WO2015129538A1 - ポリビニルアルコールフィルムおよびその製造方法 - Google Patents
ポリビニルアルコールフィルムおよびその製造方法 Download PDFInfo
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- WO2015129538A1 WO2015129538A1 PCT/JP2015/054560 JP2015054560W WO2015129538A1 WO 2015129538 A1 WO2015129538 A1 WO 2015129538A1 JP 2015054560 W JP2015054560 W JP 2015054560W WO 2015129538 A1 WO2015129538 A1 WO 2015129538A1
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- Prior art keywords
- film
- pva
- polyvinyl alcohol
- orientation axis
- polarizing
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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
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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
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention relates to a polyvinyl alcohol film, a method for producing the same, and an optical film such as a polarizing film produced from the film. More specifically, the present invention relates to polyvinyl alcohol that provides an optical film such as a polarizing film that has a narrow color spot and is less noticeable as a spot even when the light transmittance is high or the light intensity of the backlight is high.
- the present invention relates to a film, a manufacturing method thereof, and an optical film such as a polarizing film manufactured from the film.
- a polarizing plate having a light transmission and shielding function is a basic component of a liquid crystal display (LCD) together with a liquid crystal that changes a polarization state of light.
- LCD liquid crystal display
- Many polarizing plates have a structure in which a protective film such as a cellulose triacetate (TAC) film is bonded to the surface of a polarizing film.
- TAC cellulose triacetate
- Such a polarizing film is obtained by uniaxially stretching a polyvinyl alcohol film containing a dichroic dye in advance, adsorbing a dichroic dye simultaneously with uniaxial stretching of the polyvinyl alcohol film, or uniaxially stretching the polyvinyl alcohol film. Manufactured by adsorbing dichroic dyes.
- LCDs are used in a wide range of applications, including small devices such as calculators and wristwatches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measuring devices used indoors and outdoors. .
- small devices such as calculators and wristwatches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measuring devices used indoors and outdoors.
- reduction of power consumption is particularly strongly demanded, it has become important for LCDs to maintain high screen brightness even when the light intensity of the backlight is low.
- a high-polarizing plate is more prominent in color spots than a polarizing plate having a low light transmittance.
- Patent Document 1 As a polyvinyl alcohol film for reducing color spots of a polarizing film, a polyvinyl alcohol film (see Patent Document 1) in which birefringence spots and thickness spots are reduced, between two points separated by 1 cm in the width direction of the film A polyvinyl alcohol film having a retardation difference in a specific range (see Patent Document 2), a polyvinyl alcohol film having a thickness variation per mm in the width direction of the film in a specific range (see Patent Document 3), and the like are known. .
- the inclination of the optical axis over the entire film width direction of the film can be reduced with respect to the longitudinal direction of the film, as it can reduce the generation of wrinkles when the polyvinyl alcohol film swells and streak-like stained spots existing in the longitudinal direction of the polarizing film.
- a polyvinyl alcohol film having an angle of 45 to 135 ° is known (see Patent Document 4).
- the above-mentioned conventional polyvinyl alcohol film has a relatively wide color spot even if the color difference of the color spot can be reduced, for example, when the polarizing film is used for manufacturing a polarizing plate. It has been found that there is a problem that it is easily noticeable as spots.
- An object of the present invention is to provide a polyvinyl alcohol film that can easily produce an optical film such as a polarizing film that has a narrow color spot and is less noticeable as a spot, and a method for producing the same. Furthermore, this invention aims at providing optical films, such as a polarizing film manufactured using the said polyvinyl alcohol film.
- an optical film such as Furthermore, when manufacturing the film using the film-forming stock solution containing polyvinyl alcohol, the inventors of the present invention use the film-forming stock solution on a support such as a roll or a belt from a discharge port of a discharge device. It has been found that smooth production can be achieved by blowing a specific wind speed to the discharged film within a specific time after discharging into a film. The present inventors have further studied based on these findings and completed the present invention.
- the present invention [1] In the distribution of orientation axis angles obtained by measuring the orientation axis angle in the plane of the film at a pitch of 0.8 mm in the width direction of the film, the maximum distance between adjacent peaks is 6 cm or less. It is the characteristic polyvinyl alcohol film. And this invention, [2] In the distribution of the orientation axis angles obtained by measuring the orientation axis angles in the plane of the film at a pitch of 0.8 mm in the width direction of the film, the maximum difference between the orientation axis angles in adjacent peaks is 10 ° or less.
- the present invention provides [4] A method for producing a polyvinyl alcohol film by discharging a film-forming stock solution containing polyvinyl alcohol in the form of a film from a discharge port of a discharge device onto a support, and producing a polyvinyl alcohol film within 10 seconds after discharge.
- a method for producing a polyvinyl alcohol film comprising a step of spraying a film of 3 to 5 m / sec.
- the present invention also provides: [5] An optical film produced using the polyvinyl alcohol film of any one of [1] to [3]; [6] The optical film according to [5], which is a polarizing film; It is.
- the polyvinyl alcohol film of the present invention As a raw material, even if the light transmittance is high or a backlight having a higher light intensity is used, the polarizing film has a narrow color spot and is hardly noticeable as a spot. An optical film such as can be obtained.
- the polyvinyl alcohol film of the present invention having the above-described excellent characteristics can be produced smoothly.
- FIG. 1 is a diagram schematically showing an orientation axis angle in a film plane of a polyvinyl alcohol film.
- FIG. 2 is a schematic view showing an example of measurement points when measuring the orientation axis angle in the film plane of the polyvinyl alcohol film.
- the present invention is described in detail below.
- the polyvinyl alcohol film of the present invention (hereinafter, polyvinyl alcohol may be referred to as “PVA”) has an orientation axis angle obtained by measuring the orientation axis angle in the plane of the film at a pitch of 0.8 mm in the width direction of the film. In the distribution, the maximum distance between adjacent peaks is 6 cm or less.
