WO2013146146A1 - Film polymère à base d'alcool polyvinylique (pva) et film polarisant - Google Patents

Film polymère à base d'alcool polyvinylique (pva) et film polarisant Download PDF

Info

Publication number
WO2013146146A1
WO2013146146A1 PCT/JP2013/056149 JP2013056149W WO2013146146A1 WO 2013146146 A1 WO2013146146 A1 WO 2013146146A1 JP 2013056149 W JP2013056149 W JP 2013056149W WO 2013146146 A1 WO2013146146 A1 WO 2013146146A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
polymer film
drying roll
drying
pva polymer
Prior art date
Application number
PCT/JP2013/056149
Other languages
English (en)
Japanese (ja)
Inventor
良治 勝野
伊木　隆
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 KR1020137029866A priority Critical patent/KR20140130362A/ko
Priority to KR1020137029799A priority patent/KR101397899B1/ko
Priority to JP2013538389A priority patent/JP5390052B1/ja
Priority to CN201380018351.9A priority patent/CN104204046B/zh
Publication of WO2013146146A1 publication Critical patent/WO2013146146A1/fr

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/46—Heating or cooling
    • 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
    • G02B5/3025—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
    • 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
    • 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
    • C08J2429/00—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
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—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 polymer film (hereinafter, “polyvinyl alcohol” may be abbreviated as “PVA”), a production method thereof, and a polarizing film produced from the PVA polymer film. More specifically, the PVA polymer film capable of producing a polarizing film with less unevenness in transmittance between the center portion and the end portion and the production method thereof, and the PVA polymer film are produced.
  • the present invention relates to a polarizing film with little unevenness in transmittance between a central portion and an end portion.
  • 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 having a light switching function.
  • LCD liquid crystal display
  • This LCD can also be used in small devices such as calculators and wristwatches in the early days of development, and in recent years, laptop computers, word processors, liquid crystal projectors, in-vehicle navigation systems, liquid crystal televisions, personal phones, and measurements used indoors and outdoors. It shows a wide range of equipment.
  • a neutral gray polarizing plate that has higher polarization performance than conventional products and has excellent hue for improving color display quality.
  • a polarizing plate is obtained by uniaxially stretching and dyeing a PVA polymer film, or by dyeing and uniaxially stretching and then fixing with a boron compound (in some cases, dyeing, stretching and fixing treatment) Two or more of these operations may be performed at the same time.
  • the resulting polarizing film is made up of a protective film such as a cellulose triacetate (TAC) film or an acetic acid / butyric acid cellulose (CAB) film. Yes.
  • TAC cellulose triacetate
  • CAB acetic acid / butyric acid cellulose
  • a film is formed from a modified PVA polymer having a polymerization degree of 1500 to 5000, an ethylene unit content of 1 to 4 mol%, and a 1,2-glycol bond content of 1.4 mol% or less.
  • a polarizing film having a b value of 3 or less produced by uniaxially stretching a PVA film having a YI value of 20 or less is known (see Patent Document 1).
  • group polymer film obtained by using a heat roll (dry roll) with a larger roll diameter of the edge part side than the roll diameter of a center part is used.
  • a heat roll dry roll
  • the polymer film it is known that it is possible to obtain a polarizing film having high transparency and high polarization properties and excellent in-plane uniformity of polarization performance (see Patent Document 2).
  • the present invention is produced from a PVA polymer film that can produce a polarizing film with less unevenness in transmittance between the center and the end, a production method thereof, and the PVA polymer film.
  • An object of the present invention is to provide a polarizing film with little unevenness in transmittance between the central portion and the end portion.
  • a film forming apparatus having a plurality of drying rolls whose rotation axes are parallel to each other is used, and the first position located on the most upstream side of the film forming apparatus.
  • a film-forming stock solution containing a PVA polymer is discharged onto a drying roll in a film shape and dried, and further dried with a drying roll after the second drying roll following the downstream side of the first drying roll.
  • the present invention [1] On the straight line in the width direction (perpendicular to the length direction) of the PVA polymer film, the amount of dimensional change in water in the center is W (mm), and the change in size in water at a point 0.3 m from both ends.
  • the amount (average value) is set to W 0 (mm) (where the amount of dimensional change in water is 250 mm in the length direction before immersion when a PVA polymer film sample is immersed in pure water at 30 ° C. for 5 minutes.
  • the outer diameter of the central portion is used as at least one of the drying rolls after the second drying roll.
  • a method for producing a PVA polymer film using a drying roll having a diameter 0.5 to 3 mm larger than the outer diameter of both ends; and [8] A polarizing film produced from the PVA polymer film of [6] above; About.
  • a PVA polymer film capable of producing a polarizing film with little unevenness in transmittance between the central portion and the end portion; producing the PVA polymer film smoothly and continuously. And a polarizing film produced from the PVA polymer film with little unevenness in transmittance between the central portion and the end portion.
  • the PVA polymer film of the present invention has an underwater dimensional change of W (mm) at the center and 0.3 m from both ends on the straight line in the width direction (perpendicular to the length direction).
  • W 0 (mm) When the dimensional change amount (average value) is W 0 (mm), 0.5 mm ⁇ W 0 ⁇ W ⁇ 5 mm is satisfied. In the present invention, it is important to satisfy 0.5 mm ⁇ W 0 ⁇ W ⁇ 5 mm.
  • permeability between a center part and an edge part can be obtained.
  • W 0 -W is preferably 1 mm or more, more preferably 1.5 mm or more, further preferably 2 mm or more, and 4.5 mm or less from the viewpoint of uneven transmittance in the polarizing film. Preferably, it is 4 mm or less, more preferably 3.5 mm or less.
  • the amount of dimensional change in water refers to the amount of elongation in the length direction (unit; in the length direction 250 mm before immersion) when a PVA polymer film sample is immersed in pure water at 30 ° C. for 5 minutes. mm) and can be determined by the following method. That is, on an arbitrary straight line in the width direction (perpendicular to the length direction; hereinafter sometimes abbreviated as TD) of the PVA polymer film, it is 0.3 m away from the center (one place) and both ends. A rectangular sample of 27 cm in width direction (TD) ⁇ length direction (hereinafter sometimes abbreviated as MD) is cut out at a total of three points (two locations).
