, and the orientation axis angle is measured in the film plane at each measurement position. I got the data.
  • the measurement of the orientation axis angle at each measurement position was performed with light having a wavelength of 543 nm traveling in a direction perpendicular to the film surface, using “WPA-100-L” manufactured by Photonic Lattice.
  • a total of 500 points from the measurement point to 250 points (for 250 pitches) continuous on one side in the film width direction (TD) and 250 points (for 250 pitches) continuous on the other side.
  • the average value of the orientation axis angles of the points was obtained, and this average value was subtracted from the value of the orientation axis angle at the target measurement point.
  • data indicating fluctuations in the orientation axis angle from which long-period noise was eliminated was obtained.
  • peak detection of the distribution of the orientation axis angle is performed based on the data indicating the change in the orientation axis angle from which the long-period noise has been eliminated. went.
  • To detect the peak of the distribution of the orientation axis angle set “constant (average)” as the baseline mode, and set “based on height (threshold height 30%)” as the peak fit filtering method.
  • Peaks smaller than the threshold were excluded.
  • the position in the width direction of each peak is obtained, the distance in the width direction between adjacent peaks (between adjacent peaks) is calculated, and is set as the “distance between adjacent peaks”, of which The maximum value was determined.
  • the difference in orientation axis angle between adjacent peaks (between adjacent peaks) is calculated between the respective peaks, The maximum value was determined.
  • Color spots on the polarizing film An polarizing plate for observation (using a polarizing film having a transmittance of about 43%) is placed on a surface light source (backlight) in a dark room, and a polarizing film produced in the following examples or comparative examples on the surface light source (backlight). was placed so as to be in a crossed Nicol state with respect to the polarizing plate for observation, and then the polarizing film was irradiated with light from the backlight through the polarizing plate for observation (luminance 15,000 cd). The polarizing film was visually observed from the position, and color spots of the polarizing film were evaluated by sensory evaluation based on the following criteria. A: Color spots are not visually recognized. ⁇ : Color spots are visible, but are not noticeable and are practically acceptable. X: Color spots of a level causing a practical problem were visually recognized.
  • Example 1 From 100 parts by weight of PVA (saponified vinyl acetate homopolymer, degree of polymerization 2,400, degree of saponification 99.9 mol%), 12 parts by weight of glycerin, 0.1 parts by weight of lauric acid diethanolamide and water A T-type slit is formed on a first roll (support) of a drum-type film forming apparatus using a film-forming stock solution having a volatile content of 66 mass% and a temperature of 100 ° C., and a plurality of drying rolls whose rotation axes are parallel to each other.
  • PVA synthetic vinyl acetate homopolymer, degree of polymerization 2,400, degree of saponification 99.9 mol
  • glycerin 0.1 parts by weight of lauric acid diethanolamide and water
  • a T-type slit is formed on a first roll (support) of a drum-type film forming apparatus using a film-forming stock solution having a volatile content of 66 mass% and a temperature of 100
  • Examples 2 to 5 and Comparative Examples 1 to 6 PVA film in the same manner as in Example 1 except that the wind blowing start time, the wind blowing time, the wind speed, and the volatile content of the PVA film when peeled from the first roll were changed as shown in Table 1. And calculating the maximum value of the distance between adjacent peaks in the distribution of the orientation axis angles of the obtained PVA film and the maximum difference of the orientation axis angles in the adjacent peaks, and the polarization obtained. The color spots of the film were evaluated. The results are shown in Table 1.
  • the PVA films of Examples 1 to 5 had a maximum distance between adjacent peaks in the distribution of orientation axis angles of 6 cm or less.
  • a high-quality polarizing film having a level in which no color spots are visually recognized or is not noticeable even when the color spots are visually recognized is obtained.
  • the maximum distance between adjacent peaks in the distribution of the orientation axis angles exceeds 6 cm. Spots occurred.
  • the PVA film of the present invention is used, an optical film such as a polarizing film that has a narrow color spot and is not noticeable as a spot even when a light transmittance is high or a backlight having a higher light intensity is used. Therefore, the PVA film of the present invention is extremely useful as a raw film for an optical film such as a polarizing film, and the production method of the present invention allows the PVA film of the present invention to be smoothly and continuously produced with high productivity. It is useful as a method for manufacturing.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
PCT/JP2015/054560 2014-02-27 2015-02-19 ポリビニルアルコールフィルムおよびその製造方法 WO2015129538A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201580010788.7A CN106029755B (zh) 2014-02-27 2015-02-19 聚乙烯醇膜及其制造方法
JP2016505162A JP6556693B2 (ja) 2014-02-27 2015-02-19 ポリビニルアルコールフィルムおよびその製造方法
KR1020167022570A KR102387498B1 (ko) 2014-02-27 2015-02-19 폴리비닐알코올 필름 및 그 제조 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-036316 2014-02-27
JP2014036316 2014-02-27

