WO2016084836A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2016084836A1 WO2016084836A1 PCT/JP2015/083042 JP2015083042W WO2016084836A1 WO 2016084836 A1 WO2016084836 A1 WO 2016084836A1 JP 2015083042 W JP2015083042 W JP 2015083042W WO 2016084836 A1 WO2016084836 A1 WO 2016084836A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- 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
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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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- 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
Definitions
- the present invention relates to a polyvinyl alcohol polymer film (hereinafter, “polyvinyl alcohol” may be abbreviated as “PVA”), a method for producing the same, and an optical film such as a polarizing film produced from the PVA polymer film. .
- PVA polyvinyl alcohol polymer film
- a polarizing plate having a light transmission and shielding function is an important component of a liquid crystal display (LCD) together with a liquid crystal having a light switching function.
- LCD liquid crystal display
- the field of application of this liquid crystal display device is also used in small devices such as calculators and wristwatches in the early days of development, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measurements used indoors and outdoors. It has been extended to a wide range of devices, especially for LCD monitors and LCD TVs.
- a polarizing plate is obtained by uniaxially stretching a PVA polymer film and then dyeing it with iodine or a dichroic dye, and then performing a fixing treatment with a boron compound after dyeing and uniaxially stretching the PVA polymer film.
- a protective film such as a cellulose triacetate film or an acetic acid / butyric acid cellulose film is produced on one side or both sides of the polarizing film obtained by producing a polarizing film by the method, a method of performing fixing treatment simultaneously with dyeing in any of the above methods It is manufactured by pasting together.
- Patent Document 1 A method of setting the speed of the drum located at the uppermost stream] to 0.8 to 1.3 is known (Patent Document 1).
- a stretched film such as a polarizing film that is hard to break when stretched and has an optical performance equal to or higher than that of a conventional product with good workability, high yield, low cost, and high productivity.
- a value ( ⁇ n (MD) Ave ) obtained by averaging the birefringence in the machine flow direction of the PVA polymer film in the thickness direction of the film and the birefringence in the width direction of the PVA polymer film A PVA polymer film is known in which a value ( ⁇ n (TD) Ave ) obtained by averaging the rate in the thickness direction of the film satisfies a specific relationship (see Patent Documents 2 and 3).
- JP 2001-315141 A International Publication No. 2012/132984 International Publication No. 2013/137056
- a method of stretching to a relatively high stretching ratio may be employed at the time of dyeing when producing the polarizing film.
- a relatively high temperature may also be adopted in main stretching called stretching.
- the PVA polymer films described in Patent Documents 1 to 3 have room for further improvement in that a high limit drawing ratio is expressed even in the above case.
- the PVA polymer films described in Patent Documents 1 to 3 have a problem that the film width is narrowed by stretching to a high magnification, and the finally obtained polarizing film area is reduced.
- the object of the present invention is that even when a method of stretching to a relatively high stretch ratio at the time of dyeing is employed or when a relatively high stretch temperature is employed, the limit stretch ratio is high and high without causing breakage.
- the film can be stretched at a magnification, and by suppressing the decrease in the film width during stretching, a stretched film such as a polarizing film can be produced with good workability, high yield, low cost, and high productivity.
- the objective of this invention is providing the method which can manufacture the PVA-type polymer film which has the above-mentioned outstanding characteristic smoothly and continuously with high productivity.
- the objective of this invention is providing optical films, such as a polarizing film manufactured from the said PVA-type polymer film.
- a stretched film such as a polarizing film having excellent optical performance can be produced with high yield, low cost and high productivity without interrupting the stretching operation.
- the value obtained by averaging the birefringence in the machine flow direction (length direction) of the PVA polymer film in the thickness direction of the film and the birefringence in the width direction of the PVA polymer film in the thickness direction of the film are thinner than the PVA polymer film that has been conventionally used in the production of polarizing films.
- the present inventors discharged the above-mentioned PVA polymer film having a high limit drawing ratio onto a first drying roll of a film forming apparatus including a plurality of drying rolls, as a film forming stock solution containing the PVA polymer. After that, the plurality of drying rolls are sequentially dried to form a film. At that time, the ratio of the peripheral speed of the final drying roll to the peripheral speed of the first drying roll is set to a specific range, and the volatile content ratio is specified. It was found that by making the shrinkage rate calculated from the film width of the PVA polymer film when the value reached a specific range, it can be produced smoothly and continuously with high productivity.
- each drying roll when the volatile fraction of the PVA polymer film is in a specific range is in a specific range. It is preferable that these average values are in a specific range, that the volatile fraction of the film-forming stock solution is in a specific range, and the peripheral speed of the first drying roll is specified in a specific range. It was found that it is preferable to make the range.
- the present inventors have further studied based on the above findings and completed the present invention.
- the present invention [1] A PVA polymer film characterized by satisfying the following formulas (I) and (II): ⁇ n (MD) Ave ⁇ 1.3 ⁇ 10 ⁇ 3 (I) ⁇ n (TD) Ave ⁇ 1.3 ⁇ 10 ⁇ 3 (II) [In the above formula, ⁇ n (MD) Ave represents a value obtained by averaging the birefringence in the machine flow direction of the PVA polymer film in the thickness direction of the film, and ⁇ n (TD) Ave represents the PVA polymer. A value obtained by averaging the birefringence in the width direction of the film in the thickness direction of the film is shown.
- the PVA polymer film of the present invention has a high limit stretch ratio even when a method of stretching to a relatively high stretch ratio at the time of dyeing is employed or when a relatively high stretch temperature is employed. Therefore, when producing a stretched film, even if it is uniaxially stretched at a high magnification, the film is not easily broken, and thus a stretched film such as a polarizing film can be produced at a high yield without interrupting the stretching operation. It can be manufactured with high cost and high productivity.
- the PVA polymer film of the present invention has a thickness of about 10 to 65 ⁇ m, which is thinner than the thickness of the PVA polymer film conventionally used for producing a polarizing film or the like.
- FIG. 1 is a schematic view showing a method for collecting a sample when measuring ⁇ n (MD) Ave of a PVA polymer film.
- FIG. 2 is a schematic view showing a method of collecting a sample when measuring ⁇ n (TD) Ave of a PVA polymer film.
- the present invention is described in detail below.
- a transparent film manufactured using a transparent polymer such as a PVA polymer
- the polymer chain is oriented in the flow direction (machine flow direction: length direction) due to plastic deformation or strain due to shear stress.
- the polarization directions of the constituent atomic groups are macroscopically aligned, thereby causing the birefringence unique to the polymer.
- the birefringence [ ⁇ n (MD)] in the machine flow direction in the PVA polymer film is obtained from the following formula [i]
- the birefringence [ ⁇ n (TD)] in the width direction is given by the following formula [ii]. It is requested from.
- ⁇ n (MD) nMD ⁇ nz [i]
- ⁇ n (TD) nTD ⁇ nz [ii] [Where nMD is the refractive index in the machine flow direction (length direction) of the film, nTD is the refractive index in the width direction of the film, and nz is the refractive index in the thickness direction of the film. ]
- the PVA polymer film of the present invention is different from conventional PVA polymer films in that the following formulas (I) and (II) are satisfied.