  • the center of gravity of each sample is set at each position on the straight line.
  • mark lines are made with oil-based magic (the thickness of the line is 0.3 mm) on the inside 1 cm from each 27 cm long end of each sample.
  • the outer part from the marked lines at both ends is sandwiched with commercially available clips (chuck width 4 cm, mass 7.8 g (weight 7.3 g in water)), and one clip is fixed with a rod-shaped jig such as a number wire.
  • a rod-shaped jig is hooked on the upper part of the water tank so that the long side of the sample is fixed vertically. Then, a metal ruler is immersed in water, and the distance between marked lines is measured 5 minutes after immersion. By subtracting the original distance between marked lines (250 mm) from the measured value read in 0.5 mm increments, the amount of extension (underwater dimensional change: W (mm), and underwater at a point 0.3 m from both ends. Dimensional change: W 0 (mm)) is calculated.
  • W 0 (mm) is obtained by averaging two elongations obtained from a sample at a point 0.3 m away from both ends.
  • requiring underwater dimensional variation in the point of 0.3 m from both ends instead of both ends is that the thickness spot becomes large after the part less than 0.3 m from both ends is processed into a polarizing film. This is because most of them are often removed for reasons such as these, which are not preferable as measurement positions.
  • (W + W 0 ) / 2 which means the average value of the above-described underwater dimensional changes W and W 0 , is preferably 50 to 65 mm, more preferably 52 to 62 mm, and 55 to 60 mm. More preferably.
  • a PVA polymer film it is possible to easily obtain a polarizing film having a high degree of polarization and improved absorbance in the long wavelength region.
  • the said polarizing film in which the light absorbency in a long wavelength region improved, red discoloration at the time of setting it as LCD can be reduced.
  • the amount of dimensional change in water is inclined and decreased from a point of 0.3 m from the both ends to the center on a straight line in the width direction of the PVA polymer film.
  • a polarizing film having a high degree of polarization and improved absorbance in a long wavelength region can be easily obtained. It is preferable to be within a range of 55 to 59 mm. Further, as a specific value of the above-described underwater dimensional change amount W 0 , a polarizing film having a high degree of polarization and an improved absorbance in a long wavelength region can be easily obtained. It is preferably within the range, and more preferably within the range of 60 to 63 mm.
  • PVA polymers that form PVA polymer films include PVA (unmodified PVA) obtained by saponifying polyvinyl ester obtained by polymerizing vinyl ester, and graft copolymerization of a comonomer on the main chain of PVA.
  • PVA unmodified PVA
  • the modified PVA polymer produced by saponifying the modified polyvinyl ester copolymerized with vinyl ester and comonomer, unmodified PVA or modified PVA polymer examples thereof include so-called polyvinyl acetal resins crosslinked with aldehydes such as butyraldehyde and benzaldehyde.
  • the amount of modification in the PVA polymer is preferably 15 mol% or less, more preferably 5 mol% or less. preferable.
  • vinyl ester used in the production of the PVA polymer examples include vinyl acetate, vinyl formate, vinyl laurate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl stearate, and benzoic acid. Vinyl etc. can be mentioned. These vinyl esters can be used alone or in combination. Of these vinyl esters, vinyl acetate is preferred from the viewpoint of productivity.
  • Examples of the comonomer described above include olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene (such as ⁇ -olefin); acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, Acrylic esters such as n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
  • olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene (such as ⁇ -olefin); acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, Acrylic esters such as n-propyl acrylate,
  • acrylic acid having 1 to 18 carbon atoms of acrylic acid methacrylic acid or a salt thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i -Butyl, t-butyl methacrylate, Methacrylic acid esters such as 2-ethylhexyl crylate, dodecyl methacrylate, octadecyl methacrylate (for example, alkyl esters of 1 to 18 carbon atoms of methacrylic acid); acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N Acrylamide derivatives such as dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid or salts thereof, acrylamide propyl dimethylamine or salts thereof, N-methylol acrylamide or derivatives thereof; methacrylamide, N
  • the average degree of polymerization of the PVA polymer forming the PVA polymer film is preferably 1000 or more, more preferably 1500 or more, and still more preferably 2000 or more, from the viewpoint of the polarizing performance and durability of the obtained polarizing film.
  • the average degree of polymerization is preferably 8000 or less, particularly preferably 6000 or less, from the viewpoint of ease of production of a homogeneous PVA polymer film and stretchability.
  • the “average degree of polymerization” of the PVA polymer in the present specification refers to the average degree of polymerization measured according to JIS K6726-1994, and is 30 ° C. after re-saponifying and purifying the PVA polymer. It is obtained from the intrinsic viscosity measured in water.
  • the saponification degree of the PVA polymer forming the PVA polymer film is preferably 95.0 mol% or more, more preferably 98.0 mol% or more from the viewpoint of the polarizing performance and durability of the obtained polarizing film. 99.0 mol% or more is more preferable, and 99.3 mol% or more is most preferable.
  • the “degree of saponification” of the PVA polymer in the present specification refers 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. The percentage of the number of moles of the vinyl alcohol unit (mol%).
  • the degree of saponification of the PVA polymer can be measured according to the description of JIS K6726-1994.
  • the PVA polymer film contains, in addition to the above PVA polymer, a plasticizer, a surfactant, various additives other than those described below as an explanation of the production method of the present invention, for example, in the amounts described below. You may contain.
  • the volatile fraction (typically moisture content) of the PVA polymer film is preferably in the range of 1 to 5% by mass, more preferably in the range of 2 to 4% by mass.
  • the thickness of the PVA polymer film is not particularly limited, but is preferably 5 to 80 ⁇ m when used as a raw material for producing a polarizing film. A more preferable thickness is 20 to 80 ⁇ m.
  • the thickness of the PVA polymer film is less than or equal to the above upper limit, drying when producing a polarizing film is facilitated quickly, while the thickness of the PVA polymer film is greater than or equal to the above lower limit, The occurrence of film breakage can be more effectively suppressed during uniaxial stretching for producing a polarizing film.