Publications (1)

Publication Number Publication Date
WO2015129538A1 true WO2015129538A1 (ja) 2015-09-03

Family

ID=54008859

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/054560 WO2015129538A1 (ja) 2014-02-27 2015-02-19 ポリビニルアルコールフィルムおよびその製造方法

Country Status (5)

Country Link
JP (1) JP6556693B2 (zh)
KR (1) KR102387498B1 (zh)
CN (2) CN106029755B (zh)
TW (1) TWI641643B (zh)
WO (1) WO2015129538A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017102437A (ja) * 2015-11-19 2017-06-08 日本合成化学工業株式会社 偏光膜製造用ポリビニルアルコール系フィルム、およびそれを用いた偏光膜、偏光板、ならびに偏光膜製造用ポリビニルアルコール系フィルムの製造方法
JP2017102421A (ja) * 2015-11-19 2017-06-08 日本合成化学工業株式会社 ポリビニルアルコール系フィルム、偏光膜及び偏光板

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7367286B2 (ja) * 2019-01-30 2023-10-24 株式会社アイセロ ポリビニルアルコール系樹脂フィルム

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001315144A (ja) * 2000-05-12 2001-11-13 Kuraray Co Ltd ポリビニルアルコール系重合体フィルムの製造法
JP2005324355A (ja) * 2004-05-12 2005-11-24 Kuraray Co Ltd ポリビニルアルコール系重合体フィルムおよびその製造方法
JP2006027263A (ja) * 2004-06-16 2006-02-02 Fuji Photo Film Co Ltd ポリマーフィルム及び溶液製膜方法
JP2006342236A (ja) * 2005-06-08 2006-12-21 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルムの製法およびそれによって得られたポリビニルアルコール系フィルムならびにそのポリビニルアルコール系フィルムを用いた偏光フィルムおよび偏光板
WO2012132984A1 (ja) * 2011-03-29 2012-10-04 株式会社クラレ ポリビニルアルコール系重合体フィルムおよびその製造方法
WO2013137056A1 (ja) * 2012-03-15 2013-09-19 株式会社クラレ エチレン変性ポリビニルアルコール系重合体フィルム
WO2013146146A1 (ja) * 2012-03-30 2013-10-03 株式会社クラレ ポリビニルアルコール系重合体フィルムおよび偏光フィルム
WO2013146147A1 (ja) * 2012-03-30 2013-10-03 株式会社クラレ ポリビニルアルコール系重合体フィルムおよびその製造方法
WO2014050696A1 (ja) * 2012-09-26 2014-04-03 株式会社クラレ ポリビニルアルコール系重合体フィルムおよびその製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3342516B2 (ja) 1992-10-27 2002-11-11 株式会社クラレ Ｐｖａ系フィルム及び光学用フィルムの製造方法
JP3514386B2 (ja) 2000-05-02 2004-03-31 株式会社クラレ ポリビニルアルコール系重合体フィルムとその製造法
JP3516397B2 (ja) 2000-05-12 2004-04-05 株式会社クラレ ポリビニルアルコールフィルムの製造法
KR101544626B1 (ko) * 2007-08-24 2015-08-17 가부시키가이샤 구라레 폴리비닐알코올 필름 및 그 제조법
JP5680805B1 (ja) * 2013-06-28 2015-03-04 株式会社クラレ ポリビニルアルコール系重合体フィルムおよびその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001315144A (ja) * 2000-05-12 2001-11-13 Kuraray Co Ltd ポリビニルアルコール系重合体フィルムの製造法
JP2005324355A (ja) * 2004-05-12 2005-11-24 Kuraray Co Ltd ポリビニルアルコール系重合体フィルムおよびその製造方法
JP2006027263A (ja) * 2004-06-16 2006-02-02 Fuji Photo Film Co Ltd ポリマーフィルム及び溶液製膜方法
JP2006342236A (ja) * 2005-06-08 2006-12-21 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルムの製法およびそれによって得られたポリビニルアルコール系フィルムならびにそのポリビニルアルコール系フィルムを用いた偏光フィルムおよび偏光板
WO2012132984A1 (ja) * 2011-03-29 2012-10-04 株式会社クラレ ポリビニルアルコール系重合体フィルムおよびその製造方法
WO2013137056A1 (ja) * 2012-03-15 2013-09-19 株式会社クラレ エチレン変性ポリビニルアルコール系重合体フィルム
WO2013146146A1 (ja) * 2012-03-30 2013-10-03 株式会社クラレ ポリビニルアルコール系重合体フィルムおよび偏光フィルム
WO2013146147A1 (ja) * 2012-03-30 2013-10-03 株式会社クラレ ポリビニルアルコール系重合体フィルムおよびその製造方法
WO2014050696A1 (ja) * 2012-09-26 2014-04-03 株式会社クラレ ポリビニルアルコール系重合体フィルムおよびその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017102437A (ja) * 2015-11-19 2017-06-08 日本合成化学工業株式会社 偏光膜製造用ポリビニルアルコール系フィルム、およびそれを用いた偏光膜、偏光板、ならびに偏光膜製造用ポリビニルアルコール系フィルムの製造方法
JP2017102421A (ja) * 2015-11-19 2017-06-08 日本合成化学工業株式会社 ポリビニルアルコール系フィルム、偏光膜及び偏光板

Also Published As

Publication number Publication date
CN106029755B (zh) 2021-10-26
JPWO2015129538A1 (ja) 2017-03-30
KR102387498B1 (ko) 2022-04-15
JP6556693B2 (ja) 2019-08-07
TW201538591A (zh) 2015-10-16
TWI641643B (zh) 2018-11-21
CN113416333A (zh) 2021-09-21
KR20160126987A (ko) 2016-11-02
CN106029755A (zh) 2016-10-12

Similar Documents

Publication Publication Date Title
JP6483792B2 (ja) ポリビニルアルコール系重合体フィルムおよびその製造方法
JP5390052B1 (ja) ポリビニルアルコール系重合体フィルムおよび偏光フィルム
KR102599701B1 (ko) 폴리비닐알코올 필름 및 그 제조 방법
JP6402096B2 (ja) ポリビニルアルコールフィルム
JP2022008895A (ja) 偏光フィルムの製造方法
JP2017003834A (ja) 偏光フィルムの製造方法
JP6556693B2 (ja) ポリビニルアルコールフィルムおよびその製造方法
JP2018135426A (ja) ポリビニルアルコールフィルム及びその製造方法、並びにそれを用いた偏光フィルム
JP4104916B2 (ja) 光学用ポリビニルアルコールフィルムおよびその製造方法
JP2014167654A (ja) 偏光フィルムの製造方法
JP6077626B2 (ja) ポリビニルアルコールフィルム
JP6444858B2 (ja) 偏光フィルムの製造方法
JP6667989B2 (ja) 偏光フィルムの製造方法
JP6592509B2 (ja) ポリビニルアルコールフィルム
JP6534305B2 (ja) ポリビニルアルコールフィルムの光学斑の評価方法
JP5832921B2 (ja) ポリビニルアルコールフィルム
JP6456235B2 (ja) 偏光フィルムの検査方法
WO2022113958A1 (ja) 偏光フィルムの製造方法及び偏光フィルム
JP6571955B2 (ja) ポリビニルアルコールフィルム
JP2017032732A (ja) 偏光フィルム
TW201539064A (zh) 偏光薄膜

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15754763

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016505162

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20167022570

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15754763

Country of ref document: EP

Kind code of ref document: A1