- the PVA film of the present invention since the said distance is large, in the polarizing film manufactured using it, and a polarizing plate, there existed a problem that the width
- the PVA film of the present invention has a maximum distance of 6 cm or less, which is different from conventional PVA films.
- the orientation axis angle in the plane of the film in the present invention refers to the angle ⁇ between the longitudinal direction (MD) and the orientation axis (slow axis) in the plane of the film, and the orientation axis angle. It depends on the orientation state of the PVA molecules at the measurement position.
- the orientation axis angle can be measured based on light (for example, light having a wavelength of 543 nm) traveling in a direction perpendicular to the film surface (film thickness direction) using a birefringence measurement device, a cell gap measurement device, or the like. Specifically, it can be measured by the method described later in the examples.
- a virtual straight line A1-A2 in the width direction orthogonal to the length direction of the PVA film is defined at an arbitrary position in the length direction (MD) of the PVA film, and the virtual straight line A1-A2 is The orientation axis angle is measured by light traveling in a direction perpendicular to the film surface (thickness direction of the film) at a pitch of 0.8 mm over the entire width of the virtual straight line A1-A2 (full width of the film).
- the measurement position for measuring the orientation axis angle is not particularly limited.
- an arbitrary point (for example, the center) on the imaginary straight line connecting A1 and A2 is A3, and a pitch of 0.8 mm from A3 toward A1.
- a method of measuring the orientation axis angle at a pitch of 0.8 mm from A3 to A2 and the like can be adopted.
- the width direction of the film is a direction (TD) in the plane of the film orthogonal to the length direction (MD) of the film.
- the length direction (MD) of the film coincides with the direction in which the PVA film should be uniaxially stretched when producing an optical film such as a polarizing film, and the direction in the plane of the film orthogonal to the length direction.
- the width direction (TD) In the case of a non-long PVA film, the direction to be uniaxially stretched when manufacturing an optical film such as a polarizing film is the length direction (MD) of the film, and the direction in the plane of the film orthogonal thereto
- the width direction (TD) may be used.
- the long-period noise can be eliminated as follows. That is, for each measurement point, a total of 500 points of 250 points (250 pitches) continuous on one side of the film width direction (TD) and 250 points (250 pitches) continuous on the other side from the measurement points.
- the average value of the orientation axis angles is obtained, and this average value is subtracted from the orientation axis angle value at the target measurement point.
- data indicating the variation of the orientation axis angle from which long-period noise has been eliminated can be obtained.
- the “distance between adjacent peaks” can be obtained by analyzing the data indicating the variation in the orientation axis angle from which long-period noise has been eliminated by the following method. In the case of eliminating the long-period noise, both end portions in the film width direction (TD) without data of orientation axis angles for 250 points continuous on one side in the film width direction (TD). (Each portion having a width of about 20 cm) is often not manufactured because it is usually slit in the optical film manufacturing process, and can therefore be excluded from the analysis of “distance between adjacent peaks”.
- the peak detection of the orientation axis angle distribution is performed based on the data indicating the orientation axis angle fluctuation from which the long-period noise has been eliminated. Do. To detect the peak of the distribution of the orientation axis angle, set “constant (average)” as the baseline mode, and set “based on height (threshold height 30%)” as the peak fit filtering method. Peaks smaller than the threshold are excluded. Next, the position in the width direction at each peak is obtained, the distance in the width direction between adjacent peaks is calculated, and this is defined as “distance between adjacent peaks”. In the present invention, the peak in “distance between adjacent peaks” includes a positive peak and a negative peak.
- the maximum distance between adjacent peaks obtained as described above is 6 cm or less, and the distance between adjacent peaks is all 6 cm or less.
- the maximum value of the distance between adjacent peaks is larger than 6 cm, the width of the color spot becomes thick when the polarizing film and the polarizing plate are used, and the spot becomes easily noticeable as a spot.
- the maximum distance between adjacent peaks in the PVA film is preferably 5.5 cm or less, more preferably 5 cm or less, and in some cases 4 cm or less, 2 cm or less, and further 1 cm or less. It may be.
- the lower limit of the maximum distance between adjacent peaks is not particularly limited, but a PVA film having a very small maximum distance between adjacent peaks is difficult to produce with high productivity.
- the value is preferably 0.1 cm or more, more preferably 0.2 cm or more, and further preferably 0.3 cm or more.
- the maximum value of the difference in orientation axis angles at adjacent peaks is preferably 10 ° or less.
- the maximum value of the difference in the orientation axis angle between adjacent peaks is 10 ° or less, the difference in color shading when the polarizing film and the polarizing plate are formed can be reduced.
- the maximum value of the difference in the orientation axis angle in the adjacent peak is preferably 0.01 ° or more.
- the orientation in the adjacent peak is
- the maximum value of the difference in the shaft angle is more preferably 0.01 to 10 °, further preferably 0.02 to 8 °, and particularly preferably 0.05 to 5 °.
- the difference in orientation axis angle between adjacent peaks can be determined from the value of the orientation axis angle at the peak detected in the above-mentioned “distance between adjacent peaks”.
- the thickness of the PVA film of the present invention is not particularly limited, but if it is too thick, drying when producing an optical film such as a polarizing film is difficult to be performed quickly, while if too thin, it is difficult to produce an optical film.
- the thickness of the PVA film is preferably in the range of 5 to 150 ⁇ m, more preferably in the range of 8 to 120 ⁇ m, since the film is likely to break during uniaxial stretching. More preferably, it is particularly preferably in the range of 12 to 50 ⁇ m.
- the width of the PVA film of the present invention is not particularly limited, in recent years, liquid crystal televisions and monitors have become larger in screen, so that they can be effectively used for them, preferably 2 m or more. More preferably.
- an optical film such as a polarizing film is manufactured with a realistic production machine, if the width of the film is too wide, uniform uniaxial stretching may be difficult, so the width of the PVA film is 8 m or less. It is preferable.