  • the width of the PVA polymer film is not particularly limited, since the liquid crystal television and the monitor have recently been enlarged, the width is preferably 2 m or more in order to be able to be used effectively for those uses. It is more preferably 3 m or more, and further preferably 4 m or more.
  • the width of the PVA polymer film is 7.5 m or less. It is preferable that it is 7 m or less.
  • the length of the PVA polymer film is not particularly limited, and can be, for example, 50 to 30000 m.
  • the retardation value of the PVA polymer film is not particularly limited, but the retardation value in the width direction of the obtained polarizing film tends to be improved as the retardation value is smaller. Therefore, the retardation value is preferably 40 nm or less.
  • the production method of the PVA polymer film of the present invention is not particularly limited, but according to the following production method of the present invention, the PVA polymer film of the present invention can be produced smoothly and continuously.
  • the production method of the present invention for producing a PVA polymer film comprises a plurality of drying rolls having rotating shafts parallel to each other (in order from the most upstream side to the downstream side, the first drying roll and the second drying roll).
  • a film-forming apparatus comprising a roll, and a film-forming stock solution containing a PVA polymer is discharged into a film on the first drying roll of the film-forming apparatus and dried, followed by the second
  • the outer diameter of the central portion is the outer diameter of both ends.
  • a drying roll larger by 0.5 to 3 mm is used.
  • a film-forming apparatus including a plurality of drying rolls whose rotation axes are parallel to each other is used, and a film-forming stock solution containing a PVA polymer is formed into a film on the first drying roll of the film-forming apparatus. It discharges and dries, It dries further with the drying roll after the 2nd drying roll following the downstream of the said 1st drying roll, and forms a PVA polymer film.
  • the number of drying rolls (the number of drying rolls including the first drying roll (cast roll)) is preferably 9 to 30, and more preferably 12 to 26.
  • the plurality of drying rolls are preferably formed from a metal such as nickel, chromium, copper, iron, stainless steel, and the like, and in particular, the surface of the drying roll is formed from a metal material that is resistant to corrosion and has a specular gloss. More preferably. In order to increase the durability of the drying roll, it is more preferable to use a drying roll plated with a single layer or a combination of two or more layers such as a nickel layer, a chromium layer, and a nickel / chromium alloy layer.
  • first drying roll contact surface 1st drying Film surface in contact with the roll
  • first drying roll non-contact surface film surface not in contact with the first drying roll
  • a known film-like discharge device such as a die may be used to discharge (cast) a film-forming stock solution containing a PVA polymer onto the first drying roll.
  • the PVA polymer is mixed with a liquid medium to form a solution, or a PVA polymer pellet containing the liquid medium is melted to form a molten liquid.
  • a liquid medium used in this case include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylenediamine, and diethylenetriamine. These liquid media are used alone. Or two or more of them may be used in combination. Among these, water, dimethyl sulfoxide, or a mixture of both are preferably used, and water is more preferably used.
  • polyhydric alcohol is preferably used, and examples thereof include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like. 1 type may be used independently or 2 or more types may be used together. Among these, one or more of glycerin, diglycerin, and ethylene glycol are preferable because they are excellent in the effect of improving stretchability.
  • the addition amount of the plasticizer is preferably 0 to 30 parts by mass, more preferably 3 to 25 parts by mass, and particularly preferably 5 to 20 parts by mass with respect to 100 parts by mass of the PVA polymer.
  • the addition amount of the plasticizer is 30 parts by mass or less with respect to 100 parts by mass of the PVA polymer, the resulting PVA polymer film is not excessively soft and can be prevented from being deteriorated in handleability. .
  • a surfactant to the film-forming stock solution from the viewpoint of improving the peelability from the drying roll when producing the PVA polymer film and the handleability of the resulting PVA polymer film.
  • the type of the surfactant is not particularly limited, but an anionic surfactant or a nonionic surfactant is preferably used.
  • anionic surfactant for example, anionic surfactants such as carboxylic acid types such as potassium laurate, sulfate ester types such as octyl sulfate, and sulfonic acid types such as dodecylbenzene sulfonate are suitable.
  • Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether, alkylphenyl ether types such as polyoxyethylene octylphenyl ether, alkyl ester types such as polyoxyethylene laurate, and polyoxyethylene.
  • Alkylamine type such as laurylamino ether
  • alkylamide type such as polyoxyethylene lauric acid amide
  • polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether
  • alkanolamide type such as lauric acid diethanolamide, oleic acid diethanolamide
  • Nonionic surfactants such as allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether are preferred. These surfactants may be used alone or in combination of two or more.
  • the addition amount of the surfactant is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.5 part by mass, and 0.05 to 0.3 part by mass with respect to 100 parts by mass of the PVA polymer. Is particularly preferred.
  • an improvement effect such as film forming property and releasability is likely to appear. By being, it can suppress that a surfactant elutes on the film surface and causes a blocking, or that handleability falls.
  • the film forming stock solution contains various additives such as stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), compatibilizers, antiblocking agents, flame retardants, antistatic agents. , Lubricants, dispersants, fluidizing agents, antibacterial agents and the like. These additives may be used alone or in combination of two or more.
  • the volatile fraction of the film-forming stock solution used for the production of the PVA polymer film is preferably 50 to 90% by mass, more preferably 55 to 80% by mass, further preferably 60 to 75% by mass, and 65 to 70% by mass. Particularly preferred. If the volatile fraction of the film-forming stock solution is too low, the viscosity of the film-forming stock solution may become too high, making filtration and defoaming difficult, or making the film itself difficult. On the other hand, when the volatile fraction of the film-forming stock solution is too high, the viscosity becomes too low and the thickness uniformity of the PVA polymer film may be impaired.
  • the volatile fraction of the film-forming stock solution in the present specification refers to the volatile fraction obtained by the following formula (I).
