WO2013146146A1 - Polyvinyl alcohol-type polymer film and polarizing film - Google Patents
Polyvinyl alcohol-type polymer film and polarizing film Download PDFInfo
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- 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
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- pva polymer
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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.
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Abstract
Description
[1]PVA系重合体フィルムの幅方向(長さ方向に対し直角方向)の直線上において、中央部の水中寸法変化量をW(mm)、両端部から0.3mの地点の水中寸法変化量(平均値)をW0(mm)とする(ここで水中寸法変化量は、PVA系重合体フィルムのサンプルを30℃の純水に5分間浸漬したときの、浸漬前の長さ方向250mmの部分における長さ方向の伸び量である)とき、0.5mm≦W0-W≦5mmを満足するPVA系重合体フィルム;
[2](W+W0)/2が50~65mmである、上記[1]のPVA系重合体フィルム;
[3]Wが50~60mmであり、W0が55~65mmである、上記[1]または[2]のPVA系重合体フィルム;
[4]揮発分率が1~5質量%である、上記[1]~[3]のいずれか1つのPVA系重合体フィルム;
[5]幅が2~7.5mである、上記[1]~[4]のいずれか1つのPVA系重合体フィルム;
[6]偏光フィルム製造用原反フィルムである、上記[1]~[5]のいずれか1つのPVA系重合体フィルム;
[7]回転軸が互いに平行な複数の乾燥ロールを備える製膜装置を使用し、当該製膜装置の第1乾燥ロール上にPVA系重合体を含む製膜原液を膜状に吐出して乾燥し、それに続く第2乾燥ロール以降の乾燥ロールで更に乾燥してPVA系重合体フィルムを製膜する際に、第2乾燥ロール以降の乾燥ロールのうちの少なくとも1つとして、中央部の外径が両端部の外径より0.5~3mm大きい乾燥ロールを用いる、PVA系重合体フィルムの製造方法;および、
[8]上記[6]のPVA系重合体フィルムから製造される偏光フィルム;
に関する。 That is, 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 PVA polymer film satisfying 0.5 mm ≦ W 0 -W ≦ 5 mm;
[2] The PVA polymer film of [1], wherein (W + W 0 ) / 2 is 50 to 65 mm;
[3] The PVA polymer film of [1] or [2] above, wherein W is 50 to 60 mm and W 0 is 55 to 65 mm;
[4] The PVA polymer film according to any one of the above [1] to [3], having a volatile content of 1 to 5% by mass;
[5] The PVA polymer film according to any one of the above [1] to [4], having a width of 2 to 7.5 m;
[6] The PVA polymer film according to any one of [1] to [5], which is a raw film for producing a polarizing film;
[7] Using a film-forming apparatus provided with a plurality of drying rolls whose rotation axes are parallel to each other, 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. Then, when the PVA polymer film is further dried with a subsequent drying roll after the second drying roll to form a PVA polymer film, 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.
PVA系重合体フィルムを形成するPVA系重合体が変性PVA系重合体である場合は、PVA系重合体における変性量は15モル%以下であることが好ましく、5モル%以下であることがより好ましい。 Examples of 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. A part of the hydroxyl groups of the modified PVA polymer, 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.
When the PVA polymer forming the PVA polymer film is a modified PVA polymer, the amount of modification in the PVA polymer is preferably 15 mol% or less, more preferably 5 mol% or less. preferable.
ここで、本明細書におけるPVA系重合体の「平均重合度」とは、JIS K6726-1994に準じて測定される平均重合度をいい、PVA系重合体を再けん化し、精製した後に30℃の水中で測定した極限粘度から求められる。 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. On the other hand, with respect to the upper limit of the average degree of polymerization of the PVA polymer, 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.
Here, 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.
ここで、本明細書におけるPVA系重合体の「けん化度」とは、けん化によりビニルアルコール単位に変換され得る構造単位(典型的にはビニルエステル単位)とビニルアルコール単位との合計モル数に対して当該ビニルアルコール単位のモル数が占める割合(モル%)をいう。PVA系重合体のけん化度は、JIS K6726-1994の記載に準じて測定することができる。 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.
Here, 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.
その際に用いる液体媒体としては、例えば、水、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、N-メチルピロリドン、エチレンジアミン、ジエチレントリアミンなどを挙げることができ、これらの液体媒体は、1種を単独で使用してもまたは2種以上を併用してもよい。これらの中でも水、ジメチルスルホキシド、または両者の混合物が好ましく用いられ、特に水がより好ましく用いられる。 As a film-forming stock solution containing a PVA polymer film, 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. Can be prepared.