- ⁇ n (MD) Ave ⁇ 1.3 ⁇ 10 ⁇ 3 (I)
- ⁇ n (TD) Ave ⁇ 1.3 ⁇ 10 ⁇ 3 (II)
- ⁇ n (MD) Ave represents a value obtained by averaging the birefringence in the machine flow direction of the PVA polymer film in the thickness direction of the film
- ⁇ n (TD) Ave represents the PVA polymer. A value obtained by averaging the birefringence in the width direction of the film in the thickness direction of the film is shown.
- the machine flow direction of the PVA polymer film (line when continuously forming the PVA polymer film) Direction) [hereinafter referred to as “length direction (MD)” birefringence averaged in the thickness direction of the film, “ ⁇ n (MD) Ave ”, and the width of the PVA polymer film “ ⁇ (TD) Ave ” which is a value obtained by averaging the birefringence of the direction (direction perpendicular to the length direction) [hereinafter sometimes referred to as “width direction (TD)”] in the thickness direction of the film, Each has the characteristic of being in the above range.
- the PVA polymer film of the present invention employs a method of stretching to a relatively high stretching ratio during dyeing or a relatively high stretching temperature by satisfying the above formulas (I) and (II). Even when the film is made, it has a high limit draw ratio, which makes it difficult for the film to break even if it is uniaxially stretched at a high magnification during the production of a stretched film such as a polarizing film. Thus, a stretched film having a thin film and excellent optical performance such as polarization performance can be produced with high yield and high productivity.
- the PVA polymer film of the present invention has a ⁇ n (MD) Ave of less than 1.3 ⁇ 10 ⁇ 3 from the viewpoints of the effects of the present invention being more remarkable and the ease of production thereof.
- a ⁇ n (MD) Ave of less than 1.3 ⁇ 10 ⁇ 3 from the viewpoints of the effects of the present invention being more remarkable and the ease of production thereof.
- it is 1.0 ⁇ 10 ⁇ 3 or less, more preferably 0.9 ⁇ 10 ⁇ 3 or less, particularly preferably 0.8 ⁇ 10 ⁇ 3 or less, Further, it is preferably 0.7 ⁇ 10 ⁇ 3 or more, and more preferably 0.75 ⁇ 10 ⁇ 3 or more.
- the PVA polymer film of the present invention has a ⁇ n (TD) Ave of 1.2 ⁇ 10 ⁇ 3 from the viewpoints of the remarkable effects of the present invention and the ease of production thereof. Is preferably 1.15 ⁇ 10 ⁇ 3 or less, more preferably 1.1 ⁇ 10 ⁇ 3 or less, and 1.0 ⁇ 10 ⁇ 3 or more. Is preferably 1.05 ⁇ 10 ⁇ 3 or more.
- the value of ⁇ n (MD) Ave and / or ⁇ n (TD) Ave often varies in the width direction (TD) of the film, and particularly ⁇ n (MD) at both ends in the width direction. Ave tends to be high, but at least the center of the width direction (TD) of the PVA polymer film should satisfy the formulas (I) and (II), and the width direction (TD) of the PVA polymer film It is preferable that the formulas (I) and (II) are satisfied in the entire region of 80% or more of the width direction (TD) centering on the center portion of. Both ends in the width direction (TD) of the PVA polymer film not satisfying the formulas (I) and (II) are removed by cutting before the PVA polymer film is stretched in the length direction (MD). Take).
- ⁇ n (MD) Ave of the PVA polymer film [value obtained by averaging the birefringence in the length direction (MD) of the PVA polymer film in the thickness direction of the film] and “ ⁇ n (TD) Ave ”
- the [value obtained by averaging the birefringence in the width direction (TD) of the PVA polymer film in the thickness direction of the film] can be measured by the following method.
- an average value of retardation is adopted with a line width of 300 pixels.
- V The value of retardation distribution in the thickness direction of the film obtained above is divided by the thickness measured with a microscope to obtain a birefringence ⁇ n (MD) distribution in the thickness direction of the film, and the thickness direction of the film is determined. The average value of the birefringence ⁇ n (MD) distribution is taken. The average value of the birefringence ⁇ n (MD) distribution in the thickness direction of each film obtained for the five slice pieces is further averaged to obtain “ ⁇ n (MD) Ave ”.
- ⁇ n (TD) Ave Measurement Method (Here, a method for measuring ⁇ n (TD) Ave at the center in the width direction (TD) of the PVA polymer film is exemplified.)
- MD ⁇ TD 10 mm ⁇ 2 mm from the center in the width direction (TD) of the film Is cut out, sandwiched on both sides with a 100 ⁇ m thick PET film, and further sandwiched between wooden frames and attached to a microtome apparatus.
- the strips collected in the above are parallel to the width direction (TD) of the strips at intervals of 10 ⁇ m.
- an average value of retardation is adopted with a line width of 300 pixels.
- V The value of retardation distribution in the thickness direction of the film obtained above is divided by the thickness measured with a microscope to obtain the birefringence ⁇ n (TD) distribution in the thickness direction of the film, and the thickness direction of the film is determined. The average value of the birefringence ⁇ n (TD) distribution is taken. The average value of the birefringence ⁇ n (TD) distribution in the thickness direction of each film obtained for five slice pieces is further averaged to obtain “ ⁇ n (TD) Ave ”.
- the thickness of the PVA polymer film of the present invention can be in the range of 5 to 150 ⁇ m, but is preferably 10 to 65 ⁇ m when used as a raw film for producing a polarizing film.
- the PVA polymer film of the present invention has a high limit stretch ratio even when a method of stretching to a relatively high stretch ratio at the time of dyeing is employed or when a relatively high stretch temperature is employed.
- the film thickness is 10 to 65 ⁇ m, which is thinner than the PVA polymer film having a thickness of about 75 ⁇ m, which is often used as a raw film for producing a polarizing film, the film does not break.
- the thickness of the stretched film can be made thinner than before, and It is possible to shorten the drying time for forming a film, it is possible to improve the production rate of the polarizing film.
- the thickness of the PVA polymer film is more preferably 60 ⁇ m or less, further preferably 50 ⁇ m or less, and may be 40 ⁇ m or less, and further 30 ⁇ m or less.
- the thickness of the PVA polymer film is 15 ⁇ m or more. Is more preferably 18 ⁇ m or more, and particularly preferably 20 ⁇ m or more.
- the width of the PVA polymer film of the present invention is not particularly limited. However, since liquid crystal televisions and monitors have recently become larger, the width is preferably 2 m or more so that they can be used effectively. It is more preferably 3 m or more, and further preferably 4 m or more. Moreover, when manufacturing a polarizing plate with a realistic production machine, if the width of the film is too large, uniform uniaxial stretching may be difficult. Therefore, the width of the PVA polymer film may be 8 m or less. preferable.
- the mass swelling degree of the PVA polymer film of the present invention is preferably 180 to 250%, more preferably 185 to 240%, still more preferably 190 to 230%. If the mass swelling degree of the PVA polymer film is too low, it tends to be difficult to stretch and it becomes difficult to produce a stretched film having excellent optical performance. On the other hand, if the mass swelling degree is too high, Process passability may deteriorate, or a highly durable polarizing film may not be obtained.
- the mass swelling degree here is a value obtained by dividing the mass when the PVA polymer film is immersed in distilled water at 30 ° C. for 30 minutes by the mass after drying at 105 ° C. for 16 hours after the immersion. It can be measured by the method described in the following examples.
- the PVA polymer for forming the PVA polymer film of the present invention for example, PVA obtained by saponifying polyvinyl ester obtained by polymerizing vinyl ester, and a comonomer is graft copolymerized on the main chain of PVA.
- Modified PVA polymer modified PVA polymer produced by saponification of modified polyvinyl ester copolymerized with vinyl ester and comonomer, some of hydroxyl groups of unmodified PVA or modified PVA polymer are formalin, butyraldehyde And so-called polyvinyl acetal resins crosslinked with aldehydes such as benzaldehyde.
- the PVA polymer forming the PVA polymer film of the present invention is a modified PVA polymer
- the amount of modification in the PVA polymer is preferably 15 mol% or less, preferably 5 mol% or less. It is more preferable.
- vinyl ester used for the production of the PVA polymer examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valelate, vinyl pivalate, vinyl laurate, vinyl stearate, vinyl benzoate. And vinyl versatate. 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 ( For example, an acrylic ester 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-methacryl
- the average degree of polymerization of the PVA polymer forming the PVA polymer film of the present invention is preferably 1000 or more, more preferably 1500 or more, and more preferably 2000 or more, from the viewpoint of the polarizing performance and durability of the obtained polarizing film. Further preferred.
- the upper limit of the average degree of polymerization of the PVA polymer 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 of the present invention is preferably 95.0 mol% or more, and 98.0 mol% or more from the viewpoint of the polarizing performance and durability of the obtained polarizing film. Is more preferably 99.0 mol% or more, most preferably 99.3 mol% or more.
- 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 production method of the PVA polymer film of the present invention is not particularly limited, and any method may be used as long as it can produce a PVA polymer film satisfying the above-described formulas (I) and (II).
- the PVA polymer film of the present invention is (A) A part in which 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 discharged into a film on the first drying roll of the film forming apparatus.
- a film forming stock solution containing a PVA polymer film is prepared by mixing a PVA polymer with a liquid medium to form a solution, or by melting a PVA polymer pellet containing the liquid medium or the like into a melt. can do.
- the dissolution of the PVA polymer in the liquid medium and the melting of the PVA polymer pellets including the liquid medium can be performed using a stirring mixer, a melt extruder, or the like.
- the liquid medium used in this case include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylenediamine, diethylenetriamine, and the like. These liquid media can be used alone or in combination. More than one species can be used in combination. Among these, water, dimethyl sulfoxide, or a mixture of both are preferably used, and water is more preferably used.
- a plasticizer is added to the film-forming stock solution from the viewpoints of accelerating dissolution and melting of the PVA polymer in a liquid medium, improving process passability during film production, and improving the stretchability of the resulting PVA polymer film. It is preferable.
- 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 can be used individually or in combination of 2 or more types. Among these, one or more of glycerin, diglycerin and ethylene glycol are preferably used 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 exceeds 30 parts by mass with respect to 100 parts by mass of the PVA polymer, the resulting PVA polymer film may become too soft and handleability may deteriorate.
- 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.
- an anionic surfactant for example, a carboxylic acid type such as potassium laurate, a sulfate type such as octyl sulfate, and a sulfonic acid type anionic surfactant such as dodecylbenzene sulfonate are suitable.
- nonionic surfactants include alkyl ether types such as polyoxyethylene oleyl ether, alkylphenyl ether types such as polyoxyethylene octylphenyl ether, alkyl ester types such as polyoxyethylene laurate, 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
- An allyl phenyl ether type nonionic surfactant such as polyoxyalkylene allyl phenyl ether is preferred.
- These surfactants can 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. When the amount is less than 0.01 parts by mass, the effect of improving the film-forming property and the peelability may be difficult to appear. On the other hand, when the amount is more than 1 part by mass, the surfactant elutes on the film surface and causes blocking. , The handleability may be reduced.
- the raw material for film formation is various additives such as stabilizers (for example, antioxidants, ultraviolet absorbers, heat stabilizers, etc.), compatibilizers as long as the properties of the PVA polymer film of the present invention are not impaired. Further, it may contain an antiblocking agent, a flame retardant, an antistatic agent, a lubricant, a dispersing agent, a fluidizing agent, an antibacterial agent and the like. These additives can be used alone or in combination of two or more.
- stabilizers for example, antioxidants, ultraviolet absorbers, heat stabilizers, etc.
- compatibilizers as long as the properties of the PVA polymer film of the present invention are not impaired.
- it may contain an antiblocking agent, a flame retardant, an antistatic agent, a lubricant, a dispersing agent, a fluidizing agent, an antibacterial agent and the like.
- the volatile fraction of the film-forming stock solution used for the production of the PVA polymer film is preferably 60 to 75% by mass, and more preferably 65 to 70% by mass. If the volatile fraction of the film-forming stock solution is less than 60% by mass, the viscosity of the film-forming stock solution becomes high, making filtration and defoaming difficult, and film-forming itself may be difficult. On the other hand, when the volatile fraction of the film-forming stock solution is larger than 75% by mass, 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 refers to the volatile fraction determined by the following formula [iii].
- Volatile fraction (% by mass) of the film-forming stock solution ⁇ (W a ⁇ W b ) / W a ⁇ ⁇ 100 [iii]
- W a represents the mass (g) of the film-forming stock solution
- W b represents the mass (g) after drying the film-forming stock solution of W a (g) for 16 hours in an electrothermal dryer at 105 ° C.
- the number of drying rolls is preferably 3 or more, more preferably 4 or more. More preferably, the number is 5 to 30.
- the plurality of drying rolls are preferably formed of a metal such as nickel, chromium, copper, iron, stainless steel, and the like, and in particular, the roll surface is hardly corroded and is formed of a metallic material having a specular gloss. It is more preferable.
- 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.
- the roll surface temperature of each drying roll in the plurality of drying rolls is preferably 65 ° C. or higher, more preferably 75 ° C. or higher, and still more preferably 85 ° C. or higher. Further, the roll surface temperature of each drying roll is preferably 90 to 130 ° C., preferably 100 to 120 ° C. with respect to the roll surface temperature of the drying roll that can be used as a heat treatment roll in the final step or a step close thereto. However, the roll surface temperature of the other drying rolls is preferably 100 ° C. or lower.
- the film forming apparatus used in the above manufacturing method may have a hot air oven type hot air drying apparatus, a heat treatment apparatus, a humidity control apparatus, etc., if necessary, following a plurality of drying rolls.
- a film-forming stock solution containing a PVA polymer on the first drying roll of the film-forming apparatus into a film shape
- a T-type slit die, a hopper plate, an I-die, a lip coater die, etc. are known.
- the film-forming stock solution containing the PVA polymer is discharged (cast) in the form of a film onto the first drying roll using the film-like discharge device (film-like casting device).
- the film-forming stock solution containing the PVA polymer discharged in the form of a film on the first drying roll is dried on the first drying roll, and the volatile fraction of the PVA polymer film is preferably 16 to 30% by mass, More preferably 17 to 29% by mass, and still more preferably 18 to 28% by mass, when peeling from the first drying roll.
- the volatile content rate of the PVA polymer film at the time of peeling from the first drying roll is not less than the above lower limit, it is possible to suppress the ⁇ n (MD) Ave value from becoming too large.
- the volatile content ratio of the PVA polymer film when peeling from the first drying roll is too high, peeling from the first drying roll tends to be difficult, and in some cases, breakage or unevenness occurs. It may be easy to do.
- the volatile fraction of the PVA polymer film or PVA polymer film in the present specification refers to the volatile fraction determined by the following formula [iv].
- a (mass%) ⁇ (W c ⁇ W d ) / W c ⁇ ⁇ 100 [iv]
- W c is the mass (g) of the sample taken from the PVA polymer film or PVA polymer film.
- W d represents the mass (g) when the sample W c (g) is placed in a vacuum dryer at a temperature of 50 ° C. and a pressure of 0.1 kPa or less and dried for 4 hours.
- a polyhydric alcohol (plasticizer) such as glycerin
- glycerin a surfactant
- water When dried under the conditions of “50 ° C., pressure of 0.1 kPa or less for 4 hours”, only water is volatilized, and most of the other components other than water are not volatilized, and PVA polymer film or PVA polymer film.
- the volatile fraction of the PVA polymer film or PVA polymer film is determined by measuring the amount of water (moisture content) contained in the PVA polymer film or PVA polymer film. It can ask for.
- the roll surface temperature of the first drying roll is preferably 80 to 120 ° C. from the viewpoint of uniform drying property, drying speed, etc., and the surface temperature is 85 ° C. or more. More preferably, it is 90 degreeC or more, It is more preferable that it is 105 degreeC or less, It is still more preferable that it is 99 degreeC or less. If the surface temperature of the first drying roll exceeds 120 ° C., the film tends to foam, whereas if it is less than 80 ° C., the drying on the first drying roll tends to be insufficient, which causes the peeling failure. It is easy to become.
- the peripheral speed (S 1 ) of the first drying roll is uniform drying, drying speed, productivity of the PVA polymer film, etc., as well as easier production of the PVA polymer film of the present invention.
- the peripheral speed (S 1 ) is preferably 10 m / min or more, more preferably 12 m / min or more, and 23 m / min or less. More preferably, it is 22 m / min or less.
- productivity decreases and the birefringence tends to increase.
- the peripheral speed (S 1 ) of the first drying roll exceeds 25 m / min, drying on the first drying roll tends to be insufficient.
- the partial drying on the first drying roll of the film-forming stock solution containing the PVA polymer discharged in the form of a film may be performed only by the heat from the first drying roll. 1 Drying by blowing hot air to the film surface not in contact with the drying roll (hereinafter sometimes referred to as “first drying roll non-contact surface”) and applying heat from both sides of the PVA polymer film, It is preferable from the viewpoints of uniform drying property, drying speed and the like.
- first drying roll non-contact surface the hot air with a wind speed of 1 to 10 m / sec is applied to the entire area of the first dry roll non-contact surface.
- the temperature of the hot air blown to the non-contact surface of the first drying roll of the PVA polymer film is preferably 50 to 150 ° C., and preferably 70 to 120 ° C. from the viewpoints of drying efficiency and drying uniformity. More preferably, it is 80 to 95 ° C.
- the dew point temperature of the hot air blown to the non-contact surface of the first drying roll of the PVA polymer film is preferably 10 to 15 ° C. If the temperature of the hot air blown on the non-contact surface of the first drying roll of the PVA polymer film is too low, the drying efficiency, uniform drying properties, etc. are likely to be lowered, while if too high, foaming is likely to occur.
- the method for blowing hot air to the non-contact surface of the first dry roll of the PVA polymer film is not particularly limited, and hot air having a uniform wind speed and temperature is applied to the non-contact surface of the first dry roll of the PVA polymer film.
- Any of the methods that can be sprayed uniformly on the entire surface can be preferably employed, and among them, the nozzle method, the current plate method, or a combination thereof is preferably employed.
- the first drying roll non-contact surface of the PVA polymer film May be in a direction substantially along the circumferential shape (direction substantially along the circumference of the roll surface of the first drying roll) or in other directions.
- the PVA polymer film when the PVA polymer film is dried on the first drying roll, it is preferable to exhaust the volatile matter generated from the PVA polymer 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 cause wind speed spots and temperature spots of hot air sprayed on the non-contact surface of the first drying roll of the PVA polymer film.
- the PVA polymer film dried to a volatile content of 16 to 30% by mass on the first drying roll is preferably peeled off from the first drying roll, and this time, the first drying roll non-contact surface of the PVA polymer film It is preferable to dry with a 2nd drying roll facing a 2nd drying roll.
- 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 1.090, and 1.010 More preferably, it is ⁇ 1.080.
- the ratio (S 2 / S 1 ) is less than 1.005, the peeling point of the PVA polymer film from the first drying roll tends to be non-uniform, and the birefringence unevenness in the width direction tends to increase. .
- the ratio (S 2 / S 1 ) exceeds 1.090, it tends to be difficult to satisfy the ratio (S L / S 1 ) described later.
- the roll surface temperature of the second drying roll is preferably 65 to 100 ° C., and preferably 75 to 98 ° C. from the viewpoint of uniform drying property, drying speed, and the like. More preferably, the temperature is 85 to 96 ° C.
- the PVA polymer film dried by the second drying roll is peeled from the second drying roll, and the third drying roll, the fourth drying roll, and the fifth drying are selected according to the number of drying rolls provided in the film forming apparatus.
- a plurality of drying rolls such as rolls,.
- the ratio (S L / S 1 ) of the peripheral speed (S L ) of the final drying roll to the peripheral speed (S 1 ) of the first drying roll is 0.955 to 0.980. Then, drying is performed while adjusting the tension applied to the PVA polymer film.
- the ratio (S L / S 1 ) in the above-described range, the birefringence in the length direction (MD) can be obtained without causing problems such as sagging or winding of the film in the drying process of the PVA polymer film.
- the value [ ⁇ n (MD) Ave ] obtained by averaging the rate in the thickness direction of the film and the value [ ⁇ n (TD) Ave ] obtained by averaging the birefringence in the width direction (TD) in the thickness direction of the film are the above formulas.
- the PVA polymer film of the present invention that satisfies (I) and (II) can be produced smoothly.
- the above-described ratio (S L / S 1 ) when producing the PVA polymer film is preferably 0.975 or less, more preferably 0.970 or less, and 0.960 or less. Is more preferable.
- the volatile content of the PVA polymer film is 20% by mass.
- the rate ((1-H 9 / H 20 ) ⁇ 100) (%) is set to 1% or more.
- [ ⁇ n (TD) Ave ] can smoothly produce the PVA polymer film of the present invention satisfying the above formulas (I) and (II).
- the shrinkage rate is preferably 1.5% or more, and more preferably 2% or more.
- the shrinkage rate is too high, film sagging and wrapping tend to occur and process passability tends to be inferior.
- the shrinkage rate is preferably 4% or less, and 3.5% or less. It is more preferable that it is 3% or less.
- the method of setting the shrinkage rate in the above range for example, a method of gradually narrowing the film width while holding the end of the PVA film between adjacent drying rolls, improving the slipping of the drying roll surface, etc. Examples thereof include a method of shrinking in the width direction on a drying roll, a method of relatively increasing the distance between adjacent drying rolls, and the like.
- the volatilization of the PVA polymer film from the drying roll when the volatile content of the PVA polymer film reaches 20% by mass.
- the surface temperature of each drying roll (all the drying rolls existing in the section) up to the drying roll when the fraction becomes 9% by mass it is preferable to set these average values to 85 ° C. or higher, and 87 ° C. More preferably, it is more preferably 90 ° C. or more, particularly preferably 93 ° C. or more, more preferably 100 ° C. or less, and even more preferably 95 ° C. or less.
- the drying roll when the volatile content of the PVA polymer film is 20% by mass and “the drying roll when the volatile content of the PVA polymer film is 20% by mass” It means the drying roll in which the PVA polymer film was located when the volatile fraction of the PVA polymer film was 20% by mass and 9% by mass, respectively.
- the PVA polymer film usually has a reduced volatile content on the drying roll.
- the upstream drying rolls were respectively designated as “drying rolls when the volatile fraction of the PVA polymer film was 20% by mass.
- the final drying roll or the drying roll close to the final and the final drying roll may be used as a heat treatment roll by increasing the surface temperature.
- the roll surface temperature is preferably 90 to 130 ° C, more preferably 100 to 120 ° C.
- the PVA polymer film subjected to the above-described drying treatment is subjected to heat treatment, humidity conditioning treatment, etc., if necessary, and finally wound into a roll with a predetermined length, whereby the PVA polymer film of the present invention is used. Can be obtained.
- the volatile content of the PVA polymer film finally obtained by the series of treatments described above is preferably in the range of 1 to 5% by mass, and more preferably in the range of 2 to 4% by mass.
- PVA-type polymer film of this invention has high limit stretch ratio, and even if it is uniaxially stretched by high magnification at the time of manufacture of a stretched film The film is less likely to break, and the stretched film with excellent optical performance can be produced with high yield and high productivity without causing interruption of the stretching work accompanying the breakage of the film. It is preferably used as an original film for producing an optical film such as a retardation film. Such an optical film can be produced, for example, by subjecting the PVA polymer film of the present invention to a treatment such as uniaxial stretching.
- a polarizing film from the PVA polymer film of the present invention it may be dyed and uniaxially stretched using the PVA polymer film of the present invention.
- Dyeing, uniaxial stretching, fixing treatment, drying treatment, and heat treatment may be performed 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.
- the PVA polymer film of the present invention has a high limit stretch ratio even when a method of stretching to a relatively high stretch ratio at the time of dyeing is adopted, the PVA polymer of the present invention is Such a case is particularly preferable.
- the draw ratio at the end of dyeing is preferably 3 times or more based on the length of the initial PVA polymer film, from the viewpoint of improving the polarization performance of the obtained polarizing film, and 3.4 times or more. More preferably, it is 3.5 times or more, more preferably 5 times or less.
- the uniaxial stretching may be performed by either a wet stretching method or a dry heat stretching method, but a wet stretching method is preferable from the viewpoint of the performance and quality stability of the obtained polarizing film.
- a 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.
- Uniaxial stretching is preferably performed in the length direction (MD) of the PVA polymer film.
- the stretching temperature in the uniaxial stretching treatment is not particularly limited, but in the case of the wet stretching method, it is preferably in the range of 30 to 90 ° C, more preferably in the range of 40 to 70 ° C, and 45 to The temperature is more preferably in the range of 65 ° C., and in the case of the dry heat stretching method, the temperature is preferably in the range of 50 to 180 ° C.
- 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.
- the thickness of the stretched film (polarizing film) is preferably 1 to 35 ⁇ m, particularly 5 to 25 ⁇ m.
- 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 decomposition of the dye.
- a polarizing plate can be obtained by attaching optically transparent protective films having mechanical strength to both surfaces or one surface of the polarizing film obtained as described above.
- 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-based pressure-sensitive adhesive and then being bonded to a glass substrate. When the polarizing plate is bonded to the glass substrate, a retardation film, a viewing angle improving film, a brightness improving film, or the like may be bonded simultaneously.
- the volatile fraction of the film-forming stock solution the volatile fraction (moisture content) of the PVA polymer film or PVA polymer film, and the physical properties of the PVA polymer film are as follows: Measured by the method.
- ⁇ n (MD) Ave of PVA polymer film ⁇ n (MD) Ave at the center in the width direction (TD) of the PVA polymer film is obtained by the method described above in the section “ ⁇ 1 >> ⁇ n (MD) Ave Measurement Method”, and this is obtained. ⁇ n (MD) Ave.
- ⁇ n (TD) Ave at the center in the width direction (TD) of the PVA polymer film is determined by the method described above in the section “ ⁇ 2 >> ⁇ n (TD) Ave Measurement Method”, and this is obtained. ⁇ n (TD) Ave.
- the film was uniaxially stretched in the length direction (MD) to the original length of 2.2 times the original length (stretching at the first stage) at a stretching speed of 12 cm / min, and 0.03% by mass of iodine. And at a stretching rate of 12 cm / min up to 3.5 times the original length while immersed in an aqueous solution of iodine / potassium iodide at a temperature of 30 ° C. containing 3% by weight of potassium iodide for 90 seconds.
- Neck-in degree of PVA polymer film From the limit draw ratio, polarizing film width, and pre-stretch film width (5 cm) obtained from the sample collected by the above method, the following formula [vii] The degree of neck-in of the polymer film was determined.
- Neck-in degree Polarized film width ⁇ (Film width before stretching ⁇ ⁇ Limit stretching ratio) [vii]
- the higher the numerical value of the neck-in degree the wider the polarizing film width with respect to the limit draw ratio, and the larger the polarizing film area that can be collected.
- Example 1 Production of PVA polymer film: (I) 100 parts by mass of PVA (saponification degree 99.9 mol%, polymerization degree 2400) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide and water
- the first drying roll surface temperature 93 ° C., peripheral speed (S 1 ) 16.0 m
- S 1 peripheral speed
- a film-forming apparatus provided with a plurality of drying rolls having rotation axes parallel to each other from a T-die with a film-forming stock solution having a volatile content of 66 mass% / Min
- the volatile fraction is 21% by mass while blowing hot air of 90 ° C.
- Example 1 the ratio (S L / S 1 ) of the peripheral speed (S L ) of the final drying roll to the peripheral speed (S 1 ) of the first drying roll was 0.958, and the volatile fraction was 20% by mass.
- Example 2 and 3 and Comparative Examples 1 to 3 (1)
- the PVA polymer was prepared in the same manner as in Example 1 (1) by changing the film forming conditions for producing the PVA polymer film as described in Table 1 below. A film was produced. Table 1 below shows ⁇ n (MD) Ave , ⁇ n (TD) Ave , mass swelling degree, limit draw ratio, and neck-in degree of each PVA polymer film thus obtained. It was as follows.
- the PVA polymer films of Examples 1 to 3 were found to have ⁇ n (MD) Ave [average birefringence in the machine flow direction of the PVA polymer film in the thickness direction of the film.
- ⁇ n (TD) Ave value obtained by averaging the birefringence in the width direction of the PVA polymer film in the thickness direction of the film] satisfies the formulas (I) and (II).
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Abstract
Description
特に、PVA系重合体フィルムの機械流れ方向(長さ方向)の複屈折率をフィルムの厚み方向に平均化した値、および、PVA系重合体フィルムの幅方向の複屈折率をフィルムの厚み方向に平均化した値がそれぞれ特定の範囲にある前記したPVA系重合体フィルムは、当該フィルムの厚みが、偏光フィルムの製造に従来一般に用いられてきたPVA系重合体フィルムの厚みよりも薄い、10~65μm程度の厚みであっても、高い限界延伸倍率を有しているために、破断を生ずることなく、高倍率で円滑に一軸延伸することができ、それによって偏光フィルムの製造時の一層の薄膜化が可能で、偏光フィルムを製造する際の乾燥時間を一層短縮できることを見出した。
本発明者らは、上記の知見に基づいて更に検討を重ねて本発明を完成した。
[1]下記の式(I)および(II)を満足することを特徴とするPVA系重合体フィルム、
Δn(MD)Ave ≦ 1.3×10-3 (I)
Δn(TD)Ave ≦ 1.3×10-3 (II)
[上記式中、Δn(MD)Aveは、PVA系重合体フィルムの機械流れ方向の複屈折率を当該フィルムの厚み方向に平均化した値を示し、Δn(TD)Aveは、PVA系重合体フィルムの幅方向の複屈折率を当該フィルムの厚み方向に平均化した値を示す。]
[2]厚みが10~65μmの範囲内にある、前記[1]のPVA系重合体フィルム、
[3]光学フィルム製造用原反フィルムである、前記[1]または[2]のPVA系重合体フィルム、
[4]光学フィルムが偏光フィルムである、前記[3]のPVA系重合体フィルム、
[5]PVA系重合体フィルムの製造方法であって、
(a) 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部分乾燥した後にそれに続く乾燥ロールで更に乾燥して製膜し;その際に、
(b) 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(SL)の比(SL/S1)を0.955~0.980にし;
(c) 揮発分率が20質量%になったときのPVA系重合体膜の膜幅(H20)および揮発分率が9質量%になったときのPVA系重合体膜の膜幅(H9)より計算される収縮率((1-H9/H20)×100)(%)を1%以上にする;ことを特徴とする製造方法、
[6]PVA系重合体膜の揮発分率が20質量%になったときの乾燥ロールから、PVA系重合体膜の揮発分率が9質量%になったときの乾燥ロールまでの各乾燥ロールの表面温度について、これらの平均値を85℃以上にする、前記[5]の製造方法、
[7]製膜原液の揮発分率が60~75質量%である、前記[5]または[6]の製造方法、
[8]第1乾燥ロールの周速(S1)を8~25m/分にする、前記[5]~[7]のいずれか1つの製造方法、
[9]前記[3]のPVA系重合体フィルムから製造した光学フィルム、
[10]偏光フィルムである、前記[9]の光学フィルム、
に関する。
特に、本発明のPVA系重合体フィルムは、フィルムの厚みが、偏光フィルムなどを製造するために従来一般に用いられてきたPVA系重合体フィルムの厚みよりも薄い、10~65μm程度の厚みであっても、高い限界延伸倍率を有しているために、破断を生ずることなく、高倍率で円滑に一軸延伸することができ、それに伴って延伸フィルムを製造する際の一層の薄膜化が可能になり、偏光フィルムなどを製造する際の乾燥時間の一層の短縮化およびそれによる生産性の向上が可能になる。
また、近年、偏光フィルム製造用の原反フィルムとして、長さが5000mを超えるPVA系重合体フィルムも用いられているが、本発明のPVA系重合体フィルムは高い限界延伸倍率を有しているため、従来のものよりも一層高倍率で延伸することができ、それによってPVA系重合体フィルムからの偏光フィルムの取得量を従来よりも多くすることができる。
更に、本発明の製造方法を採用することによって、上記した優れた特性を有する本発明のPVA系重合体フィルムを高い生産性で円滑に連続して製造することができる。
一般に、PVA系重合体などの透明なポリマーを用いて製造した透明なフィルムでは、ポリマー鎖がずり応力による塑性変形や歪みなどによって流れ方向(機械流れ方向:長さ方向)に配向してポリマーを構成する原子団の分極方向がマクロ的に揃い、それによってポリマー特有の複屈折が生ずる。
PVA系重合体フィルムにおける機械流れ方向の複屈折率[Δn(MD)]は下記の式
[i]から求められ、また幅方向の複屈折率[Δn(TD)]は下記の式[ii]から求められる。
Δn(MD)=nMD-nz [i]
Δn(TD)=nTD-nz [ii]
[式中、nMDはフィルムの機械流れ方向(長さ方向)の屈折率、nTDはフィルムの幅方向の屈折率、nzはフィルムの厚み方向の屈折率を示す。]
Δn(MD)Ave ≦ 1.3×10-3 (I)
Δn(TD)Ave ≦ 1.3×10-3 (II)
[上記式中、Δn(MD)Aveは、PVA系重合体フィルムの機械流れ方向の複屈折率を当該フィルムの厚み方向に平均化した値を示し、Δn(TD)Aveは、PVA系重合体フィルムの幅方向の複屈折率を当該フィルムの厚み方向に平均化した値を示す。]
(i) PVA系重合体フィルムの長さ方向(MD)の任意の位置で、図1の(a)に示すように、フィルムの幅方向(TD)における中央部からMD×TD=2mm×10mmの大きさの細片を切り出し、その細片を厚み100μmのPETフィルムで両側を挟み、それを更に木枠に挟んでミクロトーム装置に取り付ける。
(ii) 次に、前記で採取した細片を、図1の(b)に示すように(PETフィルムおよび木枠は図示せず)、細片の長さ方向(MD)と平行に10μm間隔でスライスし、図1の(c)に示す観察用のスライス片(MD×TD=2mm×10μm)を10個作製する。このスライス片の中から、スライス面が平滑で且つスライス厚み斑のないスライス片5個を選び、それぞれをスライドガラス上に載せてマイクロスコープ(キーエンス社製)でスライス厚みを測定する。なお、観察は接眼10倍、対物20倍(トータル200倍)の視野で行う。
(iii) 次いで、スライス面が観察できるように、スライス片を図1の(d)のように倒してスライス面を上向きとしてスライドガラス上に載せてカバーガラスとシリコーンオイル(屈折率1.04)で封じ、二次元光弾性評価システム「PA-micro」(株式会社フォトニックラティス製)を用いてスライス片5個のレタデーションを測定する。
(iv) 各スライス片のレタデーション分布を「PA-micro」の測定画面に表示した状態で、スライス片を横切るように当初のフィルムの表面に垂直な線αを引き、その線分α上でライン解析を行ってフィルムの厚み方向のレタデーション分布データを取得する。なお、観察は接眼10倍、対物20倍(トータル200倍)の視野で行う。また、スライス片上で線分αの通る位置が変わることによる誤差を抑えるため、線幅を300画素としてレタデーションの平均値を採用する。
(v) 上記で得られたフィルムの厚み方向のレタデーション分布の値をマイクロスコープで測定した厚みで除してフィルムの厚み方向の複屈折率Δn(MD)分布を求め、当該フィルムの厚み方向の複屈折率Δn(MD)分布の平均値を採る。スライス片5個について求めたそれぞれのフィルムの厚み方向の複屈折率Δn(MD)分布の平均値を更に平均して、「Δn(MD)Ave」とする。
(ここでは、PVA系重合体フィルムの幅方向(TD)の中央部におけるΔn(TD)Aveの測定法を例示する。)
(i) PVA系重合体フィルムの長さ方向(MD)の任意の位置で、図2の(a)に示すように、フィルムの幅方向(TD)における中央部からMD×TD=10mm×2mmの大きさの細片を切り出し、その細片を厚み100μmのPETフィルムで両側を挟み、それを更に木枠に挟んでミクロトーム装置に取り付ける。
(ii) 次に、前記で採取した細片を、図2の(b)に示すように(PETフィルムおよび木枠は図示せず)、細片の幅方向(TD)と平行に10μm間隔でスライスし、図2の(c)に示す観察用のスライス片(MD×TD=10μm×2mm)を10個作製する。このスライス片の中から、スライス面が平滑で且つスライス厚み斑のないスライス片5個を選び、それぞれをスライドガラス上に載せてマイクロスコープ(キーエンス社製)でスライス厚みを測定する。なお、観察は接眼10倍、対物20倍(トータル200倍)の視野で行う。
(iii) 次いで、スライス面が観察できるように、スライス片を図2の(d)のように倒してスライス面を上向きとしてスライドガラス上に載せてカバーガラスとシリコーンオイル(屈折率1.04)で封じ、二次元光弾性評価システム「PA-micro」(株式会社フォトニックラティス製)を用いてスライス片5個のレタデーションを測定する。
(iv) 各スライス片のレタデーション分布を「PA-micro」の測定画面に表示した状態で、スライス片を横切るように当初のフィルムの表面に垂直な線βを引き、その線分β上でライン解析を行ってフィルムの厚み方向のレタデーション分布データを取得する。なお、観察は接眼10倍、対物20倍(トータル200倍)の視野で行う。また、スライス片上で線分βの通る位置が変わることによる誤差を抑えるため、線幅を300画素としてレタデーションの平均値を採用する。
(v) 上記で得られたフィルムの厚み方向のレタデーション分布の値をマイクロスコープで測定した厚みで除してフィルムの厚み方向の複屈折率Δn(TD)分布を求め、当該フィルムの厚み方向の複屈折率Δn(TD)分布の平均値を採る。スライス片5個について求めたそれぞれのフィルムの厚み方向の複屈折率Δn(TD)分布の平均値を更に平均して、「Δn(TD)Ave」とする。
一方、PVA系重合体フィルムの厚みが薄すぎると、偏光フィルムを製造するための一軸延伸時にフィルムの破断が生じ易くなる傾向があることから、PVA系重合体フィルムの厚みは15μm以上であることがより好ましく、18μm以上であることが更に好ましく、20μm以上であることが特に好ましい。
ここでいう質量膨潤度とは、PVA系重合体フィルムを30℃の蒸留水中に30分間浸漬した際の質量を、前記浸漬後105℃で16時間乾燥した後の質量で除して得られる値の百分率を意味し、具体的には以下の実施例に記載する方法により測定することができる。
本発明の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。
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。
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。
(a) 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部分乾燥した後にそれに続く乾燥ロールで更に乾燥して製膜し;その際に、
(b) 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(SL)の比(SL/S1)を0.955~0.980にし;
(c) 揮発分率が20質量%になったときのPVA系重合体膜の膜幅(H20)および揮発分率が9質量%になったときのPVA系重合体膜の膜幅(H9)より計算される収縮率((1-H9/H20)×100)(%)を1%以上にする;
本発明の製造方法によって、高い生産性で円滑に連続して製造することができる。
PVA系重合体フィルムを含む製膜原液は、PVA系重合体を液体媒体と混合して溶液にしたり、液体媒体などを含むPVA系重合体ペレットなどを溶融して溶融液にしたりすることによって調製することができる。
PVA系重合体の液体媒体への溶解、液体媒体などを含むPVA系重合体ペレットの溶融は、撹拌式混合装置、溶融押出機などを使用して行うことができる。
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種を単独でまたは2種以上を組み合わせて使用することができる。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。
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種を単独でまたは2種以上を組み合わせて使用することができる。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種以上が好ましく使用される。
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などのカルボン酸型、オクチルサルフェートなどの硫酸エステル型、ドデシルベンゼンスルホネートなどのスルホン酸型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など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など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など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など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など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など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など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などのアリルフェニルエーテル型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種を単独でまたは2種以上を組み合わせて使用することができる。
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[iii]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[iii]
[式中、Waは製膜原液の質量(g)、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)を示す。]
第1乾燥ロールから剥離する際のPVA系重合体膜の揮発分率が上記下限以上であることにより、Δn(MD)Aveの値が大きくなりすぎるのを抑制することができる。一方、第1乾燥ロールから剥離する際のPVA系重合体膜の揮発分率があまりに高すぎると、第1乾燥ロールからの剥離が困難になる傾向があり、場合によっては破断したりムラが発生し易くなったりすることがある。
A(質量%) = {(Wc-Wd)/Wc}×100 [iv]
[式中、Aは、PVA系重合体膜またはPVA系重合体フィルムの揮発分率(質量%)、WcはPVA系重合体膜またはPVA系重合体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。]
第1乾燥ロール上にあるPVA系重合体膜の第1乾燥ロール非接触面に熱風を吹き付けるに当っては、第1乾燥ロール非接触面の全領域に対して風速1~10m/秒の熱風を吹き付けることが好ましく、風速2~8m/秒の熱風を吹き付けることがより好ましく、風速3~8m/秒の熱風を吹き付けることが更に好ましい。
第1乾燥ロール非接触面に吹き付ける熱風の風速が小さ過ぎると、本発明で目的としている限界延伸倍率の高いPVA系重合体フィルムが得られにくくなるとともに、第1乾燥ロール上での乾燥時に水蒸気などの結露が発生し、その水滴がPVA系重合体膜に滴下して最終的に得られるPVA系重合体フィルムにおける欠陥が生じ易くなる。一方、第1乾燥ロール非接触面に吹き付ける熱風の風速が大き過ぎると、本発明で目的としている限界延伸倍率の高いPVA系重合体フィルムが得られにくくなるとともに、最終的に得られるPVA系重合体フィルムに厚み斑が発生し、それに伴って染色斑の発生などのトラブルが発生し易くなる。
PVA系重合体フィルムを製造する際の前記した比(SL/S1)は、0.975以下であることが好ましく、0.970以下であることがより好ましく、0.960以下であることが更に好ましい。
上記した一連の処理によって最終的に得られるPVA系重合体フィルムの揮発分率は1~5質量%の範囲にあることが好ましく、2~4質量%の範囲にあることがより好ましい。
延伸後のフィルム(偏光フィルム)の厚みは、1~35μm、特に5~25μmであることが好ましい。
以上のようにして得られた偏光板は、アクリル系などの粘着剤を被覆した後、ガラス基板に貼り合わせて液晶ディスプレー装置の部品として使用することができる。偏光板をガラス基板に貼り合わせる際に、位相差フィルム、視野角向上フィルム、輝度向上フィルムなどを同時に貼り合わせてもよい。
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、PVA系重合体膜またはPVA系重合体フィルムの揮発分率(水分率)、および、PVA系重合体フィルムの各物性は以下の方法により測定した。
上記した方法にしたがって、上記の式[iii]により求めた。
上記した方法にしたがって、上記の式[iv]により求めた。なお、PVA系重合体膜またはPVA系重合体フィルムの揮発分率(水分率)の測定は、乾燥ロールから取り出したPVA系重合体膜またはPVA系重合体フィルムの幅方向(TD)中央部から採取したサンプルを用いて行った。
PVA系重合体フィルムの幅方向(TD)の中央部におけるΔn(MD)Aveを「《1》Δn(MD)Aveの測定法」の項目において上記した方法により求め、これをPVA系重合体フィルムのΔn(MD)Aveとした。
PVA系重合体フィルムの幅方向(TD)の中央部におけるΔn(TD)Aveを「《2》Δn(TD)Aveの測定法」の項目において上記した方法により求め、これをPVA系重合体フィルムのΔn(TD)Aveとした。
PVA系重合体フィルムを1.5gとなるようにカットし、30℃の蒸留水1000g中に30分間浸漬し、30分間浸漬後にPVA系重合体フィルムを取り出し、濾紙で表面の水を吸い取った後、その質量(We)を測定した。続いてそのPVA系重合体フィルムを105℃の乾燥機で16時間乾燥した後、その質量(Wf)を測定した。得られた質量WeおよびWfから、以下の式[vi]によって、PVA系重合体フィルムの質量膨潤度を求めた。
質量膨潤度(%) = (We/Wf)×100 [vi]
以下の実施例または比較例で得られた延伸前のPVA系重合体フィルムの幅方向(TD)の中央部から長さ方向(MD)×幅方向(TD)=10cm×5cmの試験片を採取し、当該試験片の長さ方向の両端を、延伸部分のサイズが長さ方向(MD)×幅方向(TD)=5cm×5cmとなるように延伸治具に固定し、30℃の水中に38秒間浸漬している間に12cm/分の延伸速度で元の長さの2.2倍に長さ方向(MD)に一軸延伸(1段目延伸)した後、ヨウ素を0.03質量%およびヨウ化カリウムを3質量%の濃度で含有する温度30℃のヨウ素/ヨウ化カリウム水溶液中に90秒間浸漬している間に12cm/分の延伸速度で元の長さの3.5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3質量%およびヨウ化カリウムを3質量%の濃度で含有する温度30℃のホウ酸/ヨウ化カリウム水溶液中に約20秒間浸漬している間に12cm/分の延伸速度で元の長さの3.9倍まで長さ方向(MD)に一軸延伸(3段目延伸)し、続いてホウ酸を4質量%およびヨウ化カリウムを約5質量%の濃度で含有する温度約63℃のホウ酸/ヨウ化カリウム水溶液中に浸漬しながら12cm/分の延伸速度で試験片が破断するまで長さ方向(MD)に一軸延伸し、試験片が破断したときの延伸倍率(元の長さに対する破断時の長さの比)と、破断時の試験片幅を読み取った。
同じPVA系重合体フィルムについて、上記した延伸試験を5回行って、その平均値をとってPVA系重合体フィルムの限界延伸倍率(倍)と、偏光フィルム幅とした。
上記の方法で採取したサンプルより得られた限界延伸倍率、偏光フィルム幅、延伸前フィルム幅(5cm)から、以下の式[vii]によって、PVA系重合体フィルムのネックイン度を求めた。
ネックイン度 = 偏光フィルム幅 ÷(延伸前フィルム幅 ÷ √限界延伸倍率) [vii]
ここで、ネックイン度の数値が高くなる程、限界延伸倍率に対する偏光フィルム幅が広いことを示しており、採取できる偏光フィルム面積が大きくなることを表す。
(1)PVA系重合体フィルムの製造:
(i) 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%、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93℃、周速(S1)16.0m/分)上に膜状に吐出し、当該第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21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、第2乾燥ロール以降の乾燥ロールで更に乾燥し、その後、表面温度102℃の乾燥ロール(熱処理ロール)で熱処理を行った後、巻き取ってPVA系重合体フィルム(厚み60μm、幅3m、揮発分率3質量%)を得た。
この実施例1では、第1乾燥ロールの周速(S1)に対する最終乾燥ロールの周速(SL)の比(SL/S1)を0.958とし、揮発分率が20質量%になったときのPVA系重合体膜の膜幅(H20)および揮発分率が9質量%になったときのPVA系重合体膜の膜幅(H9)より計算される収縮率((1-H9/H20)×100)を2.03%とし、PVA系重合体膜の揮発分率が20質量%になったときの乾燥ロールからPVA系重合体膜の揮発分率が9質量%になったときの乾燥ロールまでの各乾燥ロールの表面温度について、これらの平均値を90.0℃とした。
(ii) 上記(i)で得られたPVA系重合体フィルムのΔn(MD)Ave、Δn(TD)Ave、質量膨潤度、限界延伸倍率およびネックイン度を上記した方法で測定したところ、下記の表1に示すとおりであった。
(1) 実施例1において、PVA系重合体フィルムを製造する際の製膜条件を、下記の表1に記載するように変えて、実施例1の(1)と同様にしてPVA系重合体フィルムを製造した。
これにより得られた各PVA系重合体フィルムのΔn(MD)Ave、Δn(TD)Ave、質量膨潤度、限界延伸倍率およびネックイン度を上記した方法で測定したところ、下記の表1に示すとおりであった。
それに対して、比較例1~3のPVA系重合体フィルムは式(I)および(II)を満たしていないために、実施例1~3のPVA系重合体フィルムに比べて、いずれも、限界延伸倍率およびネックイン度が低かった。
Claims (10)
- 下記の式(I)および(II)を満足することを特徴とするポリビニルアルコール系重合体フィルム。
Δn(MD)Ave ≦ 1.3×10-3 (I)
Δn(TD)Ave ≦ 1.3×10-3 (II)
[上記式中、Δn(MD)Aveは、ポリビニルアルコール系重合体フィルムの機械流れ方向の複屈折率を当該フィルムの厚み方向に平均化した値を示し、Δn(TD)Aveは、ポリビニルアルコール系重合体フィルムの幅方向の複屈折率を当該フィルムの厚み方向に平均化した値を示す。] - 厚みが10~65μmの範囲内にある、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。
- 光学フィルム製造用原反フィルムである、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。
- 光学フィルムが偏光フィルムである、請求項3に記載のポリビニルアルコール系重合体フィルム。
- ポリビニルアルコール系重合体フィルムの製造方法であって、
(a) 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部分乾燥した後にそれに続く乾燥ロールで更に乾燥して製膜し;その際に、
(b) 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(SL)の比(SL/S1)を0.955~0.980にし;
(c) 揮発分率が20質量%になったときのポリビニルアルコール系重合体膜の膜幅(H20)および揮発分率が9質量%になったときのポリビニルアルコール系重合体膜の膜幅(H9)より計算される収縮率((1-H9/H20)×100)(%)を1%以上にする;
ことを特徴とする製造方法。 - ポリビニルアルコール系重合体膜の揮発分率が20質量%になったときの乾燥ロールから、ポリビニルアルコール系重合体膜の揮発分率が9質量%になったときの乾燥ロールまでの各乾燥ロールの表面温度について、これらの平均値を85℃以上にする、請求項5に記載の製造方法。
- 製膜原液の揮発分率が60~75質量%である、請求項5または6に記載の製造方法。
- 第1乾燥ロールの周速(S1)を8~25m/分にする、請求項5~7のいずれか1項に記載の製造方法。
- 請求項3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した光学フィルム。
- 偏光フィルムである、請求項9に記載の光学フィルム。
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