  • Volatile fraction (mass%) of the film-forming stock solution ⁇ (Wa ⁇ Wb) / Wa ⁇ ⁇ 100 (I) (Wa represents the mass (g) of the film-forming stock solution, and Wb represents the mass (g) after drying the film-forming stock solution of Wa (g) for 16 hours in an electrothermal dryer at 105 ° C.)
  • the roll surface temperature of the first drying roll is preferably 80 to 120 ° C., more preferably 85 to 105 ° C. from the viewpoint of uniform drying property, drying speed, and the like. .
  • the film-forming stock solution discharged in the form of a film may be dried on the first drying roll only by heating from the first drying roll, the first drying roll non-contact surface is simultaneously heated with the first drying roll. It is preferable from the viewpoints of uniform drying property, drying speed, and the like to dry by blowing hot air onto the film and applying heat from both sides of the film.
  • hot air having a wind speed of 1 to 10 m / sec is blown over the entire area of the first drying roll non-contact surface.
  • hot air having a wind speed of 2 to 8 m / sec is more preferably blown
  • hot air having a wind speed of 3 to 8 m / sec is more preferably blown.
  • the temperature of the hot air blown on the non-contact surface of the first drying roll of the film is preferably 50 to 150 ° C., more preferably 70 to 120 ° C. from the viewpoint of drying efficiency, drying uniformity, and the like. More preferably, it is -95 ° C. If the temperature of the hot air sprayed on the non-contact surface of the first drying roll of the film is too low, condensation such as water vapor occurs, and the water droplets may fall on the film, possibly resulting in defects in the PVA polymer film finally obtained. There is. On the other hand, when the temperature is too high, dry spots are generated along the direction of hot air, and there is a possibility that thickness spots of the finally obtained PVA polymer film are generated.
  • the dew point temperature of the hot air blown on the non-contact surface of the first drying roll of the film is preferably 5 to 20 ° C, more preferably 10 to 15 ° C, and further preferably 11 to 13 ° C. If the dew point temperature of the hot air blown on the non-contact surface of the first drying roll of the film is too low, the drying efficiency, uniform drying property and the like are liable to be lowered, while if the dew point temperature is too high, foaming is likely to occur.
  • the method for blowing hot air to the non-contact surface of the first drying roll of the film is not particularly limited, and the hot air having a uniform wind speed and uniform temperature is uniformly applied to the non-contact surface of the first drying roll, preferably the entire surface thereof. Any of the methods that can be sprayed can be employed, and among them, the nozzle method, the current plate method, or a combination thereof is preferably employed.
  • the blowing direction of the hot air to the first drying roll non-contact surface of the film was substantially along the circumferential shape of the first drying roll non-contact surface of the film, even in the direction facing the first drying roll non-contact surface.
  • the direction may be the direction (direction substantially along the circumference of the roll surface of the first drying roll) or the other direction.
  • the film when the film is dried on the first drying roll, it is preferable to exhaust the volatile matter generated from the film by drying and the hot air after spraying.
  • the exhaust method is not particularly limited, but it is preferable to employ an exhaust method that does not generate wind speed spots and temperature spots of hot air sprayed on the non-contact surface of the first drying roll of the film.
  • the peripheral speed (S 1 ) of the first drying roll is preferably 5 to 30 m / min, and preferably 7 to 25 m / min from the viewpoints of uniform drying, drying speed, and productivity of the PVA polymer film. More preferably.
  • productivity is lowered and stretchability of the obtained PVA polymer film tends to be lowered.
  • the peripheral speed (S 1 ) of the first drying roll exceeds 30 m / min, peeling from the first drying roll tends to be non-uniform and defects tend to occur.
  • the film-forming stock solution discharged in the form of a film on the first drying roll is dried on the first drying roll and peeled off from the first drying roll. If the volatile content of the film at the time of peeling from the first drying roll is too low, the productivity of the PVA polymer film tends to decrease, while the film volatilization at the time of peeling from the first drying roll. If the fraction is too high, peeling from the first drying roll is likely to be difficult, and in some cases, breakage or spots are likely to occur. From the above viewpoint, the volatile fraction of the film at the time of peeling from the first drying roll is preferably 10% by mass or more, more preferably 15% by mass or more, and 18% by mass or more.
  • the volatile fraction of the film in the present specification refers to the volatile fraction determined by the following formula (II).
  • M (mass%) ⁇ (Wc ⁇ Wd) / Wc ⁇ ⁇ 100 (II) (Where M is the volatile fraction (% by mass) of the film, Wc is the mass (g) of the sample taken from the film, and Wd is the vacuum drying of the sample Wc (g) at a temperature of 50 ° C. and a pressure of 0.1 kPa or less.
  • the film dried on the first drying roll is peeled off from the first drying roll, and this time, preferably the first drying roll non-contact surface of the film is opposed to the second drying roll and the film is dried with the second drying roll. To do.
  • the ratio (S 2 / S 1 ) of the peripheral speed (S 2 ) of the second drying roll to the peripheral speed (S 1 ) of the first drying roll is preferably 1.005 to 1.060, and 1.010 More preferably, it is ⁇ 1.050. If the ratio (S 2 / S 1 ) is too low, the peeling from the first drying roll tends to be uneven and defects tend to occur. On the other hand, if the ratio (S 2 / S 1 ) is too high, when the obtained PVA polymer film is stretched and processed into a polarizing film, the absorbance in the long wavelength region of the polarizing film tends to be low.
  • a drying roll having an outer diameter of 0.5 to 3 mm larger than the outer diameter of both ends is used as at least one of the drying rolls after the second drying roll.
  • a cylindrical drying roll (flat roll) having the same outer diameter at the center and the outer diameter at both ends is used.
  • the outer diameter at the center is used.
  • the outer diameter of the central portion in the drying roll is preferably 0.7 mm or more larger than the outer diameter of both end portions, and 2.5 mm. It is preferably smaller, more preferably 2 mm or less, still more preferably 1 mm or less.
  • the outer diameter of each edge part should just satisfy
  • the specific outer diameter of the central portion of the drying roll can be set to, for example, 300 to 800 mm (more preferably 350 to 700 mm).
  • the outer diameter of the drying roll is inclined from both end portions toward the central portion, and the inclination is linearly inclined, curvedly inclined, or straight and curved.
  • the center part is suitable for the center part to have a slightly flat part.