Examples of the 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.
可塑剤としては多価アルコールが好ましく用いられ、例えば、エチレングリコール、グリセリン、ジグリセリン、プロピレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、トリメチロールプロパンなどを挙げることができ、これらの可塑剤は、1種を単独で使用してもまたは2種以上を併用してもよい。これらの中でも延伸性の向上効果に優れる点から、グリセリン、ジグリセリンおよびエチレングリコールのうちの1種または2種以上が好ましい。 From the viewpoints of accelerating dissolution and melting of PVA polymer in a liquid medium, improving process passability during the production of PVA polymer film, and improving the stretchability of the resulting PVA polymer film, It is preferable to add an agent.
As the plasticizer, 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.
アニオン性界面活性剤としては、例えば、ラウリン酸カリウム等のカルボン酸型、オクチルサルフェート等の硫酸エステル型、ドデシルベンゼンスルホネート等のスルホン酸型などのアニオン性界面活性剤が好適である。
また、ノニオン性界面活性剤としては、例えば、ポリオキシエチレンオレイルエーテル等のアルキルエーテル型、ポリオキシエチレンオクチルフェニルエーテル等のアルキルフェニルエーテル型、ポリオキシエチレンラウレート等のアルキルエステル型、ポリオキシエチレンラウリルアミノエーテル等のアルキルアミン型、ポリオキシエチレンラウリン酸アミド等のアルキルアミド型、ポリオキシエチレンポリオキシプロピレンエーテル等のポリプロピレングリコールエーテル型、ラウリン酸ジエタノールアミド、オレイン酸ジエタノールアミド等のアルカノールアミド型、ポリオキシアルキレンアリルフェニルエーテル等のアリルフェニルエーテル型などのノニオン性界面活性剤が好適である。
これらの界面活性剤は1種を単独で使用してもまたは2種以上を併用してもよい。 It is preferable to add 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.
As the 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.
ここで、本明細書でいう「製膜原液の揮発分率」とは、下記の式(I)により求めた揮発分率をいう。
製膜原液の揮発分率(質量%)={(Wa-Wb)/Wa}×100 (I)
(ここで、Waは製膜原液の質量(g)を表し、WbはWa(g)の製膜原液を105℃の電熱乾燥機中で16時間乾燥した後の質量(g)を表す。) 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.
Here, “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.)
ここで、本明細書における「フィルムの揮発分率」とは、下記の式(II)により求めた揮発分率をいう。
M(質量%)={(Wc-Wd)/Wc}×100 (II)
(ここで、Mはフィルムの揮発分率(質量%)、Wcはフィルムから採取したサンプルの質量(g)、Wdは前記サンプルWc(g)を温度50℃、圧力0.1kPa以下の真空乾燥機中に入れて4時間乾燥した時の質量(g)を示す。)
なお、PVA系重合体、グリセリンなどの多価アルコール(可塑剤)、界面活性剤および水を用いて調製した製膜原液から形成されるフィルムでは、前記した「温度50℃、圧力0.1kPa以下で4時間」という条件下で乾燥したときには主として水のみが揮発し、水以外の他の成分のほとんどは揮発せずにフィルム中に残留するので、フィルムの揮発分率は、フィルム中に含まれている水分量(水分率)を測定することにより求めることができる。 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. Is more preferably 30% by mass or less, more preferably 29% by mass or less, still more preferably 28% by mass or less, and particularly preferably 27% by mass or less.
Here, “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 mass (g) when put in the machine and dried for 4 hours is shown.)
In addition, in the film formed from the film forming stock solution prepared using polyhydric alcohol (plasticizer), surfactant, and water, such as PVA polymer and glycerin, the above-mentioned “temperature 50 ° C., pressure 0.1 kPa or less” When dried under the condition of “4 hours”, only water is volatilized, and most of the other components other than water are not volatilized and remain in the film. Therefore, the volatile content of the film is included in the film. It can be determined by measuring the amount of water (water content).
以下の実施例および比較例において、製膜原液の揮発分率(水分率)、フィルムの揮発分率(水分率)、乾燥ロール表面温度、水中寸法変化量、および偏光フィルムの光学性能は、以下の方法により測定または評価した。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
In the following examples and comparative examples, 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.
ガラス製の耐熱容器に製膜原液を約10g採取して、耐熱容器を密閉し、風袋を除いた製膜原液の質量Wa(g)を小数点以下4桁まで測定した。続いて、その製膜原液を耐熱容器ごと温度105℃の電熱乾燥機中に入れて、耐熱容器のふたを開けた状態で16時間乾燥した後、風袋を除いた製膜原液の質量Wb(g)を小数点以下4桁まで測定した。得られた質量WaおよびWbから、上記の式(I)によって、製膜原液の揮発分率(質量%)を求めた。 (1) Volatile content (water content) of the stock solution
About 10 g of the film-forming stock solution was collected in a glass heat-resistant container, the heat-resistant container was sealed, and the mass Wa (g) of the film-forming stock solution excluding the tare was measured to 4 digits after the decimal point. Subsequently, the film-forming stock solution was put together with a heat-resistant container in an electric heat dryer having a temperature of 105 ° C., dried for 16 hours with the lid of the heat-resistant container being opened, and then the mass Wb (g ) Was measured to 4 digits after the decimal point. From the obtained masses Wa and Wb, the volatile fraction (mass%) of the film-forming stock solution was determined by the above formula (I).
隣接する乾燥ロールの間で、乾燥ロールの間を通過するフィルムの幅方向(TD)の中央部からカットした約5gのフィルムサンプル、または得られたPVAフィルムの幅方向(TD)の中央部からカットした約5gのフィルムサンプルについて、これをガラス製の耐熱容器に入れて密閉し、風袋を除いたフィルムの質量Wc(g)を小数点以下4桁まで測定した。続いて、そのフィルムを耐熱容器ごと温度50℃、圧力0.1kPa以下の真空乾燥機中に入れて、耐熱容器のふたを開けた状態で4時間乾燥した後、風袋を除いたフィルムの質量Wd(g)を小数点以下4桁まで測定した。得られた質量WcおよびWdから、上記の式(II)によって、フィルムの揮発分率M(質量%)を求めた。 (2) Film volatile content (water content)
Between adjacent drying rolls, about 5 g of a film sample cut from the central part in the width direction (TD) of the film passing between the drying rolls, or from the central part in the width direction (TD) of the obtained PVA film About 5 g of the cut film sample, this was put in a glass heat-resistant container and sealed, and the mass Wc (g) of the film excluding the tare was measured to 4 digits after the decimal point. Subsequently, the film was put together with the heat-resistant container in a vacuum dryer at a temperature of 50 ° C. and a pressure of 0.1 kPa or less, dried for 4 hours with the lid of the heat-resistant container opened, and then the mass Wd of the film excluding the tare (G) was measured to 4 digits after the decimal point. From the obtained masses Wc and Wd, the volatile fraction M (% by mass) of the film was determined by the above formula (II).
非接触式の表面温度計で、乾燥ロールの表面温度(℃)を小数点以下1桁まで測定した。 (3) Drying roll surface temperature The surface temperature (° C) of the drying roll was measured to one decimal place with a non-contact type surface thermometer.
PVAフィルムの幅方向(TD)の任意の直線上において、中央部(1箇所)および両端部から0.3m離れた地点(2箇所)の合計3箇所で、それぞれ、幅方向(TD)4cm×長さ方向(MD)27cmの矩形のサンプルを切り出した。ここで、各サンプルの重心が上記直線上の各位置にあるようにした。そして各サンプルの27cm長の両端から1cmずつ内側に油性マジック(線の太さが0.3mm)で標線を入れた。両端の標線から外側の部分を市販のクリップ(チャック幅4cm、質量7.8g(水中での重量7.3g))で挟み、一方のクリップは番線などの棒状冶具で固定した。標線間距離が250mmであることを確認後、円筒状の透明な水槽に蓄えた30℃に調温した純水に、クリップが付いたサンプルをサンプル全体が水中に入るように、速やかにサンプル長辺を垂直(鉛直)に浸漬した。浸漬直後に水槽上部に棒状冶具を引っ掛けてサンプル長辺を垂直(鉛直)になるように固定した。その後、金属製の物差しを水中に浸漬して、浸漬から5分後に標線間距離を測定した。0.5mm刻みで読み取った当該測定値から元の標線間距離(250mm)を引いて伸び量(中央部の水中寸法変化量:W(mm)、および両端部から0.3mの地点の水中寸法変化量:W0(mm))を算出した。ここで、W0(mm)は両端部から0.3m離れた地点のサンプルから得られた2つの伸び量を平均して求めた。 (4) Underwater dimensional change amount On an arbitrary straight line in the width direction (TD) of the PVA film, at a total of three places, a central part (one place) and a point (two places) 0.3 m away from both ends, A rectangular sample of 4 cm in the width direction (TD) × 27 cm in the length direction (MD) was cut out. Here, the center of gravity of each sample was set at each position on the straight line. Each sample was marked with a marker line with oily magic (line thickness: 0.3 mm) 1 cm inside from both ends of 27 cm length. 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. After confirming that the distance between the marked lines is 250 mm, 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. Immediately after the immersion, 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. 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)) was calculated. Here, W 0 (mm) was obtained by averaging two elongations obtained from a sample at a point 0.3 m away from both ends.
(i)透過率43.5%における偏光度
下記の実施例および比較例に記載するように、各実施例または比較例において、2段目延伸時におけるヨウ素/ヨウ化カリウム/ホウ酸水溶液中のヨウ素濃度を変更して製造した5種類の偏光フィルムのそれぞれについて、下記の方法で単体透過率(Y)および偏光度(V)を求め、各実施例または比較例ごとに、単体透過率(Y)を横軸、偏光度(V)を縦軸として5つの点をグラフにプロットして近似曲線を作成し、当該近似曲線から単体透過率(Y)が43.5%であるときの偏光度(V)の値を求め、これを「透過率43.5%における偏光度」とした。 (5) Optical performance of polarizing film (i) Polarization degree at transmittance of 43.5% As described in the following Examples and Comparative Examples, in each Example or Comparative Example, 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”.
偏光フィルムの幅方向の中央部から、4cm(一軸延伸の延伸方向)×4cm(一軸延伸の延伸方向に対して垂直の方向)の正方形のサンプルを2枚採取した。これらのサンプルについて、日本分光株式会社製の分光光度計「V-7100」を用いて、その光の透過率を測定した。なお測定に際しては、JIS Z 8722(物体色の測定方法)に準拠し、C光源を用いて、2度視野の可視光領域の視感度補正を行った。1枚のサンプルについて、一軸延伸の延伸方向に対して+45度傾けた場合の光の透過率と、一軸延伸の延伸方向に対して-45度傾けた場合の光の透過率とを測定して、それらの平均値(Y1)(%)を求めた。もう1枚のサンプルについても、同様に、+45度傾けた場合の光の透過率と-45度傾けた場合の光の透過率とを測定して、それらの平均値(Y2)(%)を求めた。そして、求めたY1とY2とを以下の式(III)で平均してその偏光フィルムの単体透過率(Y)(%)とした。
単体透過率(Y)(%)=(Y1+Y2)/2 (III) << 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. Similarly, for the other sample, 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)
上記の「《1》単体透過率(Y)の測定法」において採取した2枚のサンプルを、それらの一軸延伸の延伸方向が平行になるように重ねた場合の光の透過率(Y∥)(%)、および、それらの一軸延伸の延伸方向が直交するように重ねた場合の光の透過率(Y⊥)(%)を測定した。透過率(Y∥)および(Y⊥)は、上記の「《1》単体透過率(Y)の測定法」と同様にして、一方のサンプルの一軸延伸の延伸方向に対して+45度傾けた場合の光の透過率と-45度傾けた場合の光の透過率との平均値として求めた。透過率(Y∥)および(Y⊥)から、以下の式(IV)に基づいてその偏光フィルムの偏光度(V)(%)を求めた。
偏光度(V)(%)={(Y∥-Y⊥)/(Y∥+Y⊥)}1/2×100 (IV) << 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)”. The average value of the light transmittance in this case and the light transmittance in the case of tilting by −45 degrees was obtained. From the transmittances (Y∥) and (Y そ の), the degree of polarization (V) (%) of the polarizing film was determined based on the following formula (IV).
Polarization degree (V) (%) = {(Y∥−Y⊥) / (Y∥ + Y⊥)} 1/2 × 100 (IV)
はじめに、下記の実施例および比較例に記載するように、各実施例または比較例において、2段目延伸時におけるヨウ素/ヨウ化カリウム/ホウ酸水溶液中のヨウ素濃度を変更して製造した5種類の偏光フィルムのそれぞれ(いずれも単体透過率(Y)が42~44%の範囲にあった)について、測定波長700nmでの吸光度(A)を次のようにして求めた。すなわち、日本分光株式会社製の分光光度計「V-7100」にグランテーラプリズムを取り付けて、光軸に直交する位置に偏光フィルムのサンプル1枚(上記の「(i)透過率43.5%における偏光度 《1》単体透過率(Y)の測定法」において各偏光フィルムについて採取した2枚のサンプルのうちの任意の1枚)を設置して、光源からプリズムを通って直線偏光となった測定波長380~780nmの光線を上記サンプルに透過させたときの波長700nmの光についての透過率を測定した。このとき、上記サンプルを光軸に直交する平面内で回転させて、透過率変化を測定し、透過率の最大値T0および透過率の最小値T90を求め、以下の式(V)からその偏光フィルムの測定波長700nmでの直交透過率Tcを算出した。
Tc=T0×T90/100 (V)
そして、当該直交透過率Tcを用いて以下の式(VI)からその偏光フィルムの測定波長700nmでの吸光度(A)を算出した。
A=2-logTc (VI)
次いで、上記の「(i)透過率43.5%における偏光度 《1》単体透過率(Y)の測定法」、および、測定波長700nmでの吸光度(A)の結果から、偏光フィルムの単体透過率(Y)を横軸、測定波長700nmでの吸光度(A)を縦軸として、上記の5種類の偏光フィルムに対応する5つの点をグラフにプロットして近似直線を作成し、当該近似直線から偏光フィルムの単体透過率(Y)が43.5%であるときの測定波長700nmでの吸光度(A)を求め、これを「透過率43.5%における測定波長700nmでの吸光度(A)」とした。 (Ii) Absorbance at a measurement wavelength of 700 nm at a transmittance of 43.5% (A)
First, as described in the following Examples and Comparative Examples, in each Example or Comparative Example, five types produced by changing the iodine concentration in the iodine / potassium iodide / boric acid aqueous solution at the time of second-stage stretching The absorbance (A) at a measurement wavelength of 700 nm was determined as follows for each of the polarizing films (each having a single transmittance (Y) in the range of 42 to 44%). In other words, 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. At this time, 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 orthogonal transmittance Tc of the polarizing film at a measurement wavelength of 700 nm was calculated.
Tc = T 0 × T 90/100 (V)
And the light absorbency (A) in the measurement wavelength 700nm of the polarizing film was computed from the following formula | equation (VI) using the said orthogonal transmittance | permeability Tc.
A = 2-logTc (VI)
Next, from the result of the above-mentioned “(i) Polarization degree at transmittance 43.5% << 1 >> Method for measuring single transmittance (Y)” and absorbance (A) at a measurement wavelength of 700 nm, the polarizing film alone Using the transmittance (Y) as the horizontal axis and the absorbance (A) at the measurement wavelength of 700 nm as the vertical axis, plot the five points corresponding to the above five types of polarizing films on a graph to create an approximate straight line. 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 ) ”.
以下の実施例または比較例で連続的に製造した偏光フィルムを、1枚の偏光板(単体透過率43.5%、偏光度99.9%)の上に完全なクロスニコル状態になるように設置して、輝度15000カンデラのバックライトを用いて、偏光フィルムの幅方向(TD)の中央部と端部との間の透過率のムラ(光学ムラ)を観察し、以下の基準で光学ムラを評価した。
○・・・中央部と両端部に透過率の差による明暗の差が見えず均一である。
×・・・中央部が両端部に対して明るくまたは暗く、濃淡差がある。 (Iii) 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.
(1)PVA系重合体フィルムの製造
ポリ酢酸ビニルをけん化することにより得られたPVA(けん化度99.9モル%、平均重合度2400)100質量部、グリセリン12質量部、ラウリン酸ジエタノールアミド0.1質量部および水からなる揮発分率66質量%の製膜原液を、Tダイから、回転軸が互いに平行な複数の乾燥ロールを備える製膜装置の第1乾燥ロール(表面温度90℃、周速(S1)10.0m/分)上に膜状に吐出し、第1乾燥ロール上で、第1乾燥ロール非接触面の全体に90℃の熱風を5m/秒の風速で吹き付けながら揮発分率18質量%になるまで乾燥し、次いで第1乾燥ロールから剥離して、フィルムの任意の部分における表面と裏面とが各乾燥ロールに交互に接触するように第2乾燥ロール以降の乾燥を行った。ここで、第2乾燥ロール以降の乾燥ロールとしては、中央部の外径が両端部の外径より2mm大きく、中央部から端部へ曲線的に径が減少している乾燥ロール(クラウンロール)を16本用い、これらの乾燥ロールの表面温度は75℃とし、但し最後の2本については、その表面温度を105℃にして熱処理ロールとした。また、最終乾燥ロール(第17乾燥ロール(熱処理ロール))の周速(S17)は9.8m/分とした。その後、ロール状に巻き取ってPVAフィルム(厚み60μm、幅4m、揮発分率(水分率)3質量%、中央部の水中寸法変化量(W)58mm、両端部から0.3mの地点の水中寸法変化量(平均値;W0)61mm)を得た。
この実施例1では、第1乾燥ロールの周速(S1)に対する第2乾燥ロールの周速(S2)の比(S2/S1)を1.025とし、第1乾燥ロールの周速(S1)に対する最終乾燥ロールの周速(S17)の比(S17/S1)を0.980とした。上記の製膜条件を下記の表1に示す。 Example 1
(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. is blown on the entire surface of the first drying roll non-contact on the first drying roll at a wind speed of 5 m / second Dry until the volatile content is 18% by mass, then peel from the first drying roll, and dry after the second drying roll so that the front and back surfaces of any part of the film are alternately in contact with each drying roll. The Was Tsu. Here, as a drying roll after the second drying roll, a drying roll (crown roll) in which the outer diameter of the central portion is 2 mm larger than the outer diameters of both end portions, and the diameter decreases in a curved manner from the central portion to the end portion. 16 were used, and the surface temperature of these drying rolls was 75 ° C. However, the last two rolls were heat-treated rolls having a surface temperature of 105 ° C. 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 μm, 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.
In 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.
(i)上記(1)で得られたPVAフィルムの幅方向(TD)の中央部から採取した試験片を、温度30℃の水中に浸漬している間に元の長さの1.5倍に長さ方向(MD)に一軸延伸(1段目延伸)した後、ヨウ素を0.028質量%およびヨウ化カリウムを1質量%およびホウ酸を1質量%の濃度で含有する温度30℃のヨウ素/ヨウ化カリウム/ホウ酸水溶液中に浸漬している間に元の長さの2.25倍まで長さ方向(MD)に一軸延伸(2段目延伸)し、次いでホウ酸を4質量%およびヨウ化カリウムを4質量%の濃度で含有する温度53℃のホウ酸/ヨウ化カリウム水溶液中に浸漬している間に元の長さの5.8倍まで長さ方向(MD)に一軸延伸(3段目延伸)し、その後60℃の乾燥機で乾燥して偏光フィルムを製造した。
(ii)上記(i)において、2段目延伸時の温度30℃のヨウ素/ヨウ化カリウム/ホウ酸水溶液中のヨウ素の濃度を0.028質量%から0.03質量%に変えたこと以外は上記(i)と同じ操作を行って、偏光フィルムを製造した。
(iii)上記(i)において、2段目延伸時の温度30℃のヨウ素/ヨウ化カリウム/ホウ酸水溶液中のヨウ素の濃度を0.028質量%から0.032質量%に変えたこと以外は上記(i)と同じ操作を行って、偏光フィルムを製造した。
(iv)上記(i)において、2段目延伸時の温度30℃のヨウ素/ヨウ化カリウム/ホウ酸水溶液中のヨウ素の濃度を0.028質量%から0.034質量%に変えたこと以外は上記(i)と同じ操作を行って、偏光フィルムを製造した。
(v)上記(i)において、2段目延伸時の温度30℃のヨウ素/ヨウ化カリウム/ホウ酸水溶液中のヨウ素の濃度を0.028質量%から0.036質量%に変えたこと以外は上記(i)と同じ操作を行って、偏光フィルムを製造した。
(vi)上記(i)~(v)で製造した5種類の偏光フィルムを用いて「(5)偏光フィルムの光学性能 (i)透過率43.5%における偏光度」の項目において上記した方法により当該偏光度を測定したところ、99.9%であった。また、「(5)偏光フィルムの光学性能 (ii)透過率43.5%における測定波長700nmでの吸光度(A)」の項目において上記した方法により当該吸光度(A)を測定したところ、2.9であった。 (2) Manufacture of polarizing film (i) While the test piece collected from the central part in the width direction (TD) of the PVA film obtained in (1) above was immersed in water at a temperature of 30 ° C. After uniaxial stretching (first-stage stretching) in the length direction (MD) to 1.5 times the length, 0.028% by mass of iodine, 1% by mass of potassium iodide, and 1% by mass of boric acid Is uniaxially stretched (MD) in the length direction (MD) up to 2.25 times its original length while immersed in an aqueous solution of iodine / potassium iodide / boric acid at a temperature of 30 ° C. Then up to 5.8 times the original length while immersed in a boric acid / potassium iodide aqueous solution at a temperature of 53 ° C. containing 4% by weight boric acid and 4% by weight potassium iodide. Uniaxially stretched in the length direction (MD) (third-stage stretching) and then dried in a dryer at 60 ° C. Film was produced.
(Ii) In (i) above, except that the concentration of iodine in the iodine / potassium iodide / boric acid aqueous solution at a temperature of 30 ° C. at the second stage stretching was changed from 0.028% by mass to 0.03% by mass. Performed the same operation as the above (i) to produce a polarizing film.
(Iii) In the above (i), except that the concentration of iodine in the iodine / potassium iodide / boric acid aqueous solution at a temperature of 30 ° C. at the second stage stretching is changed from 0.028 mass% to 0.032 mass%. Performed the same operation as the above (i) to produce a polarizing film.
(Iv) In the above (i), except that the concentration of iodine in the iodine / potassium iodide / boric acid aqueous solution at a temperature of 30 ° C. at the second stage stretching is changed from 0.028 mass% to 0.034 mass%. Performed the same operation as the above (i) to produce a polarizing film.
(V) In (i) above, except that the concentration of iodine in the iodine / potassium iodide / boric acid aqueous solution at a temperature of 30 ° C. during the second stage stretching was changed from 0.028 mass% to 0.036 mass%. Performed the same operation as the above (i) to produce a polarizing film.
(Vi) Using the five types of polarizing films produced in (i) to (v) above, the method described above in the section of “(5) Optical performance of polarizing film (i) Polarization degree at 43.5% transmittance” The degree of polarization was measured by means of 99.9%. Further, when the absorbance (A) was measured by the method described above in the section of “(5) Optical performance of polarizing film (ii) Absorbance at a measurement wavelength of 700 nm at a transmittance of 43.5% (A)”, 2. It was 9.
これらの結果を下記の表1に示す。 Furthermore, for the evaluation of optical unevenness, a polarizing film was continuously produced using the PVA film obtained above under the same conditions as in (i) above, and “(5) Optical performance of polarizing film (iii) Optical When the optical unevenness was evaluated by the above-described method in the item of “unevenness”, the result was ○.
These results are shown in Table 1 below.
実施例1において、PVAフィルムの製膜条件(製膜装置を含む)を下記の表1に記載するように変更したこと以外は実施例1と同様にしてPVAフィルムおよび偏光フィルムを製造した。
製造されたPVAフィルムと偏光フィルムについて、実施例1と同様に各測定または評価を行った。結果を表1に示す。 << Examples 2 and 3, Comparative Examples 1 and 2 >>
In 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.
Claims (8)
- ポリビニルアルコール系重合体フィルムの幅方向(長さ方向に対し直角方向)の直線上において、中央部の水中寸法変化量をW(mm)、両端部から0.3mの地点の水中寸法変化量(平均値)をW0(mm)とする(ここで水中寸法変化量は、ポリビニルアルコール系重合体フィルムのサンプルを30℃の純水に5分間浸漬したときの、浸漬前の長さ方向250mmの部分における長さ方向の伸び量である)とき、0.5mm≦W0-W≦5mmを満足するポリビニルアルコール系重合体フィルム。 On the straight line in the width direction (perpendicular to the length direction) of the polyvinyl alcohol polymer film, the amount of dimensional change in water at the center is W (mm), and the amount of dimensional change in water at a point 0.3 m from both ends ( (Average value) is set to W 0 (mm) (here, the amount of dimensional change in water is when the sample of the polyvinyl alcohol polymer film is immersed in pure water at 30 ° C. for 5 minutes in the length direction of 250 mm before immersion). Polyvinyl alcohol polymer film satisfying 0.5 mm ≦ W 0 -W ≦ 5 mm.
- (W+W0)/2が50~65mmである、請求項1に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to claim 1, wherein (W + W 0 ) / 2 is 50 to 65 mm.
- Wが50~60mmであり、W0が55~65mmである、請求項1または2に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to claim 1 or 2, wherein W is 50 to 60 mm and W 0 is 55 to 65 mm.
- 揮発分率が1~5質量%である、請求項1~3のいずれか1項に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to any one of claims 1 to 3, having a volatile content of 1 to 5 mass%.
- 幅が2~7.5mである、請求項1~4のいずれか1項に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to any one of claims 1 to 4, wherein the width is 2 to 7.5 m.
- 偏光フィルム製造用原反フィルムである、請求項1~5のいずれか1項に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to any one of claims 1 to 5, which is a raw film for producing a polarizing film.
- 回転軸が互いに平行な複数の乾燥ロールを備える製膜装置を使用し、当該製膜装置の第1乾燥ロール上にポリビニルアルコール系重合体を含む製膜原液を膜状に吐出して乾燥し、それに続く第2乾燥ロール以降の乾燥ロールで更に乾燥してポリビニルアルコール系重合体フィルムを製膜する際に、第2乾燥ロール以降の乾燥ロールのうちの少なくとも1つとして、中央部の外径が両端部の外径より0.5~3mm大きい乾燥ロールを用いる、ポリビニルアルコール系重合体フィルムの製造方法。 Using a film-forming apparatus comprising a plurality of drying rolls whose rotation axes are parallel to each other, a film-forming stock solution containing a polyvinyl alcohol polymer is discharged into a film on the first drying roll of the film-forming apparatus, and dried. When the polyvinyl alcohol polymer film is further dried by a subsequent drying roll after the second drying roll to form a polyvinyl alcohol polymer film, the outer diameter of the central portion is at least one of the second and subsequent drying rolls. A method for producing a polyvinyl alcohol polymer film, which uses a drying roll 0.5 to 3 mm larger than the outer diameter of both ends.
- 請求項6に記載のポリビニルアルコール系重合体フィルムから製造される偏光フィルム。 A polarizing film produced from the polyvinyl alcohol polymer film according to claim 6.
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US20210324159A1 (en) * | 2018-12-28 | 2021-10-21 | Kuraray Co., Ltd. | Water-soluble film and package |
WO2020138445A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Hydraulic transfer base film, and hydraulic transfer printing film |
JPWO2020138441A1 (en) * | 2018-12-28 | 2021-11-04 | 株式会社クラレ | Water-soluble film and packaging |
JPWO2020138445A1 (en) * | 2018-12-28 | 2021-11-11 | 株式会社クラレ | Base film for hydraulic transfer and printing film for hydraulic transfer |
WO2020138441A1 (en) * | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film and package |
JP7240423B2 (en) | 2018-12-28 | 2023-03-15 | 株式会社クラレ | Hydraulic transfer base film and Hydraulic transfer printing film |
KR20220113932A (en) | 2019-12-11 | 2022-08-17 | 주식회사 쿠라레 | Manufacturing method of polyvinyl alcohol film for optical use |
WO2022004537A1 (en) * | 2020-06-30 | 2022-01-06 | 株式会社クラレ | Polyvinyl alcohol film and polarizing film in which same is used |
WO2023074639A1 (en) * | 2021-10-25 | 2023-05-04 | 株式会社クラレ | Polyvinyl alcohol film |
Also Published As
Publication number | Publication date |
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TWI498611B (en) | 2015-09-01 |
JPWO2013146146A1 (en) | 2015-12-10 |
TW201516491A (en) | 2015-05-01 |
CN106226858A (en) | 2016-12-14 |
KR20130132665A (en) | 2013-12-04 |
TW201539068A (en) | 2015-10-16 |
KR101397899B1 (en) | 2014-05-20 |
CN104204046B (en) | 2017-06-23 |
TWI579604B (en) | 2017-04-21 |
KR20140130362A (en) | 2014-11-10 |
TWI564602B (en) | 2017-01-01 |
CN106226858B (en) | 2018-09-04 |
JP5390052B1 (en) | 2014-01-15 |
CN104204046A (en) | 2014-12-10 |
TW201344261A (en) | 2013-11-01 |
JP6030528B2 (en) | 2016-11-24 |
JP2014016649A (en) | 2014-01-30 |
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