- the length of the PVA film of the present invention is not particularly limited, but a more uniform PVA film can be continuously and smoothly manufactured, and is also used continuously when an optical film is manufactured using the PVA film. Therefore, it is preferably in the range of 5 to 50,000 m, more preferably in the range of 100 to 20,000 m.
- Examples of PVA constituting the PVA film of the present invention include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, isopropenyl acetate, etc.
- Those obtained by saponifying a polyvinyl ester obtained by polymerizing one or more of these vinyl esters can be used.
- a compound having a vinyloxycarbonyl group (H 2 C ⁇ CH—O—CO—) in the molecule is preferable from the viewpoint of ease of production, availability, and cost of PVA, More preferred is vinyl acetate.
- the polyvinyl ester is preferably obtained using only one or two or more vinyl esters as monomers, and more preferably obtained using only one vinyl ester as a monomer.
- a copolymer of one or more vinyl esters and other monomers copolymerizable therewith may be used.
- Examples of the other monomer copolymerizable with the vinyl ester include ⁇ -olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene; (meth) acrylic acid or a salt thereof; (Meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate i-propyl, (meth) acrylate n-butyl, (meth) acrylate i-butyl, ( (Meth) acrylic acid esters such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate and octadecyl (meth) acrylate; (meth) acrylamide; N-methyl ( (Meth) acrylamide, N-ethyl (meth) acrylamide, N, N
- Vinyl ether vinyl cyanide such as (meth) acrylonitrile; halo such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride Allyl compounds such as allyl acetate, allyl chloride, etc .; maleic acid or its salt, ester or acid anhydride; itaconic acid or its salt, ester or acid anhydride; vinylsilyl compound such as vinyltrimethoxysilane; unsaturated sulfone An acid or its salt can be mentioned.
- Said polyvinyl ester can have a structural unit derived from 1 type, or 2 or more types of an above described other monomer.
- the proportion of structural units derived from the other monomers in the polyvinyl ester is preferably 15 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester, and is preferably 10 mol% or less. More preferably, it is 5 mol% or less.
- those not graft-copolymerized can be preferably used, but PVA can be used for one or more kinds of graft copolymer as long as the effects of the present invention are not significantly impaired. It may be modified with a monomer.
- the said graft copolymerization can be performed with respect to at least one of polyvinyl ester and PVA obtained by saponifying it.
- the graft copolymerizable monomer include unsaturated carboxylic acids or derivatives thereof; unsaturated sulfonic acids or derivatives thereof; ⁇ -olefins having 2 to 30 carbon atoms, and the like.
- the proportion of structural units derived from the graft copolymerizable monomer in the polyvinyl ester or PVA is preferably 5 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester or PVA.
- the hydroxyl group may be cross-linked or may not be cross-linked.
- the PVA may have a hydroxyl group partially reacted with an aldehyde compound such as acetaldehyde or butyraldehyde to form an acetal structure, or may not react with these compounds to form an acetal structure. Also good.
- the polymerization degree of the above PVA is not particularly limited, but is preferably 1,000 or more.
- the degree of polymerization of PVA is 1,000 or more, the polarizing performance of the polarizing film obtained from the PVA film can be further improved. If the polymerization degree of PVA is too high, it tends to lead to an increase in the production cost of PVA and poor processability during film formation. Therefore, the polymerization degree of PVA should be in the range of 1,000 to 10,000. Is more preferably in the range of 1,500 to 8,000, particularly preferably in the range of 2,000 to 5,000.
- the degree of polymerization of PVA as used herein means the average degree of polymerization measured according to the description of JIS K6726-1994.
- the degree of saponification of PVA is preferably 98 mol% or more, more preferably 99 mol% or more, since the heat and heat resistance of an optical film such as a polarizing film obtained from the PVA film is improved. More preferably, it is 8 mol% or more, and it is especially preferable that it is 99.9 mol% or more.
- the degree of saponification of PVA refers to the vinyl alcohol relative to the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification of PVA. The ratio (mol%) occupied by the number of moles of units.
- the degree of saponification can be measured according to the description of JIS K6726-1994.
- the PVA film may contain a plasticizer together with the above PVA.
- a plasticizer polyhydric alcohol is preferably used, and specific examples include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like.
- PVA film Can contain one or more of these plasticizers. Among these, glycerin is preferable because the stretchability of the PVA film becomes better.
- the content of the plasticizer in the PVA film is preferably 3 to 20 parts by mass, more preferably 5 to 17 parts by mass, and further preferably 7 to 14 parts by mass with respect to 100 parts by mass of PVA. .
- the content of the plasticizer in the PVA film is 3 parts by mass or more with respect to 100 parts by mass of PVA, the stretchability of the PVA film is improved.
- the content of the plasticizer in the PVA film is 20 parts by mass or less with respect to 100 parts by mass of PVA, the plasticizer bleeds out on the surface of the PVA film and the handling property of the PVA film is reduced. be able to.
- surfactant that is blended in the film-forming stock solution for producing the PVA film, and thus the surfactant contained in the PVA film, but from the viewpoint of releasability from a metal roll or belt, an anion is used.
- Surfactants or nonionic surfactants are preferred, and nonionic surfactants are particularly preferred.
- anionic surfactant for example, a carboxylic acid type such as potassium laurate; a sulfate ester type such as octyl sulfate; a sulfonic acid type such as dodecylbenzene sulfonate and the like are suitable.
- nonionic surfactants include alkyl ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl ester types such as polyoxyethylene laurate; polyoxyethylene Alkylamine types such as laurylamino ether; alkylamide types such as polyoxyethylene lauric acid amide; polypropylene glycol ether types such as polyoxyethylene polyoxypropylene ether; alkanolamide types such as lauric acid diethanolamide and oleic acid diethanolamide; An allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether is preferred. These surfactants can be used alone or in combination of two or more.
- the content of the surfactant should be in the range of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of PVA contained in the film-forming stock solution. Preferably, it is in the range of 0.02 to 0.3 parts by mass.
- the content of the surfactant is 0.01 parts by mass or more with respect to 100 parts by mass of PVA, the film forming property and the peelability can be improved.
- the content of the surfactant is 0.5 parts by mass or less with respect to 100 parts by mass of PVA, the surfactant bleeds out on the surface of the PVA film, resulting in blocking, and handling properties are reduced. Can be suppressed.
- the PVA film may be composed only of PVA, or may be composed only of PVA and the above-described plasticizer and / or surfactant. If necessary, an antioxidant, an antifreeze agent, a pH adjuster, You may further contain 1 type, or 2 or more types of other components, such as a masking agent, a coloring preventing agent, and an oil agent.
- the PVA content in the PVA film is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and in the range of 85 to 100% by mass. Further preferred.
- the manufacturing method in particular of the PVA film of this invention is not restrict
- a production method including a step of blowing a wind of 0.3 to 5 m / sec on the discharged film is preferably employed since the PVA film of the present invention can be produced smoothly.
- adopted suitably in this invention (henceforth "the manufacturing method of this invention" is demonstrated.
- the film-forming stock solution examples include PVA and, if necessary, a plasticizer, a surfactant, a film-forming stock solution in which other components are dissolved in a liquid medium, PVA and, if necessary, a plasticizer and an interface.
- examples include a film-forming stock solution containing an active agent, other components, and a liquid medium and in which PVA is melted.
- the film-forming stock solution contains at least one of a plasticizer, a surfactant, and other components, it is preferable that these components are uniformly mixed.
- liquid medium used for the preparation of the membrane forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. , Trimethylolpropane, ethylenediamine, diethylenetriamine and the like, and one or more of them can be used. Among these, water is preferable from the viewpoint of a small environmental load and recoverability.
- the volatile fraction of the film-forming stock solution may vary depending on the film-forming method, the film-forming conditions, etc. It is preferably in the range of -95% by mass, more preferably in the range of 55-90% by mass, and still more preferably in the range of 60-85% by mass.
- the volatile fraction of the film-forming stock solution is 50% by mass or more, the viscosity of the film-forming stock solution does not become too high, and filtration and defoaming are smoothly performed during preparation of the film-forming stock solution, and there are few foreign matters and defects. Film production is facilitated.
- the temperature of the film forming stock solution is preferably 90 to 110 ° C.
- Examples of the discharge device for discharging the film-forming stock solution into a film include a T-type slit die, an I-die, and a lip coater die.
- the production method of the present invention includes a step of blowing wind at a wind speed of 0.3 to 5 m / second within 10 seconds after the film-forming stock solution is discharged into a film form from the discharge port. Since the PVA film of the present invention can be obtained more efficiently, the time when the wind is blown (the time when the wind is first blown to the discharged film) is preferably within 5 seconds after the discharge. It is more preferable that the time is within the range of 1 second to 1 second immediately after discharge. At that time, the length of time for blowing the wind is preferably 0.1 to 10 seconds, more preferably 0.5 to 5 seconds, and further preferably 0.8 to 2 seconds. .
- the wind speed of the blown wind is 0.3 to 5 m / second, and the PVA film of the present invention can be obtained more efficiently. Therefore, the wind speed is preferably 0.4 m / second or more, and 0.5 m / second. It is more preferably at least 2 seconds, more preferably at least 0.7 m / second, particularly preferably at least 0.77 m / second, and the wind speed is preferably less than 3 m / second, preferably 1 m. Is more preferably less than 0.9 m / sec, and even more preferably less than 0.9 m / sec.
- the temperature of the blowing air is preferably 20 to 100 ° C, more preferably 30 to 90 ° C, and further preferably 40 to 80 ° C. If the temperature of the blowing air is too low, the discharged PVA film tends to be insufficiently dried. On the other hand, if the temperature of the blowing air is too high, foaming tends to occur.
- the method of blowing the wind is not particularly limited, but a structure that reduces wind speed spots of the blowing wind is preferable, and a nozzle method, a rectifying plate method, or a combination thereof is generally used.
- a nozzle method, a rectifying plate method, or a combination thereof is generally used.
- the film forming apparatus to be used only needs to have a support for discharging the film forming stock solution.
- a drum type film forming apparatus or a belt type film forming apparatus can be used.
- a drum-type film forming apparatus is preferable, and in particular, a drum-type film forming apparatus including a plurality of drying rolls whose rotation axes are parallel to each other is more preferably used.
- volatile components are evaporated from one surface of the PVA film discharged onto the first roll, followed by drying.
- the other surface of the discharged PVA film can be dried by passing over the peripheral surface of the heated second roll that rotates.
- the volatile fraction when peeling the PVA film from the first roll is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and further preferably 20 to 30% by mass.
- the volatile content rate at the time of peeling from the first roll is too small, the stretchability tends to deteriorate during the processing to the polarizing film.
- the volatile content rate when peeling from the first roll is too large, peeling from the first roll tends to be difficult.
- the film-forming stock solution is dried with the first roll, it is further dried on the peripheral surface of one or a plurality of rotating heated rolls arranged on the downstream side, or further dried by passing through a hot air drying apparatus. Thereafter, a method of winding around a winding device can be preferably employed industrially. Drying with a heated roll and drying with a hot air dryer may be performed in an appropriate combination.
- a device for manufacturing the PVA film is provided with a heat treatment device; a humidity control device; a motor for driving each roll; a speed adjustment mechanism such as a transmission. It is preferable.
- the drying temperature during the drying process in the production process of the PVA film is preferably in the range of 50 to 150 ° C., more preferably in the range of 60 to 120 ° C. From this point of view, when producing a PVA film using a drum-type film forming apparatus comprising a plurality of drying rolls whose rotation axes are parallel to each other, the surface temperature of the first roll and the subsequent roll is 50 to 150 ° C., particularly 60 ° C. It is preferable that the temperature be ⁇ 120 ° C. When a hot air dryer is further arranged downstream of the drying roll, it is preferable that the atmospheric temperature in the hot air dryer is 50 to 150 ° C., particularly 60 to 120 ° C.
- the drying treatment may be performed until the volatile content of the PVA film is 10% by mass or less, further 5% by mass or less, particularly 2 to 4% by mass. It is preferable from the point.
- the PVA film of the present invention is preferably used as a raw material for producing an optical film.
- the optical film include a polarizing film and a retardation film. These optical films can be produced by a production method having a step of uniaxial stretching using the PVA film of the present invention.
- dyeing, uniaxial stretching, fixing treatment, drying treatment and further heat treatment may be performed using the PVA film of the present invention.
- the order of dyeing and uniaxial stretching is not particularly limited, and dyeing may be performed before uniaxial stretching, dyeing may be performed simultaneously with uniaxial stretching, or dyeing may be performed after uniaxial stretching. In addition, steps such as uniaxial stretching and dyeing may be repeated a plurality of times.
- iodine or a dichroic organic dye for example, DirectBlack 17, 19, 154; DirectBrown 44, 106, 195, 210, 223; DirectRed 2, 23, 28, 31, 37, 39, 79, 81, 240, 242, 247; DirectBlue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; DirectViolet 9, 12, 51, 98; DirectGreen 1, 85; Direct Yellow 8, 12, 44, 86, 87; dichroic dyes such as Direct Orange 26, 39, 106, 107) can be used.
- dichroic dyes may be used alone or in combination of two or more. Dyeing can usually be performed by immersing the PVA film in a solution containing the above-described dichroic dye, but the treatment conditions and treatment method are not particularly limited.
- Uniaxial stretching of the PVA film may be performed by either a wet stretching method or a dry heat stretching method.
- a wet stretching method When uniaxially stretching by a wet stretching method, it may be uniaxially stretched in warm water containing boric acid, or may be uniaxially stretched in a solution containing the above-described dichroic dye or in a fixing treatment bath described later.
- the PVA film after water absorption may be uniaxially stretched in the air or may be uniaxially stretched by other methods.
- the stretching temperature during the uniaxial stretching treatment is not particularly limited, but when the PVA film is stretched in warm water (wet stretching), it is preferably 30 to 90 ° C, more preferably 40 to 70 ° C, and still more preferably 45 to 65 ° C.
- the stretching ratio of uniaxial stretching is preferably stretched as much as possible from the point of polarization performance until just before the film is cut, and specifically 4 times or more. It is preferably 5 times or more, more preferably 5.5 times or more.
- the upper limit of the stretching ratio is not particularly limited as long as the film is not broken, but is preferably 8.0 times or less in order to perform uniform stretching.
- the draw ratio in this specification is based on the length of the film before extending
- the thickness of the stretched film (polarizing film) is preferably 3 to 35 ⁇ m, particularly 5 to 30 ⁇ m.
- uniaxial stretching in the length direction can be adopted. Therefore, uniaxial stretching in the length direction is preferable. Uniaxial stretching in the length direction can be performed by changing the peripheral speed between the rolls using a stretching apparatus including a plurality of rolls parallel to each other. On the other hand, uniaxial stretching in the transverse direction can be performed using a tenter type stretching machine.
- the fixing treatment In the production of the polarizing film, it is preferable to perform a fixing treatment in order to strengthen the adsorption of the dichroic dye to the uniaxially stretched film.
- the fixing treatment include a method of immersing the film in a fixing treatment bath to which a boron compound such as boric acid or borax is added. In that case, you may add an iodine compound in a fixed treatment bath as needed.
- the film subjected to uniaxial stretching or uniaxial stretching and fixing treatment is then subjected to a drying treatment (heat treatment).
- the temperature of the drying treatment (heat treatment) is preferably in the range of 30 to 150 ° C., more preferably in the range of 50 to 140 ° C. If the temperature of the drying treatment (heat treatment) is too low, the dimensional stability of the obtained polarizing film tends to be lowered, while if too high, the polarization performance is likely to deteriorate due to decomposition of the dichroic dye.
- the polarizing film obtained as described above can be made into a polarizing plate by attaching a protective film that is optically transparent and has mechanical strength to both sides or one side.
- a protective film in this case, a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, a cycloolefin polymer (COP) film, or the like is used.
- a PVA adhesive agent, a urethane adhesive agent, etc. are mentioned, Among these, a PVA adhesive agent is preferable.
- the polarizing plate obtained as described above can be used as a component of a liquid crystal display device after being coated with a pressure-sensitive adhesive such as acrylic and then attached to a glass substrate.
- a pressure-sensitive adhesive such as acrylic
- a retardation film, a viewing angle improving film, a brightness improving film, or the like may be bonded.
- the virtual straight line connecting A1 and A2 is defined as a central line so that the virtual straight line connecting A1 and A2 becomes the measurement site of the orientation axis angle, and 20 mm upstream of the virtual straight line.
- the tape-shaped sample over the full width of the PVA film was taken so that it might become a total of 40 mm by 20 mm downstream.
- the measurement positions are determined at a pitch of 0.8 mm, and the orientation axis angle is measured in the film plane at each measurement position. I got the data.
- the measurement of the orientation axis angle at each measurement position was performed with light having a wavelength of 543 nm traveling in a direction perpendicular to the film surface, using “WPA-100-L” manufactured by Photonic Lattice.
- a total of 500 points from the measurement point to 250 points (for 250 pitches) continuous on one side in the film width direction (TD) and 250 points (for 250 pitches) continuous on the other side.
- the average value of the orientation axis angles of the points was obtained, and this average value was subtracted from the value of the orientation axis angle at the target measurement point.
- data indicating fluctuations in the orientation axis angle from which long-period noise was eliminated was obtained.
- peak detection of the distribution of the orientation axis angle is performed based on the data indicating the change in the orientation axis angle from which the long-period noise has been eliminated. went.
- To detect the peak of the distribution of the orientation axis angle set “constant (average)” as the baseline mode, and set “based on height (threshold height 30%)” as the peak fit filtering method.
- Peaks smaller than the threshold were excluded.
- the position in the width direction of each peak is obtained, the distance in the width direction between adjacent peaks (between adjacent peaks) is calculated, and is set as the “distance between adjacent peaks”, of which The maximum value was determined.
- the difference in orientation axis angle between adjacent peaks (between adjacent peaks) is calculated between the respective peaks, The maximum value was determined.
- Color spots on the polarizing film An polarizing plate for observation (using a polarizing film having a transmittance of about 43%) is placed on a surface light source (backlight) in a dark room, and a polarizing film produced in the following examples or comparative examples on the surface light source (backlight). was placed so as to be in a crossed Nicol state with respect to the polarizing plate for observation, and then the polarizing film was irradiated with light from the backlight through the polarizing plate for observation (luminance 15,000 cd). The polarizing film was visually observed from the position, and color spots of the polarizing film were evaluated by sensory evaluation based on the following criteria. A: Color spots are not visually recognized. ⁇ : Color spots are visible, but are not noticeable and are practically acceptable. X: Color spots of a level causing a practical problem were visually recognized.
- Example 1 From 100 parts by weight of PVA (saponified vinyl acetate homopolymer, degree of polymerization 2,400, degree of saponification 99.9 mol%), 12 parts by weight of glycerin, 0.1 parts by weight of lauric acid diethanolamide and water A T-type slit is formed on a first roll (support) of a drum-type film forming apparatus using a film-forming stock solution having a volatile content of 66 mass% and a temperature of 100 ° C., and a plurality of drying rolls whose rotation axes are parallel to each other.
- PVA synthetic vinyl acetate homopolymer, degree of polymerization 2,400, degree of saponification 99.9 mol
- glycerin 0.1 parts by weight of lauric acid diethanolamide and water
- a T-type slit is formed on a first roll (support) of a drum-type film forming apparatus using a film-forming stock solution having a volatile content of 66 mass% and a temperature of 100
- Examples 2 to 5 and Comparative Examples 1 to 6 PVA film in the same manner as in Example 1 except that the wind blowing start time, the wind blowing time, the wind speed, and the volatile content of the PVA film when peeled from the first roll were changed as shown in Table 1. And calculating the maximum value of the distance between adjacent peaks in the distribution of the orientation axis angles of the obtained PVA film and the maximum difference of the orientation axis angles in the adjacent peaks, and the polarization obtained. The color spots of the film were evaluated. The results are shown in Table 1.
- the PVA films of Examples 1 to 5 had a maximum distance between adjacent peaks in the distribution of orientation axis angles of 6 cm or less.
- a high-quality polarizing film having a level in which no color spots are visually recognized or is not noticeable even when the color spots are visually recognized is obtained.
- the maximum distance between adjacent peaks in the distribution of the orientation axis angles exceeds 6 cm. Spots occurred.
- the PVA film of the present invention is used, an optical film such as a polarizing film that has a narrow color spot and is not noticeable as a spot even when a light transmittance is high or a backlight having a higher light intensity is used. Therefore, the PVA film of the present invention is extremely useful as a raw film for an optical film such as a polarizing film, and the production method of the present invention allows the PVA film of the present invention to be smoothly and continuously produced with high productivity. It is useful as a method for manufacturing.
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Abstract
Description
さらに、本発明は、当該ポリビニルアルコールフィルムを用いて製造した偏光フィルムなどの光学フィルムを提供することを目的とする。
さらに、本発明者らは、当該ポリビニルアルコールフィルムは、ポリビニルアルコールを含む製膜原液を用いてフィルムを製造する際に、製膜原液をロールやベルトなどの支持体上に吐出装置の吐出口から膜状に吐出後、特定の時間内に、吐出した膜に特定の風速の風を吹き付けることにより円滑に製造できることを見出した。
本発明らは、これらの知見に基づいてさらに検討を重ねて本発明を完成させた。
[1] フィルムの面内における配向軸角度をフィルムの幅方向に0.8mmピッチで測定して求めた配向軸角度の分布において、隣接するピーク間の距離の最大値が6cm以下であることを特徴とするポリビニルアルコールフィルムである。
そして、本発明は、
[2] フィルムの面内における配向軸角度をフィルムの幅方向に0.8mmピッチで測定して求めた配向軸角度の分布において、隣接するピークにおける配向軸角度の差の最大値が10°以下である前記[1]のポリビニルアルコールフィルム;および、
[3] 幅が2m以上である前記[1]または[2]のポリビニルアルコールフィルム;
である。
[4] ポリビニルアルコールを含む製膜原液を吐出装置の吐出口から支持体上に膜状に吐出し、乾燥してポリビニルアルコールフィルムを製造する方法であって、吐出後10秒以内に風速0.3~5m/秒の風を吐出した膜に吹き付ける工程を有することを特徴とするポリビニルアルコールフィルムの製造方法である。
[5] 前記[1]~[3]のいずれかのポリビニルアルコールフィルムを用いて製造した光学フィルム;および、
[6] 偏光フィルムである前記[5]の光学フィルム;
である。
本発明の製造方法を採用することによって、前記した優れた特性を有する本発明のポリビニルアルコールフィルムを円滑に製造することができる。
本発明のポリビニルアルコールフィルム(以下、ポリビニルアルコールを「PVA」ということがある)は、フィルムの面内における配向軸角度をフィルムの幅方向に0.8mmピッチで測定して求めた配向軸角度の分布において、隣接するピーク間の距離の最大値が6cm以下である。
従来のPVAフィルムにおいては、上記距離が大きいため、それを用いて製造した偏光フィルムひいては偏光板では、色斑の幅が太く、斑として目立ちやすいという問題があった。これに対して、本発明のPVAフィルムは上記距離の最大値が6cm以下であり、従来のPVAフィルムと異なっている。このような本発明のPVAフィルムを原反として用いれば、光透過率が高い場合やより光強度の高いバックライトを用いた場合であっても、色斑の幅が細くて斑として目立ちにくい偏光フィルムなどの光学フィルムを製造することができる。
図2に示すように、PVAフィルムの長さ方向(MD)の任意の位置で、PVAフィルムの長さ方向に対して直交する幅方向の仮想直線A1-A2を定め、仮想直線A1―A2上を、当該仮想直線A1-A2の全幅(フィルムの全幅)にわたって、0.8mmのピッチで、フィルム面に対して垂直な方向(フィルムの厚み方向)に進行する光によって配向軸角度を測定する。
配向軸角度の測定に当たっての測定位置は特に制限されず、例えば、A1とA2を結ぶ仮想直線上の任意の1点(例えば中央)をA3とし、当該A3からA1に向かって0.8mmのピッチで配向軸角度を測定し、さらにA3からA2に向かって0.8mmのピッチで配向軸角度を測定する方法などを採用することができる。
ここでフィルムの幅方向とは、フィルムの長さ方向(MD)と直交するフィルムの面内における方向(TD)である。長尺のPVAフィルムを原反として用いて偏光フィルムなどの光学フィルムを製造する場合には、通常、長尺のPVAフィルムの長さ方向(機械流れ方向;MD)に一軸延伸される。そのため、通常、フィルムの長さ方向(MD)は偏光フィルムなどの光学フィルムを製造する際にPVAフィルムが一軸延伸されるべき方向と一致し、この長さ方向と直交するフィルムの面内における方向が幅方向(TD)となる。なお長尺でないPVAフィルムの場合には、偏光フィルムなどの光学フィルムを製造する際に一軸延伸されるべき方向をフィルムの長さ方向(MD)とし、これと直交するフィルムの面内における方向を幅方向(TD)とすればよい。
すなわち、各測定点について、その測定点からフィルムの幅方向(TD)の一方の側に連続する250点(250ピッチ分)および他方の側に連続する250点(250ピッチ分)の合計500点の配向軸角度の平均値を求め、対象となる測定点における配向軸角度の値からこの平均値を差し引く。各測定点について同様の計算を行うことにより、長周期のノイズが排除された配向軸角度の変動を示すデータが得られる。この長周期のノイズが排除された配向軸角度の変動を示すデータを下記の方法で解析することにより、「隣接するピーク間の距離」が得られる。なお、上記長周期のノイズの排除を行う場合には、フィルムの幅方向(TD)の一方の側に連続する250点分の配向軸角度のデータのないフィルムの幅方向(TD)の両端部(それぞれ幅約20cmの部分)は、通常、光学フィルムの製造過程においてスリットされるなどして製品化されないことが多いため、「隣接するピーク間の距離」の解析から除外することができる。
隣接するピーク間の距離の最大値の下限は特に限定されないが、隣接するピーク間の距離の最大値があまりに小さいPVAフィルムは、生産性よく製造できにくいことから、隣接するピーク間の距離の最大値は0.1cm以上であることが好ましく、0.2cm以上であることがより好ましく、0.3cm以上であることがさらに好ましい。
隣接するピークにおける配向軸角度の差は、上記の「隣接するピーク間の距離」において検出されたピークにおける配向軸角度の値から求めることができる。
なお、本明細書におけるPVAのけん化度とはPVAが有するけん化によって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。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。
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などが好適である。
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。
以下に本発明において好適に採用し得る当該PVAフィルムの製造方法(以下「本発明の製造方法」ということがある)について説明する。
また、製膜原液の温度は、90~110℃とすることが好ましい。
PVAフィルムを製造するための装置には、PVAフィルムを適切な状態に調整するために、熱処理装置;調湿装置;各ロールを駆動するためのモータ;変速機などの速度調整機構などが付設されることが好ましい。
かかる点から、回転軸が互いに平行な複数の乾燥ロールを備えるドラム型製膜装置を用いてPVAフィルムを製造する場合は、第1ロールおよびそれに続くロールの表面温度を50~150℃、特に60~120℃とすることが好ましい。
また、乾燥ロールの下流に熱風乾燥装置をさらに配置する場合は、熱風乾燥装置内の雰囲気温度を50~150℃、特に60~120℃にすることが好ましい。
延伸後のフィルム(偏光フィルム)の厚みは、3~35μm、特に5~30μm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表示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、配向軸角度の分布における隣接するピーク間の距離および隣接するピークにおける配向軸角度の差、および、偏光フィルムの色斑は以下の方法により求めた。
(i) 上記で説明した方法で行った。
すなわち、以下の各実施例または比較例で得られた長尺のPVAフィルムの長さ方向(MD)の任意の位置から、PVAフィルムの長さ方向(MD)に40mmの長さを有する全幅長(3m)のテープ状のサンプル(テープ形状からいうと幅40mm、長さ3mのテープ)を採取した。すなわち、図2を参照して説明すると、A1とA2を結ぶ仮想直線が配向軸角度の測定部位となるように、A1とA2を結ぶ仮想直線を中央線とし、当該仮想直線の上流側に20mmおよび下流側に20mmで合計40mmとなるようにしてPVAフィルムの全幅にわたるテープ状のサンプルを採取した。
(ii) 上記(i)で採取したテープ状のサンプルについて、フィルムの幅方向中央部に測定位置を1つ定め(図2におけるA1とA2を結ぶ仮想直線の中間点A3)、この測定位置から幅方向両端部に向かって(A3→A1およびA3→A2)、それぞれ0.8mmピッチで測定位置を定めて、各測定位置でフィルム面内における配向軸角度の測定を行って、配向軸角度のデータを得た。
ここで、各測定位置での配向軸角度の測定は、フォトニックラティス社製「WPA-100-L」を用いて、フィルム面に対して垂直な方向に進行する波長543nmの光によって行った。
(iii) 各測定点について、その測定点からフィルムの幅方向(TD)の一方の側に連続する250点(250ピッチ分)および他方の側に連続する250点(250ピッチ分)の合計500点の配向軸角度の平均値を求め、対象となる測定点における配向軸角度の値からこの平均値を差し引いた。各測定点について同様の計算を行うことにより、長周期のノイズが排除された配向軸角度の変動を示すデータを得た。
次に、解析ソフトOrigin Pro 8.6J(OriginLab Corporation社製)を用いて、上記の長周期のノイズが排除された配向軸角度の変動を示すデータに基づいて配向軸角度の分布のピーク検出を行った。配向軸角度の分布のピーク検出に当たっては、基線モードとして「定数(平均)」を設定し、ピークフィットのフィルタリング方式として「高さに基づく(しきい値高さ30%)」を設定し、しきい値よりも小さいピークは除外した。
(iv) 次いで、各ピークにおける幅方向の位置を求め、互いに隣接するピーク間(互いに隣り合うピーク間)の幅方向の距離を算出し、それを「隣接するピーク間の距離」とし、そのうちの最大値を求めた。
(v) さらに、検出されたピークにおける配向軸角度の値に基づいて、互いに隣接するピーク間(互いに隣り合うピーク間)での配向軸角度の差を、それぞれのピーク間において算出し、そのうちの最大値を求めた。
暗室内で観察用偏光板(透過率が43%程度の偏光フィルムを用いたもの)を面光源(バックライト)上に載置し、その上に以下の実施例または比較例で作製した偏光フィルムを観察用偏光板に対してクロスニコルとなるように載置した後、バックライトから観察用偏光板を介して偏光フィルムに光を照射し(光度15,000cd)、偏光フィルム真上より1mの位置から偏光フィルムを目視によって観察して、以下の判定基準に基づく官能評価によって偏光フィルムの色斑の評価を行った。
◎:色斑が視認されない。
○:色斑が視認されるが、目立ちにくく実用上問題ないレベルである。
×:実用上問題となるレベルの色斑が視認された。
(1) PVA(酢酸ビニルの単独重合体のけん化物、重合度2,400、けん化度99.9モル%)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%および温度100℃の製膜原液を用い、これを回転軸が互いに平行な複数の乾燥ロールを備えるドラム型製膜装置の第1ロール(支持体)上にT型スリットダイを用いて膜状に吐出し、吐出後0.1秒の時点で風速0.81m/秒の風の吹き付けを開始し(風の吹き付け方向:PVA膜の第1ロールの非接触面に対してほぼ垂直の角度)、風の吹き付けを吐出後0.1~1秒の間行い、第1ロールから剥離する際のPVA膜の揮発分率を22質量%にし、さらにPVA膜の第1ロールの非接触面・接触面を後続する第2ロール以降の乾燥ロールに交互に接触させることにより、長尺のPVAフィルム(厚み60μm、幅3m、揮発分率4質量%)を連続的に製造した。
これにより得られたPVAフィルムについて、上記した方法により、配向軸角度の分布における隣接するピーク間の距離の最大値および隣接するピークにおける配向軸角度の差の最大値を求めた。結果を表1に示す。
これにより得られた偏光フィルムについて、上記した方法により色斑を評価した。その結果を表1に示す。
風の吹き付け開始時点、風の吹き付け時間、風速および第1ロールから剥離する際のPVA膜の揮発分率を表1に示した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て、得られたPVAフィルムの配向軸角度の分布における隣接するピーク間の距離の最大値および隣接するピークにおける配向軸角度の差の最大値の算出、並びに得られた偏光フィルムの色斑の評価を行った。その結果を表1に示す。
一方、比較例1~6のPVAフィルムは、配向軸角度の分布において隣接するピーク間の距離の最大値が6cmを超えていることにより、偏光フィルムを製造したときに、実用上問題となる色斑が発生した。
Claims (6)
- フィルムの面内における配向軸角度をフィルムの幅方向に0.8mmピッチで測定して求めた配向軸角度の分布において、隣接するピーク間の距離の最大値が6cm以下であることを特徴とするポリビニルアルコールフィルム。
- フィルムの面内における配向軸角度をフィルムの幅方向に0.8mmピッチで測定して求めた配向軸角度の分布において、隣接するピークにおける配向軸角度の差の最大値が10°以下である請求項1に記載のポリビニルアルコールフィルム。
- 幅が2m以上である、請求項1または2に記載のポリビニルアルコールフィルム。
- ポリビニルアルコールを含む製膜原液を吐出装置の吐出口から支持体上に膜状に吐出し、乾燥してポリビニルアルコールフィルムを製造する方法であって、吐出後10秒以内に風速0.3~5m/秒の風を吐出した膜に吹き付ける工程を有することを特徴とするポリビニルアルコールフィルムの製造方法。
- 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フィルムを用いて製造した光学フィルム。
- 偏光フィルムである請求項5に記載の光学フィルム。
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| JP2017102437A (ja) * | 2015-11-19 | 2017-06-08 | 日本合成化学工業株式会社 | 偏光膜製造用ポリビニルアルコール系フィルム、およびそれを用いた偏光膜、偏光板、ならびに偏光膜製造用ポリビニルアルコール系フィルムの製造方法 |
| JP2017102421A (ja) * | 2015-11-19 | 2017-06-08 | 日本合成化学工業株式会社 | ポリビニルアルコール系フィルム、偏光膜及び偏光板 |
| JP7503466B2 (ja) | 2020-09-24 | 2024-06-20 | 株式会社カネカ | フィルム製造方法及びフィルム製造装置 |
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| TWI641643B (zh) | 2018-11-21 |
| CN106029755B (zh) | 2021-10-26 |
| JP6556693B2 (ja) | 2019-08-07 |
| KR102387498B1 (ko) | 2022-04-15 |
| CN113416333A (zh) | 2021-09-21 |
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