  • the specific drying roll is used as at least one of the drying rolls subsequent to the second drying roll, but only one of the final drying rolls from the second drying roll is specified. Even if two or more of the second drying roll to the final drying roll are the specific drying roll, all of the second drying roll to the final drying roll are the specific drying roll. Any of rolls can be used.
  • the shape of a 1st drying roll is a normal cylindrical shape, ie, the outer diameter of a center part, and the outer diameter of both ends are the same shape.
  • the surface temperature of the drying roll after the second drying roll is preferably 50 to 80 ° C. because the PVA polymer film of the present invention can be produced more smoothly, and 60 to 75 ° C. in terms of production stability. Is more preferable.
  • the drying rolls after the second drying roll only the final drying roll, or one or two or more drying rolls close to the final and the final drying roll may be used as a heat treatment roll by increasing the surface temperature. That is, the drying roll in the film forming apparatus includes the heat treatment roll when the heat treatment roll is used.
  • the surface temperature of the drying roll is preferably 90 to 120 ° C, more preferably 100 to 110 ° C. By performing heat treatment at such a temperature, crystallization proceeds moderately and hot water resistance is improved.
  • the ratio of the peripheral speed (S T ) of the final drying roll to the peripheral speed (S 1 ) of the first drying roll (S T / S 1 ) is: It is preferably 0.960 to 1.100. If the ratio (S T / S 1 ) is too low, the film tends to sag between the drying rolls, and if it is too high, the retardation tends to increase and the retardation in the width direction tends to increase. From such a viewpoint, the ratio (S T / S 1 ) is more preferably 0.980 or more, further preferably 0.985 or more, and more preferably 1.050 or less. More preferably, it is 1.030 or less.
  • the film forming apparatus may have a hot air oven type hot air drying apparatus, a heat treatment apparatus, a humidity control apparatus, etc. as necessary.
  • the film forming apparatus may be prepared after drying by the drying roll (including heat treatment by the heat treatment roll). Wet treatment can be applied.
  • you may cut a film both ends (ear part) as needed.
  • the PVA polymer film finally obtained by the above series of treatments preferably has a volatile content (typically moisture content) in the range of 1 to 5% by mass, preferably in the range of 2 to 4% by mass. More preferably. If the volatile content is too high, the amount of dimensional change in water tends to be high.
  • the obtained PVA polymer film is preferably wound into a roll with a predetermined length.
  • the PVA polymer film may be dyed, uniaxially stretched, fixed, dried, and further heat treated as necessary.
  • the order of dyeing and uniaxial stretching is not particularly limited, and the dyeing process may be performed before the uniaxial stretching process, the dyeing process may be performed simultaneously with the uniaxial stretching process, or the dyeing process may be performed after the uniaxial stretching process. You may go.
  • steps such as uniaxial stretching and dyeing may be repeated a plurality of times. In particular, it is preferable to divide the uniaxial stretching into two or more stages because uniform stretching is easily performed.
  • dyes used for dyeing PVA polymer films include iodine or dichroic organic dyes (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). These dyes can be used alone or in combination of two or more. Dyeing can usually be performed by immersing the PVA polymer film in a solution containing the dye, but the treatment conditions and treatment method are not particularly limited.
  • Uniaxial stretching for stretching the PVA polymer film in the length direction (MD) or the like may be performed by either a wet stretching method or a dry heat stretching method. From the viewpoint of the performance and quality stability of the obtained polarizing film.
  • the wet stretching method is preferred.
  • the wet stretching method include a method of stretching a PVA polymer film in pure water, an aqueous solution containing various components such as an additive and an aqueous medium, or an aqueous dispersion in which various components are dispersed.
  • the uniaxial stretching method there are a method of uniaxial stretching in warm water containing boric acid, a method of uniaxial stretching in a solution containing the above-described dye or a fixing treatment bath described later, and the like.
  • the stretching temperature for uniaxial stretching is not particularly limited, but in the case of wet stretching, a temperature in the range of preferably 20 to 90 ° C, more preferably 25 to 70 ° C, and even more preferably 30 to 65 ° C is adopted. In the case of hot stretching, a temperature within the range of 50 to 180 ° C. is preferably employed.
  • the stretching ratio of the uniaxial stretching treatment (the total stretching ratio when performing uniaxial stretching in multiple stages) 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. 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.
  • fixing treatment is often performed in order to strengthen the adsorption of the dye to the uniaxially stretched film.
  • a method of immersing a film in a treatment bath to which boric acid and / or a boron compound is added is generally widely adopted. In that case, you may add an iodine compound in a processing bath as needed.
  • the film subjected to the uniaxial stretching treatment or the uniaxial stretching treatment and the fixing treatment is then subjected to a drying treatment (heat treatment).
  • the temperature of the drying treatment (heat treatment) is preferably 30 to 150 ° C., particularly 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 polarizing performance is likely to deteriorate due to the decomposition of the dye.
  • Protective films that are optically transparent and have mechanical strength can be bonded to both sides or one side of the polarizing film obtained as described above to form a polarizing plate.
  • a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like is used.
  • a PVA adhesive or a urethane adhesive is generally used, and among them, a PVA adhesive is preferably used.
  • the polarizing plate obtained as described above can be used as a component of a liquid crystal display device after being coated with an acrylic adhesive or the like and then bonded to a glass substrate.
  • a retardation film, a viewing angle improving film, a brightness improving film, or the like may be bonded simultaneously.
  • the volatile content rate (water content) of the film-forming stock solution the volatile content rate (water content) of the film, the drying roll surface temperature, the dimensional change in water, and the optical performance of the polarizing film are as follows: It was measured or evaluated by the method.
  • the outer part from the marked lines at both ends was sandwiched between commercially available clips (chuck width 4 cm, mass 7.8 g (weight in water 7.3 g)), and one clip was fixed with a rod-shaped jig such as a number wire.
  • a rod-shaped jig such as a number wire.
  • the sample with the clip is quickly put into the pure water adjusted to 30 ° C stored in a cylindrical transparent water tank so that the entire sample enters the water.
  • the long side was immersed vertically.
  • a rod-shaped jig was hooked on the upper part of the water tank, and the long side of the sample was fixed to be vertical (vertical). Thereafter, a metal ruler was immersed in water, and the distance between marked lines was measured 5 minutes after immersion.
  • Optical performance of polarizing film (i) Polarization degree at transmittance of 43.5%
  • iodine / iodine during the second stage stretching For each of the five types of polarizing films produced by changing the iodine concentration in the potassium halide / boric acid aqueous solution, the single transmittance (Y) and the degree of polarization (V) were determined by the following methods. Each time, a single transmittance (Y) is plotted on the horizontal axis and the degree of polarization (V) is plotted on the vertical axis, and an approximate curve is created by plotting five points on the graph. The value of the degree of polarization (V) at 5% was determined, and this was defined as “the degree of polarization at 43.5% transmittance”.
  • ⁇ 1 Measuring method of single transmittance (Y): Two square samples of 4 cm (uniaxial stretching direction) ⁇ 4 cm (perpendicular to the uniaxial stretching direction) were collected from the center in the width direction of the polarizing film. The light transmittance of these samples was measured using a spectrophotometer “V-7100” manufactured by JASCO Corporation. At the time of measurement, in accordance with JIS Z 8722 (object color measurement method), the visibility correction of the visible light region of the 2-degree visual field was performed using a C light source. For one sample, the light transmittance when tilted by +45 degrees with respect to the uniaxial stretching direction and the light transmittance when tilted by ⁇ 45 degrees with respect to the uniaxial stretching direction were measured.
  • the average value (Y 1 ) (%) thereof was determined.
  • the light transmittance when tilted by +45 degrees and the light transmittance when tilted by ⁇ 45 degrees were measured, and the average value (Y 2 ) (%) thereof was measured. Asked. Then, it was the Y 1 and Y 2 obtained by averaging by the following formula (III) single axis transmittance of the polarizing film (Y) (%).
  • Single transmittance (Y) (%) (Y 1 + Y 2 ) / 2 (III)
  • ⁇ 2 Measuring method of degree of polarization (V): Light transmittance (Y ⁇ ) when the two samples collected in the above “ ⁇ 1 >> Measuring method of simple substance transmittance (Y)” are overlapped so that their uniaxial stretching directions are parallel. (%) And the light transmittance (Y ⁇ ) (%) were measured when the uniaxially drawn stretching directions were orthogonal to each other. The transmittances (Y ⁇ ) and (Y ⁇ ) were tilted by +45 degrees with respect to the stretching direction of uniaxial stretching of one sample in the same manner as in “ ⁇ 1 >> Measuring method of single transmittance (Y)”.
  • a spectrophotometer “V-7100” manufactured by JASCO Corporation was fitted with a Glan-Taylor prism, and a polarizing film sample was placed at a position perpendicular to the optical axis (“(i) transmittance 43.5% described above).
  • Polarization degree in ⁇ 1 >> Measurement method of single transmittance (Y) "Arbitrary one of the two samples collected for each polarizing film) is installed, and it becomes linearly polarized light from the light source through the prism. The transmittance of light having a wavelength of 700 nm was measured when light having a measurement wavelength of 380 to 780 nm was transmitted through the sample.
  • the sample is rotated in a plane orthogonal to the optical axis, the transmittance change is measured, the maximum value T 0 of the transmittance and the minimum value T 90 of the transmittance are obtained, and the following equation (V) is obtained.
  • the light absorbency (A) in the measurement wavelength 700nm of the polarizing film was computed from the following formula
  • the absorbance (A) at a measurement wavelength of 700 nm when the single transmittance (Y) of the polarizing film is 43.5% is obtained from a straight line, and this is expressed as “absorbance at a measurement wavelength of 700 nm at a transmittance of 43.5% (A ) ”.
  • Optical unevenness A polarizing film continuously produced in the following examples or comparative examples is completely crossed Nicol on one polarizing plate (single transmittance 43.5%, polarization degree 99.9%). Installed so as to be in a state, using a backlight with a brightness of 15000 candela, observe the transmittance unevenness (optical unevenness) between the center portion and the end portion in the width direction (TD) of the polarizing film, The optical unevenness was evaluated according to the criteria.
  • ⁇ The difference between light and dark due to the difference in transmittance is not visible at the center and both ends.
  • X The central part is bright or dark with respect to both end parts, and there is a difference in shading.
  • Example 1 Production of PVA polymer film 100 parts by mass of PVA (saponification degree 99.9 mol%, average degree of polymerization 2400) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, diethanolamide 0 of lauric acid A film-forming stock solution having a volatile content ratio of 66% by mass consisting of 1 part by mass and water is transferred from a T-die to a first drying roll (surface temperature 90 ° C., surface temperature 90 ° C. The film is discharged in the form of a film at a peripheral speed (S 1 ) of 10.0 m / min), and hot air of 90 ° C.
  • PVA response degree 99.9 mol%, average degree of polymerization 2400
  • the peripheral speed (S 17 ) of the final drying roll (17th drying roll (heat treatment roll)) was 9.8 m / min. After that, it was wound up into a roll shape and PVA film (thickness 60 ⁇ m, width 4 m, volatile content (water content) 3 mass%, underwater dimensional change (W) 58 mm, underwater at a point 0.3 m from both ends. A dimensional change amount (average value: W 0 ) 61 mm) was obtained.
  • Example 1 the ratio of the peripheral speed of the first drying roll peripheral speed of the second drying roll for (S 1) (S 2) a (S 2 / S 1) and 1.025, circumference of the first drying roll fast circumferential velocity of the last drying roll against (S 1) the ratio of (S 17) (S 17 / S 1) and 0.980.
  • the film forming conditions are shown in Table 1 below.
  • Example 1 a PVA film and a polarizing film were produced in the same manner as in Example 1 except that the film forming conditions (including the film forming apparatus) of the PVA film were changed as described in Table 1 below. About the manufactured PVA film and polarizing film, each measurement or evaluation was performed similarly to Example 1. The results are shown in Table 1.
  • the PVA polymer film of the present invention it is possible to produce a polarizing film with less unevenness in transmittance between the central portion and the end portion. Therefore, the PVA polymer film is particularly a large area polarizing film. It is useful as a raw film for manufacturing.

Landscapes

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

Abstract

La présente invention concerne un film polymère à base de PVA permettant la production d'un film polarisant caractérisé par une faible irrégularité en matière de transmittance de la lumière entre sa partie centrale et sa partie périphérique. L'invention concerne, donc, un film polymère à base de PVA satisfaisant l'équation : 0,5 mm ≤ W0-W ≤ 5 mm, dans laquelle W (mm) représente la modification des dimensions d'une partie centrale du film polymère à base de PVA dans l'eau et W0 (mm) représente la modification des dimensions (valeur moyenne) d'une partie située à 0,3 mm de l'une ou de l'autre des parties périphériques du film polymère à base de PVA dans l'eau, la partie centrale et la partie périphérique étant situées sur une droite tracée dans le sens de la largeur (sens perpendiculaire au sens de la longueur) du film polymère à base de PVA. L'expression « modification des dimensions dans l'eau » correspond à l'allongement d'un échantillon du film polymère à base de PVA dans le sens de la longueur, comme mesuré au niveau d'un point placé à 250 mm du bord du film dans le sens de la longueur du film après immersion de l'échantillon dans de l'eau pure à une température de 30 °C pendant 5 minutes.
PCT/JP2013/056149 2012-03-30 2013-03-06 Film polymère à base d'alcool polyvinylique (pva) et film polarisant WO2013146146A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020137029866A KR20140130362A (ko) 2012-03-30 2013-03-06 폴리비닐알코올계 중합체 필름 및 편광 필름
KR1020137029799A KR101397899B1 (ko) 2012-03-30 2013-03-06 폴리비닐알코올계 중합체 필름 및 편광 필름
JP2013538389A JP5390052B1 (ja) 2012-03-30 2013-03-06 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
CN201380018351.9A CN104204046B (zh) 2012-03-30 2013-03-06 聚乙烯醇系聚合物膜和偏光膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012079508 2012-03-30
JP2012-079508 2012-03-30

Publications (1)

Publication Number Publication Date
WO2013146146A1 true WO2013146146A1 (fr) 2013-10-03

Family

ID=49259417

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/056149 WO2013146146A1 (fr) 2012-03-30 2013-03-06 Film polymère à base d'alcool polyvinylique (pva) et film polarisant

Country Status (5)

Country Link
JP (2) JP5390052B1 (fr)
KR (2) KR101397899B1 (fr)
CN (2) CN104204046B (fr)
TW (3) TWI579604B (fr)
WO (1) WO2013146146A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015129538A1 (fr) * 2014-02-27 2015-09-03 株式会社クラレ Film à base d'alcool polyvinylique et son procédé de fabrication
WO2016093259A1 (fr) * 2014-12-12 2016-06-16 株式会社クラレ Film polymère à base d'alcool polyvinylique, et procédé de fabrication de celui-ci
JP2016176971A (ja) * 2015-03-18 2016-10-06 株式会社クラレ ポリビニルアルコールフィルム
WO2020138441A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film hydrosoluble et emballage
WO2020138445A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film de base de transfert hydraulique et film d'impression par transfert hydraulique
JPWO2019054487A1 (ja) * 2017-09-15 2020-10-29 株式会社クラレ ポリビニルアルコールフィルム及びその製造方法
US20210324159A1 (en) * 2018-12-28 2021-10-21 Kuraray Co., Ltd. Water-soluble film and package
WO2022004537A1 (fr) * 2020-06-30 2022-01-06 株式会社クラレ Film d'alcool polyvinylique et film polarisant le comprenant
KR20220113932A (ko) 2019-12-11 2022-08-17 주식회사 쿠라레 광학용 폴리비닐알코올 필름의 제조 방법
WO2023074639A1 (fr) * 2021-10-25 2023-05-04 株式会社クラレ Film d'alcool polyvinylique

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107001671B (zh) * 2014-12-12 2023-06-20 株式会社可乐丽 聚乙烯醇膜
JP6756465B2 (ja) * 2015-07-02 2020-09-16 住友化学株式会社 偏光フィルムの製造方法
KR102400929B1 (ko) * 2016-05-27 2022-05-23 미쯔비시 케미컬 주식회사 폴리비닐알코올계 필름 및 이의 제조 방법, 및 상기 폴리비닐알코올계 필름을 사용한 편광막
JP7335697B2 (ja) * 2017-04-26 2023-08-30 三菱ケミカル株式会社 ポリビニルアルコール系フィルム、偏光膜および偏光板、ならびにポリビニルアルコール系フィルムの製造方法
WO2018199140A1 (fr) * 2017-04-26 2018-11-01 日本合成化学工業株式会社 Film d'alcool polyvinylique, film polarisant et plaque polarisante, et procédé de production de film d'alcool polyvinylique
CN110741292B (zh) * 2017-06-21 2022-08-30 株式会社可乐丽 原材料膜、拉伸光学膜的制备方法、和拉伸光学膜
JP7093349B2 (ja) * 2017-06-21 2022-06-29 株式会社クラレ 原反フィルム、延伸光学フィルムの製造方法、及び延伸光学フィルム
EP3904036A4 (fr) 2018-12-28 2022-09-14 Kuraray Co., Ltd. Film hydrosoluble et matériau d'emballage
EP3904437A4 (fr) * 2018-12-28 2022-09-21 Kuraray Co., Ltd. Film hydrosoluble et emballage

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002028939A (ja) * 2000-07-17 2002-01-29 Kuraray Co Ltd ポリビニルアルコール系重合体フィルムとその製造法および偏光フィルム
JP2007137042A (ja) * 2004-12-28 2007-06-07 Nippon Synthetic Chem Ind Co Ltd:The 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
WO2012002194A1 (fr) * 2010-07-02 2012-01-05 日本合成化学工業株式会社 Film d'alcool polyvinylique, procédé pour la production d'un film d'alcool polyvinylique, film de polarisation, et plaque de polarisation
JP2012042929A (ja) * 2010-07-21 2012-03-01 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルムの製造方法、ポリビニルアルコール系フィルム、偏光フィルム及び偏光板

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03287630A (ja) * 1990-04-05 1991-12-18 Kuraray Co Ltd ポリビニルアルコール系フイルムの製造方法および偏光フイルムの製造方法
JP2002156651A (ja) * 2000-11-16 2002-05-31 Nec Corp パターン形成方法及びそれを用いた反射型液晶表示装置の製造方法
JP3911465B2 (ja) * 2002-09-19 2007-05-09 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の製法
US9085664B2 (en) * 2004-12-28 2015-07-21 The Nippon Synthetic Chemical Industry Co., Ltd. Polyvinyl alcohol film, and polarizing film and polarizing plate using the same
JP4664100B2 (ja) * 2005-03-16 2011-04-06 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、および偏光膜、偏光板
GB2442626A (en) * 2005-06-16 2008-04-09 Nippon Synthetic Chem Ind Water-soluble film
JP4499131B2 (ja) * 2007-04-18 2010-07-07 株式会社クラレ 偏光フィルムの製造法
KR101544626B1 (ko) * 2007-08-24 2015-08-17 가부시키가이샤 구라레 폴리비닐알코올 필름 및 그 제조법
KR101177865B1 (ko) * 2010-03-17 2012-08-30 황장환 3ｄ 광학필름을 채용한 편광필름 및 이를 이용한 3ｄ 디스플레이

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002028939A (ja) * 2000-07-17 2002-01-29 Kuraray Co Ltd ポリビニルアルコール系重合体フィルムとその製造法および偏光フィルム
JP2007137042A (ja) * 2004-12-28 2007-06-07 Nippon Synthetic Chem Ind Co Ltd:The 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
WO2012002194A1 (fr) * 2010-07-02 2012-01-05 日本合成化学工業株式会社 Film d'alcool polyvinylique, procédé pour la production d'un film d'alcool polyvinylique, film de polarisation, et plaque de polarisation
JP2012042929A (ja) * 2010-07-21 2012-03-01 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルムの製造方法、ポリビニルアルコール系フィルム、偏光フィルム及び偏光板

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015129538A1 (fr) * 2014-02-27 2015-09-03 株式会社クラレ Film à base d'alcool polyvinylique et son procédé de fabrication
CN106029755A (zh) * 2014-02-27 2016-10-12 株式会社可乐丽 聚乙烯醇膜及其制造方法
JPWO2015129538A1 (ja) * 2014-02-27 2017-03-30 株式会社クラレ ポリビニルアルコールフィルムおよびその製造方法
CN106029755B (zh) * 2014-02-27 2021-10-26 株式会社可乐丽 聚乙烯醇膜及其制造方法
CN113416333A (zh) * 2014-02-27 2021-09-21 株式会社可乐丽 聚乙烯醇膜及其制造方法
WO2016093259A1 (fr) * 2014-12-12 2016-06-16 株式会社クラレ Film polymère à base d'alcool polyvinylique, et procédé de fabrication de celui-ci
JPWO2016093259A1 (ja) * 2014-12-12 2017-09-21 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
JP2016176971A (ja) * 2015-03-18 2016-10-06 株式会社クラレ ポリビニルアルコールフィルム
JP7157751B2 (ja) 2017-09-15 2022-10-20 株式会社クラレ ポリビニルアルコールフィルム及びその製造方法
JPWO2019054487A1 (ja) * 2017-09-15 2020-10-29 株式会社クラレ ポリビニルアルコールフィルム及びその製造方法
US20210324159A1 (en) * 2018-12-28 2021-10-21 Kuraray Co., Ltd. Water-soluble film and package
US20210324160A1 (en) * 2018-12-28 2021-10-21 Kuraray Co., Ltd. Water-soluble film and package
WO2020138445A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film de base de transfert hydraulique et film d'impression par transfert hydraulique
JPWO2020138441A1 (ja) * 2018-12-28 2021-11-04 株式会社クラレ 水溶性フィルムおよび包装体
JPWO2020138445A1 (ja) * 2018-12-28 2021-11-11 株式会社クラレ 水圧転写用ベースフィルムおよび水圧転写用印刷フィルム
WO2020138441A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film hydrosoluble et emballage
JP7240423B2 (ja) 2018-12-28 2023-03-15 株式会社クラレ 水圧転写用ベースフィルムおよび水圧転写用印刷フィルム
KR20220113932A (ko) 2019-12-11 2022-08-17 주식회사 쿠라레 광학용 폴리비닐알코올 필름의 제조 방법
WO2022004537A1 (fr) * 2020-06-30 2022-01-06 株式会社クラレ Film d'alcool polyvinylique et film polarisant le comprenant
WO2023074639A1 (fr) * 2021-10-25 2023-05-04 株式会社クラレ Film d'alcool polyvinylique

Also Published As

Publication number Publication date
TWI579604B (zh) 2017-04-21
TWI498611B (zh) 2015-09-01
JPWO2013146146A1 (ja) 2015-12-10
TW201516491A (zh) 2015-05-01
CN104204046B (zh) 2017-06-23
CN104204046A (zh) 2014-12-10
TW201344261A (zh) 2013-11-01
KR20130132665A (ko) 2013-12-04
CN106226858A (zh) 2016-12-14
TWI564602B (zh) 2017-01-01
TW201539068A (zh) 2015-10-16
KR20140130362A (ko) 2014-11-10
KR101397899B1 (ko) 2014-05-20
JP5390052B1 (ja) 2014-01-15
JP2014016649A (ja) 2014-01-30
CN106226858B (zh) 2018-09-04
JP6030528B2 (ja) 2016-11-24

Similar Documents

Publication Publication Date Title
JP6030528B2 (ja) 偏光フィルムの製造方法
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
JP6030529B2 (ja) 偏光フィルムの製造方法
JP5117639B2 (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
JP7157751B2 (ja) ポリビニルアルコールフィルム及びその製造方法
JPWO2016084836A1 (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
WO2013146458A1 (fr) Film de polymère à base d'alcool polyvinylique, et film polarisant
JP5405700B1 (ja) エチレン変性ポリビニルアルコール系重合体フィルム
JPWO2016093258A1 (ja) ポリビニルアルコールフィルム
JP4926548B2 (ja) 偏光フィルムの製造法
JP4104917B2 (ja) 偏光フィルムの製造法
JP7375042B2 (ja) 光学用ポリビニルアルコールフィルムの製造方法
JP5179646B2 (ja) 偏光フィルム
JP2017015415A (ja) ポリビニルアルコールフィルムの光学斑の評価方法
JP2007328253A (ja) ポリビニルアルコールフィルム

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2013538389

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20137029799

Country of ref document: KR

Kind code of ref document: A

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

Ref document number: 13768712

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 13768712

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE