WO2013146459A1 - ポリビニルアルコール系重合体フィルム - Google Patents
ポリビニルアルコール系重合体フィルム Download PDFInfo
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- WO2013146459A1 WO2013146459A1 PCT/JP2013/057792 JP2013057792W WO2013146459A1 WO 2013146459 A1 WO2013146459 A1 WO 2013146459A1 JP 2013057792 W JP2013057792 W JP 2013057792W WO 2013146459 A1 WO2013146459 A1 WO 2013146459A1
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- WIPO (PCT)
- Prior art keywords
- film
- pva
- polymer film
- polyvinyl alcohol
- defects
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
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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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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 is a polyvinyl alcohol polymer film (hereinafter, “polyvinyl alcohol” may be abbreviated as “PVA”) useful as a raw film for producing a polarizing film, a method for producing a polarizing film using the same, and
- PVA polyvinyl alcohol polymer film
- the present invention relates to a polarizing film, a film roll formed by continuously winding a PVA polymer film, and a method for producing a PVA polymer film.
- PVA polymer films are used in various applications by utilizing unique properties such as transparency, optical properties, mechanical strength, and water solubility.
- Applications as a raw material for producing a polarizing film (raw film) constituting a polarizing plate which is a basic component of a display (LCD) are expanding.
- LCD liquid crystal display
- screens are rapidly increasing.
- the yield product yield decreases. Accordingly, there is a demand for a polarizing plate with a small amount of light and a polarizing film.
- thermoplastic resin such as polyester, polyamide, or polyolefin
- a thermoplastic resin such as polyester, polyamide, or polyolefin
- the outer peripheral surface has a surface roughness of 1S or less.
- Patent Document 1 it is known to use a film production apparatus using a film production drum or roll having a chromium plating film containing 0.5 to 5% of carbon atoms as the number of atoms relative to chromium atoms on the surface.
- Patent Document 1 polyethylene terephthalate is melted at 275 ° C., extruded from a T-die and rapidly cooled with a casting drum cooled to 25 ° C. to form an amorphous sheet, and then a plurality of sheets arranged downstream of the casting drum. It is specifically described that when a metal roll is heated or cooled, a roll having a specific chromium plating film is used as a part of the plurality of metal rolls.
- Patent Document 2 a solution obtained by dissolving an aromatic polycarbonate resin in a mixed solvent of ethanol and methylene chloride and a support having a specific surface characteristic (a mirror polishing plate made of SUS-316) are used. Specifically, it is specifically described that an aromatic polycarbonate film was prepared by adjusting the temperature to about 15 ° C., hand-coating the solution on a support, and drying.
- a cooling drum is used.
- a film-like thermoplastic resin such as an alicyclic structure-containing polymer or cellulose ester
- an organic solvent is attached to the surface of the cooling drum, and then the wiping means is used to wipe the cooling drum.
- Patent Document 3 a mixture containing a hydrogenated norbornene-based ring-opening polymer and cellulose acetate propionate is melt-extruded, and a film-like resin melt is cooled with a specific cleaning means (with a Vickers hardness of 800). It is described that a resin sheet is obtained by cooling and solidifying while being in close contact with a hard chrome plating film surface or an amorphous chrome plating film surface having a Vickers hardness of 1200.
- a film-forming stock solution obtained by dissolving a PVA-based polymer in a liquid medium or a film-forming stock solution containing a PVA-based polymer and a liquid medium and melted by the PVA-based polymer is used as a method for forming a PVA polymer film.
- a method is known in which the film is cast on a metal support and dried to form a film.
- the method is a melt substantially free of a liquid medium as described in Patent Document 1. Since the method of forming a film by cooling a polymer on a casting drum is greatly different, the film manufacturing drum described in Patent Document 1 is simply used, and the film is prepared using the above-described film forming stock solution.
- the fine defects based on the fine cracks present on the surface of the chromium plating film of the film production drum are sufficient.
- the polarizing plate or polarizing film produced using the PVA based polymer film obtained can not be fully achieved the quality level required in recent years.
- Patent Document 2 relates to a film forming method in which a solution containing a polymer resin and a solvent as main components is cast on a support and then dried to remove the solvent. Even if the defects raised in the shape of protrusions on the film surface can be eliminated by adopting the film, the defects recessed from the film surface cannot be controlled sufficiently and are produced using the obtained PVA polymer film. In addition, the polarizing plates and polarizing films cannot sufficiently achieve the quality level required in recent years.
- the method of patent document 3 cools the melt of a thermoplastic resin with a cooling drum like the method of patent document 1, the method of patent document 3 is employ
- an object of the present invention is to provide a PVA polymer film capable of producing a polarizing film with few defects and thus a polarizing plate with high yield.
- the present invention is a film roll in which a long PVA polymer film is continuously wound, and the difference in surface characteristics from the winding start portion to the winding end portion of the PVA polymer film is small.
- An object of the present invention is to provide a film roll capable of producing a polarizing film having a stable quality and thus a polarizing plate.
- the PVA polymer film is often in the form of a film roll in which a long PVA polymer film is continuously wound for reasons such as ease of storage and transportation and continuous use.
- wrinkles are likely to occur on the film due to poor slip properties between the films, and such wrinkles tend to cause a deterioration in the quality of the polarizing film to be produced.
- the polarizing film may be required to reduce stained spots different from the above-described defects. Accordingly, the present invention provides, as another aspect, a PVA polymer film capable of easily producing a polarizing film in which wrinkles are unlikely to occur in a film roll and the dyeing spots are reduced, and the film is continuously wound. It aims at providing the film roll formed.
- the PVA polymer film is usually dyed, uniaxially stretched, fixed, etc., but is dry and uniaxially stretched.
- the dyeing process and the fixing process and in the case of wet uniaxial stretching, in addition to these processes, in the swelling process and uniaxial stretching process before uniaxial stretching, A part of the coalescence may be eluted, and the eluted PVA polymer is deposited in the treatment bath and adheres to the film, or deposits on the film and remains as a foreign substance in the obtained polarizing film. May reduce quality and yield.
- this invention aims at providing the manufacturing method of the polarizing film for manufacturing such a polarizing film with few foreign materials, and a polarizing film with few foreign materials manufactured by it.
- an object of this invention is to provide the manufacturing method of the PVA polymer film which can manufacture the above PVA polymer films and film rolls simply.
- the present inventors have cast a PVA polymer in a solution state or a molten state on the surface of a metal support such as a drum or a belt, and then dried the PVA polymer to obtain a PVA.
- a foreign substance that appears to be a resin deposit adheres to a very small part of the innumerable cracks that existed on the surface of the metal support, and the resulting convex shape is formed on the film.
- the quality level required in recent years cannot be sufficiently achieved or the yield of the polarizing film or polarizing plate is reduced.
- a metal support having a chrome plating layer on the surface and having a surface hardness within a specific range it is possible to perform a general process such as buffing on the surface of the metal support before starting film formation.
- the number of cracks existing on the surface of the metal support can be easily reduced, and the number of defects recessed from the film surface of the resulting PVA polymer film can be reduced as compared with the conventional PVA system. It has been found that when a polymer film is used as a raw film for producing a polarizing film, a polarizing film and a polarizing plate having few defects and satisfying a recently required quality level can be produced with high yield.
- the film surface can be formed even if a PVA polymer film is continuously formed over a long period of time.
- the variation in the number of defects recessed from the surface can be kept at a lower level than before.
- a PVA polymer film having surface characteristics on both sides of the film in a specific range can be easily obtained.
- wrinkles are unlikely to occur and the deterioration of the quality of the polarizing film can be suppressed, and according to the PVA polymer film, a polarizing film with reduced staining spots is obtained. It was found that it can be easily obtained, and that when a polarizing film is produced by a specific method using the PVA polymer film, a polarizing film with few foreign matters can be easily obtained.
- the present inventors have further studied based on such knowledge and completed the present invention.
- a PVA polymer film (hereinafter referred to as this PVA) in which the number of defects that are recessed from the film surface and have an area of 400 ⁇ m 2 or more and a depth of 0.3 ⁇ m or more is 0.25 / m 2 or less.
- PVA polymer film (1) The PVA polymer film of the above [1], wherein the number of the defects is 0.15 / m 2 or less; [3] The PVA polymer film of the above [1] or [2], wherein the polymerization degree of the PVA polymer contained in the PVA polymer film is 3,000 or more and 10,000 or less; [4] The PVA polymer film as described in any one of [1] to [3], which is a long PVA polymer film; [5] The PVA polymer film of [4], having a length of 6,000 m or more; [6] The PVA-based weight according to [4] or [5] above, wherein the defects include defects that exist at substantially the same position in the width direction of the film at substantially constant intervals in the length direction of the film. Coalesced film;
- film roll (1) Sometimes referred to as “film roll (1)”);
- the film roll of the above [7], wherein the number of the defects is 0.15 / m 2 or less;
- the film roll according to any one of the above [7] to [9], wherein the polymerization degree of the PVA polymer contained in the PVA polymer film is from 3,000 to 10,000.
- a PVA polymer film (hereinafter, this PVA polymer film may be referred to as “PVA polymer film (2)”); [14] The PVA polymer film of the above [13], wherein the larger root mean square roughness is 1 nm or more and 20 nm or less; [15] The PVA polymer film of the above [13] or [14], which is a long PVA polymer film; [16] A film roll obtained by continuously winding the PVA polymer film of the above [15] (hereinafter, this film roll may be referred to as “film roll (2)”); [17] A method for producing a polarizing film using the PVA polymer film according to any one of [13] to [15] as a raw film, comprising a dyeing step, a uniaxial stretching
- the angle formed between the liquid surface of the treatment bath and the film surface is 30 ° to 85 °, and the upper surface of the film is polyvinyl alcohol.
- a production method which is a surface having a smaller root mean square roughness in a polymer film; [18] A polarizing film produced by the production method of [17] above;
- a method for producing a PVA polymer film comprising a step of casting and drying the PVA polymer to form a film, and immediately before casting the solution or molten PVA polymer.
- a PVA polymer film capable of producing a polarizing film with few defects and thus a polarizing plate with high yield.
- it is a film roll by which a long PVA polymer film is wound up continuously, Comprising: The difference in the surface characteristics from the winding start part of a PVA polymer film to the winding completion part
- the film roll which can manufacture a polarizing film with small and stable quality and by extension, a polarizing plate can be provided.
- a PVA polymer film capable of easily producing a polarizing film in which wrinkles hardly occur in a film roll and dyeing spots are reduced, and the film is continuously wound. It is possible to provide a film roll, a method for producing a polarizing film for producing a polarizing film with little foreign matter, and a polarizing film with little foreign matter produced thereby.
- group polymer film which can manufacture the above-mentioned PVA type
- PVA polymer film (1) The PVA polymer film of the present invention (PVA polymer film (1)) is a defect that is recessed from the film surface and has an area of 400 ⁇ m 2 or more and a depth of 0.3 ⁇ m or more (hereinafter referred to as this defect).
- the number of “defects A” may be 0.25 / m 2 or less.
- voids bubbles
- fish eyes caused by foreign matter adhering to and sticking
- scratches mostly groove-shaped dents
- the present inventors are excellent in that a polarizing film and a polarizing plate with few defects can be produced with high yield by controlling the number of the defects A in particular. It was found that the effect was achieved.
- This defect A is considered to be caused by the convex transfer on the film forming apparatus described above.
- a PVA polymer film is formed using a metal support such as a drum or a belt.
- one of the causes is that the convex shape due to the foreign matter that seems to be a resin deposit adhered on the metal support is transferred to the film.
- the defect A occurs in the long PVA polymer film due to such a cause, at least a part of the defect A is at a substantially constant interval in the length direction of the film and in the width direction of the film.
- a plurality for example, three or more
- the substantially constant interval typically corresponds to the length of one round of a metal support such as a drum or a belt (the total circumference). May correspond to an integer multiple of the length.
- the convex shape by a foreign material can be formed in multiple numbers on a metal support body, the group of the fault A arranged as mentioned above may also exist.
- the number of defects A is 0.25 / m 2 or less. If the number of defects A exceeds 0.25 / m 2 , the polarizing film or polarizing plate produced therefrom has a large number of defects, and the quality level required in recent years cannot be sufficiently achieved, or a polarizing film having many defects. If the polarizing plate is discarded, the yield of these products may be reduced.
- the number of defects A is preferably 0.20 piece / m 2 or less, more preferably 0.15 piece / m 2 or less, and 0.10 piece / m 2 or less. More preferably, it is particularly preferably 0.075 / m 2 or less.
- the lower limit of the number of defects A is not necessarily limited, but in order to extremely reduce the number of defects A, there is a risk that the cost for installing the film-forming equipment may become extremely high.
- the number of defects A is preferably 0.001 piece / m 2 or more, more preferably 0.003 piece / m 2 or more, and further preferably 0.005 piece / m 2 or more.
- Defect A is a defect that is recessed from the film surface and has an area of 400 ⁇ m 2 or more and a depth of 0.3 ⁇ m or more.
- the defect A only needs to be recessed from either one of both sides of the film toward the inside of the film, but most of the defect A is usually in contact with a metal support described later used during film formation. It is recessed toward the inside of the film from the surface where it was done.
- the area of the defect A means the area of the opening of the defect A.
- the depth of the defect A means the depth in the direction perpendicular to the film surface from the opening of the defect A and the depth at the deepest position.
- the number of defects A is the PVA polymer film in which the defect A is searched from one end of the target PVA polymer film and examined until 10 defects A are found. Can be obtained by dividing 10 (units) by the area (unit: m 2 ), specifically, by the method described later in the examples.
- the determination as to whether or not each defect is the defect A can be performed using a non-contact surface shape measuring machine.
- the film is a long PVA polymer film.
- the length of the long PVA polymer film is not particularly limited, and can be appropriately set according to the use of the PVA polymer film (1). Specifically, the length is 1,000 m. Is preferably 4,000 m or more, more preferably 6,000 m or more, particularly preferably 7,000 m or more, and most preferably 8,000 m or more. .
- the number of defects A of the PVA polymer film can be reduced, and even if the PVA polymer film is continuously formed over a long period of time, Since the fluctuation of the number can be kept at a low level, it is possible to easily obtain a PVA polymer film with a reduced number of defects A even when the length is longer (for example, 6,000 m or more). it can. According to such a longer PVA polymer film, it is possible to stably produce a product satisfying the quality level required in recent years with few defects when producing a polarizing film continuously over a long period of time with a high yield.
- the upper limit of the length of the long PVA polymer film is not particularly limited. However, if it is too long, the handling property is deteriorated due to excessive increase in weight and roll diameter when used as a film roll, and storage and transportation are reduced.
- the length is preferably 30,000 m or less, more preferably 25,000 m or less, and even more preferably 20,000 m or less because it may be difficult.
- the width of the PVA-type polymer film is preferably 7 m or less.
- the thickness of the PVA polymer film (1) is not particularly limited and can be appropriately set according to the use of the PVA polymer film. Specifically, the thickness is preferably 300 ⁇ m or less, and 150 ⁇ m. Or less, more preferably 100 ⁇ m or less. In recent years, a thinner polarizing film may be required. From such a viewpoint, the thickness of the PVA polymer film (1) is preferably 45 ⁇ m or less, and more preferably 35 ⁇ m or less. Preferably, it is 25 ⁇ m or less.
- the said thickness is preferably 3 micrometers or more, and it is 5 micrometers or more. More preferred.
- a polymer produced by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester monomer can be used.
- vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like. Among these, vinyl acetate is preferable.
- the vinyl ester polymer is preferably obtained by using only one or two or more vinyl ester monomers as a monomer, and using only one vinyl ester monomer as a monomer. Although what was obtained is more preferable, the copolymer of 1 type, or 2 or more types of vinyl-ester type monomers and the other monomer copolymerizable with this may be sufficient.
- vinyl ester monomers include, for example, ethylene; olefins having 3 to 30 carbon atoms such as propylene, 1-butene and isobutene; acrylic acid or salts thereof; methyl acrylate, acrylic Such as ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
- Acrylic acid ester methacrylic acid or salt thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, methacrylic acid 2-ethylhexyl, dodecyl methacrylate
- Methacrylic acid esters such as octadecyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamide propanesulfonic acid or salt thereof, acrylamidopropyldimethylamine or salt thereof, N Acrylamide derivatives such as methylolacrylamide or derivatives thereof; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid or
- Vinyl amides such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; acrylonitrile, methacrylonitrile, etc.
- Vinyl cyanide vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid or its salt, ester or acid anhydride; itaconic acid or its salt , Esters or acid anhydrides; vinylsilyl compounds such as vinyltrimethoxysilane; isopropenyl acetate and the like.
- the vinyl ester polymer can have a structural unit derived from one or more of these other monomers.
- the proportion of the structural unit derived from the other monomer in the vinyl ester polymer is not particularly limited, but based on the number of moles of all structural units constituting the vinyl ester polymer, it is 15 mol% or less. It is preferable that it is 5 mol% or less.
- the degree of polymerization of the PVA polymer is not necessarily limited, but is preferably 200 or more, more preferably 300 or more, more preferably 400 or more, because the film strength tends to decrease as the degree of polymerization decreases. Particularly preferred is 500 or more. Further, if the degree of polymerization is too high, the viscosity of the aqueous solution or melted PVA polymer tends to be high, and film formation tends to be difficult. Therefore, it is preferably 10,000 or less, more preferably 9,000. Hereinafter, it is more preferably 8,000 or less, and particularly preferably 7,000 or less.
- the degree of polymerization of the PVA polymer means an average degree of polymerization measured according to the description of JIS K6726-1994.
- the intrinsic viscosity [ ⁇ ] (unit: deciliter / g) is obtained by the following formula.
- Degree of polymerization ([ ⁇ ] ⁇ 10 3 /8.29) (1 / 0.62)
- the degree of polymerization of the PVA polymer is more preferably 4,000 or more, and further preferably 5,000 or more.
- the degree of saponification of the PVA polymer there is no particular limitation on the degree of saponification of the PVA polymer.
- the degree of saponification of the PVA polymer is preferably 95 mol% or more, more preferably 98 mol% or more, and further preferably 99 mol% or more.
- the degree of saponification of the PVA polymer is the total number of moles of structural units (typically vinyl ester monomer units) that can be converted into vinyl alcohol units by saponification and the vinyl alcohol units of the PVA polymer. Is the ratio (mol%) occupied by the number of moles of the vinyl alcohol unit.
- the degree of saponification of the PVA polymer can be measured according to the description of JIS K6726-1994.
- one PVA polymer may be used alone, or one or more of the degree of polymerization, the degree of saponification, the degree of modification, and the like. Two or more types of PVA polymers different from each other may be used in combination.
- the content of the PVA polymer in the PVA polymer film (1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 85% by mass or more.
- the PVA polymer film (1) preferably contains a plasticizer.
- a plasticizer is preferably a polyhydric alcohol, and specific examples include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane. These plasticizers may be used alone or in combination of two or more. Among these plasticizers, ethylene glycol or glycerin is preferable from the viewpoint of compatibility with PVA-based polymers and availability.
- the content of the plasticizer in the PVA polymer film (1) is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the PVA polymer, and is in the range of 3 to 25 parts by mass. More preferably, the content is in the range of 5 to 20 parts by mass.
- the PVA polymer film (1) preferably contains a surfactant from the viewpoint of improving the peelability from the metal support used in the production and improving the handleability of the PVA polymer film.
- a surfactant from the viewpoint of improving the peelability from the metal support used in the production and improving the handleability of the PVA polymer film.
- Anionic or nonionic surfactant can be used preferably.
- the anionic surfactant include carboxylic acid types such as potassium laurate, sulfate ester types such as octyl sulfate, and sulfonic acid types such as dodecylbenzene sulfonate.
- Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether, alkylphenyl ether types such as polyoxyethylene octylphenyl ether, alkyl ester types such as polyoxyethylene laurate, and polyoxyethylene laurylamino.
- Alkylamine type such as 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
- polyoxy Examples include allyl phenyl ether type such as alkylene allyl phenyl ether.
- the content of the surfactant in the PVA polymer film (1) is 0. 0 with respect to 100 parts by mass of the PVA polymer from the viewpoints of peelability from the metal support and handleability of the PVA polymer film. It is preferably within the range of 01 to 1 part by mass, more preferably within the range of 0.02 to 0.5 part by mass, and further preferably within the range of 0.05 to 0.3 part by mass. preferable.
- the PVA polymer film (1) may further contain other components other than the PVA polymer, the plasticizer, and the surfactant as necessary.
- other components include moisture, antioxidants, ultraviolet absorbers, lubricants, colorants, fillers (inorganic particles, starch, etc.), preservatives, antifungal agents, and other components other than those described above. Examples thereof include polymer compounds.
- the film roll of the present invention is a film roll in which a long PVA polymer film is continuously wound, and the winding start portion (PVA system) of the PVA polymer film
- the winding end portion of the PVA polymer film (when the winding of the PVA polymer film is finished as a film roll) with respect to the number of defects A in the film portion when the polymer film is started as a film roll)
- the number of the defects A in the film portion) is 1.4 times or less.
- the number of the defects A in the winding end portion of the PVA polymer film with respect to the number of the defects A in the winding start portion of the PVA polymer film is 1.3 times or less. Preferably, it is 1.2 times or less, more preferably 1.1 times or less.
- the number of defects A tends to increase with time in the formation of a long PVA polymer film, the PVA weight relative to the number of defects A in the winding start portion of the PVA polymer film is increased.
- the number of the defects A at the end of winding of the combined film is usually 0.6 times or more, and from the viewpoint of producing a polarizing film having a stable quality and thus a polarizing plate,
- the number of defects A in the winding end portion of the PVA polymer film relative to the number of defects A in the winding start portion is preferably 0.7 times or more, and more preferably 0.75 times or more. 0.8 times or more is more preferable, and 0.9 times or more is particularly preferable.
- the number of defects A per unit area is not particularly limited, but the number of defects A in the PVA polymer film (1) of the present invention is described above.
- the number of defects A is 0.25 / m 2 or less (with respect to the upper limit, preferably 0.20 / m 2 or less, more preferably 0.15 / m 2 or less, Preferably it is 0.10 piece / m 2 or less, particularly preferably 0.075 piece / m 2 or less, and regarding the lower limit, it is preferably 0.001 piece / m 2 or more, more preferably 0.003 piece / m 2 or more, More preferably, 0.005 pieces / m 2 or more)
- a polarizing film is continuously produced, a product satisfying a quality level required in recent years with few defects can be stably obtained with a high yield over a long period of time.
- the length (winding length) of the PVA polymer film used in the film roll (1) of the present invention is not particularly limited, and can be appropriately set according to the use of the PVA polymer film, Specifically, the length can be 1,000 m or more. However, in recent years, a PVA polymer film longer than the conventional length of about 4,000 m may be required in order to reduce the complexity and time loss associated with film roll switching in the production of polarizing films.
- the length of the PVA polymer film is 6,000 m or more because the quality of the product can be stabilized even if the polarizing film is produced continuously for a long time using a longer PVA polymer film. It is preferably 7,000 m or more, and more preferably 8,000 m or more.
- the upper limit of the length of the long PVA polymer film is not particularly limited. However, if it is too long, the handling property is deteriorated due to excessive increase in weight and roll diameter when used as a film roll, and storage and transportation are reduced.
- the length is preferably 30,000 m or less and may be 25,000 m or less because it may be difficult and it may be difficult to produce a film roll that satisfies the provisions of the present invention. It is more preferable that it is 20,000 m or less. In addition, if the said length is 14,000 m or less, Furthermore, if it is 10,000 m or less, manufacture of the film roll which satisfy
- the other configuration relating to the PVA polymer film used in the film roll (1) of the present invention can be the same as that described above for the explanation of the PVA polymer film (1) of the present invention. Therefore, the overlapping description is omitted here.
- a long PVA polymer film is continuously wound, for example, a long PVA polymer film is continuously wound around a cylindrical core.
- a cylindrical core it is preferable that both ends of the core form protrusions that protrude from the end face of the film roll.
- cylindrical core there is no particular limitation on the type of the above-described cylindrical core, and examples thereof include a metal one, a plastic one, a paper one, and a wooden one. It is also possible to use a core in the form of a composite, such as one using both metal and plastic, one using both metal and paper, and one using both plastic and paper. Among these, in consideration of strength, durability, low dust generation, etc., a metal and / or plastic core is preferable, and a metal core is more preferable because it is not easily affected by wear and the like even when used repeatedly. . Examples of the metal include iron, stainless steel, and aluminum. One of these may be used alone, or two or more may be used in combination.
- the plastic examples include polyvinyl chloride, polyvinylidene chloride, polyester, polycarbonate, polyamide, epoxy resin, polyurethane, polyurea, and silicone resin. One of these is used alone. Moreover, you may use 2 or more types together.
- the plastic may be fiber reinforced plastic (FRP) such as carbon fiber reinforced plastic from the viewpoint of strength and the like.
- PVA polymer film (2) In the PVA polymer film of the present invention (PVA polymer film (2)), when the root mean square roughness was measured on each of both surfaces of the film, the difference between the two root mean square roughnesses obtained was 0. 3 nm or more and 10 nm or less, and the smaller root mean square roughness is 10 nm or less. In the conventional film roll in which the PVA polymer film is continuously wound, wrinkles are likely to occur in the film due to poor slip between the films, etc., but according to the PVA polymer film (2) of the present invention, Generation
- the film roll wrinkles occur when the PVA polymer film is wound up, and the stress remaining in the PVA polymer film when the film roll is stored in a warehouse or the like once In this case, the squeezing is caused by the poor slipping property between the films.
- the former wrinkles are effectively generated. Although it can be reduced, the occurrence of the latter soot can also be reduced.
- the root mean square roughness in the present invention means the root mean square roughness (Rq) described in JIS B0601: 2001, and the deviation from the mean line to the roughness curve in the roughness curve obtained from the surface of the film. It is obtained by averaging the squares.
- the root mean square roughness on each side of the PVA polymer film can be measured by the method described later in the examples.
- the difference between the two root mean square roughness obtained is 0.3 nm or more and 10 nm or less. is required.
- production of the wrinkle in a film roll can be effectively reduced because both difference is 0.3 nm or more.
- the difference between the two is 10 nm or less, stained spots in the polarizing film can be effectively reduced.
- the difference between the two is preferably 0.5 nm or more, more preferably 0.8 nm or more, further preferably 1.2 nm or more, and 1.5 nm or more. Particularly preferred is 2 nm or more, most preferred is 7 nm or less, and more preferred is 5 nm or less.
- the smaller root mean square roughness is 10 nm or less.
- the smaller root mean square roughness is preferably 8 nm or less, more preferably 6 nm or less, and further preferably 4 nm or less.
- the root mean square roughness on the smaller side is 0.3 nm or more. Is preferably 0.6 nm or more, more preferably 0.9 nm or more, and particularly preferably 1.2 nm or more.
- the larger root mean square roughness is preferably 1 nm or more and 20 nm or less.
- production of the wrinkle in a film roll can be more effectively reduced because the larger mean square roughness is 1 nm or more.
- the larger root mean square roughness is 20 nm or less, stained spots in the polarizing film can be more effectively reduced.
- the larger root mean square roughness is more preferably 2 nm or more, further preferably 4 nm or more, more preferably 15 nm or less, and further preferably 11 nm or less. 8 nm or less is particularly preferable, and 6 nm or less is most preferable.
- the film is a long PVA polymer film.
- the length of the long PVA polymer film is not particularly limited, and can be appropriately set according to the use of the PVA polymer film (2). Specifically, the length is 1,000 m. Is preferably 4,000 m or more, more preferably 6,000 m or more, particularly preferably 7,000 m or more, and most preferably 8,000 m or more. .
- the upper limit of the length of the long PVA polymer film is not particularly limited. However, if it is too long, the handling property is deteriorated due to excessive increase in weight and roll diameter when used as a film roll, and storage and transportation are reduced.
- the length is preferably 30,000 m or less, more preferably 25,000 m or less, and even more preferably 20,000 m or less because it may be difficult.
- As one of the causes of wrinkles generated when the film roll is stored there is a winding squeezing due to the stress remaining in the PVA polymer film, but this winding squeezing is longer and wider. Since it tends to appear strongly in the PVA polymer film, the effect of the present invention is more remarkably exhibited in a longer PVA polymer film.
- variety of a long PVA-type polymer film there is no restriction
- the thickness of the PVA polymer film (2) is not particularly limited and can be appropriately set according to the use of the PVA polymer film. Specifically, the thickness is preferably 300 ⁇ m or less, and 150 ⁇ m. Or less, more preferably 100 ⁇ m or less. In recent years, a thinner polarizing film may be required. From such a viewpoint, the thickness of the PVA polymer film (2) is preferably 45 ⁇ m or less, and more preferably 35 ⁇ m or less. Preferably, it is 25 ⁇ m or less.
- the said thickness is preferably 3 micrometers or more, and it is 5 micrometers or more. More preferred.
- the wrinkle in a film roll is easy to generate
- the other configuration relating to the PVA polymer film (2) of the present invention can be the same as that described above for the description of the PVA polymer film (1) of the present invention, and therefore overlaps here. Description is omitted.
- the target PVA-type polymer film (2) is simply manufactured. This is preferable because it can be performed.
- the side in contact with the surface of the metal support tends to be a surface having the larger root mean square roughness.
- the film roll of the present invention is the PVA polymer film (2) described above, and is formed by continuously winding a long PVA polymer film.
- a long PVA polymer film (2) which is a PVA polymer film (2), is continuously wound around the core.
- both ends of the core form protrusions that protrude from the end face of the film roll.
- the film roll (2) of the present invention can reduce the occurrence of wrinkles that are likely to occur when the conventional film roll is stored.
- the temperature when storing the film roll is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, because if the temperature is too high, the PVA polymer film is deformed and wrinkles are likely to occur. Preferably, it is 30 degrees C or less.
- the lower limit of the temperature when storing the film roll is not particularly limited, but the temperature is preferably ⁇ 10 ° C. or higher, more preferably ⁇ 5 ° C. or higher, and preferably 0 ° C. or higher. Further preferred.
- the production method of the present invention for producing a PVA polymer film has a chromium plating layer on the surface, the surface hardness is 550 HV or more and less than 900 HV in terms of Vickers hardness, and the surface temperature is 50 ° C. or more and 115 ° C. or less.
- the number of cracks having an area (the product of the maximum width and the maximum end-to-end distance) of 200 ⁇ m 2 or more on the surface of the metal support immediately before starting to cast the PVA polymer in the solution state or the molten state is 0.
- the metal support used in the present invention includes a drum or a belt, and has a chromium plating layer on the surface thereof.
- the surface of the metal support means a surface (film-forming surface) on which a PVA polymer in a solution state or a molten state is cast.
- chromium is formed on the outer peripheral surface of the drum. What is necessary is just to have a plating layer, and in the case of a belt, it is only necessary to have a chromium plating layer on the outer surface of the continuous surface of the belt.
- the thickness of the chrome plating layer is not particularly limited, but it can be more effectively prevented from corroding the surface of the metal support, and the number of cracks described later can be easily reduced. preferable.
- the chrome plating layer may be formed at one time or may be formed in multiple times. For example, when the chrome plating layer is formed in multiple times, After forming the chrome plating layer, the irregularities on the surface thereof may be removed by polishing or the like, and a chrome plating layer may be further formed thereon. In this way, pinholes in the chrome plating layer can be reduced.
- a nickel plating layer is provided under the chromium plating layer, cracks in the chromium plating layer can be further reduced.
- the surface hardness is required to be 550 HV or more and less than 900 HV in terms of Vickers hardness.
- a metal support having a general chrome plating layer is known (see, for example, Patent Documents 4 to 7), the reason is unknown when a metal support having a specific surface hardness as in the present invention is used.
- the number of the defects A in the PVA polymer film can be reduced as compared with the prior art, and even if the PVA polymer film is continuously formed over a long period of time, the variation in the number of the defects A can be reduced. Can also be kept at a low level. Moreover, the root mean square roughness of both surfaces of the film can be adjusted to a desired range. When the surface hardness is 900 HV or higher in terms of Vickers hardness, it becomes difficult to reduce the number of cracks present on the surface of the metal support, and a PVA polymer film is continuously formed over a long period of time. In this case, the fluctuation of the number of the defects A becomes large.
- the root mean square roughness on both sides of the film tends to deviate from the desired range.
- the surface hardness is Vickers hardness, preferably less than 800 HV, and more preferably less than 780 HV.
- the surface hardness is less than 550 HV in terms of Vickers hardness, it is easy to cause problems such as scratches during continuous film formation or cleaning of the surface of the metal support, and the PVA polymer film is continued for a long time.
- the surface hardness is preferably 600 HV or more, more preferably 650 HV or more, and further preferably 700 HV or more in terms of Vickers hardness.
- the surface hardness of the metal support can be obtained by measuring the Vickers hardness of the surface of the chrome plating layer at a plurality of locations using a hardness meter or the like and averaging them.
- the surface hardness (Vickers hardness) may be measured on the surface (film-formed surface) on which a PVA polymer in a solution state or a molten state is cast, but a PVA from which scratches generated during the measurement can be obtained. Since the quality of the polymer film may be lowered, the surface on which the PVA polymer in the solution state or the molten state is cast, such as a portion where the chromium plating layer is formed at the end of the drum or belt ( Corresponds to the film part that is removed by ear cutting etc.
- the surface hardness of the surface to be measured is measured, and the value may be set as the surface hardness defined in the present invention.
- the surface hardness of the metal support can be determined by the method described later in Examples.
- Adjustment of the surface hardness of the metal support having a chrome plating layer on the surface can be easily performed by a known method. Specifically, the temperature of the chrome plating bath used for chrome plating is specified. Method of adjusting within the range; Method of adjusting the current density during chrome plating within a specific range; Method of adjusting the composition of the chrome plating bath; Chromium plating after heat treatment (annealing) or exposure to hydrogen gas, etc. It can be performed by a method of adjusting the hydrogen concentration occluded in the plating layer.
- the method of adjusting the temperature of the chromium plating bath within a specific range because the operation is simple; the method of adjusting the current density during the chromium plating treatment within a specific range; after the chromium plating treatment
- a method of adjusting the hydrogen concentration occluded in the chromium plating layer is preferable, and a method of adjusting the temperature of the chromium plating bath within a specific range is more preferable.
- the temperature of the chrome plating bath is in the range of 40 ° C.
- the surface hardness tends to be generally lower as the temperature of the chrome plating bath is higher and the current density is lower.
- the surface hardness tends to generally decrease as the heat treatment temperature is increased or the treatment time is lengthened to decrease the concentration.
- the method for forming the chromium plating layer is not particularly limited as long as the surface hardness can be a metal support that satisfies the above range, and a known method can be adopted.
- the surface of the metal support is polished by a method such as buffing or grinder polishing to remove surface irregularities as much as possible, and then surface treatment such as immersion degreasing, electrolytic degreasing, and aqueous hydrochloric acid immersion is performed, and then chromium Examples thereof include a method of performing a chrome plating process using a plating bath and further performing a heat treatment.
- a chromium plating bath a surge bath is typical and can be preferably used.
- composition of the Sargent bath and the conditions of the chrome plating treatment are shown below.
- ⁇ Composition of surge bath> Chromic anhydride: 100 to 300 g / L (concentration based on chemicals used)
- Sulfuric acid 1/50 to 1/150 (mass ratio) of chromic anhydride used
- the temperature of the chrome plating bath greatly affects the surface hardness of the metal support obtained as described above.
- the specific temperature of the chrome plating bath is preferably 50 ° C. or more, more preferably 53 ° C. or more, although it depends on other conditions employed in the chrome plating process and heat treatment conditions after the chrome plating process. More preferably, it is more preferably 54 ° C. or higher. If the temperature of the chrome plating bath is too low, the surface hardness of the obtained metal support tends to be excessively high.
- the temperature of the chromium plating bath is preferably 66 ° C. or less, more preferably 63 ° C. or less, further preferably 61 ° C. or less, and particularly preferably 58 ° C. or less. If the temperature of the chrome plating bath is too high, the surface hardness of the obtained metal support tends to be excessively low.
- the heat treatment temperature is preferably 130 ° C. or less, more preferably 120 ° C. or less.
- the temperature of the heat treatment is preferably 70 ° C. or higher, more preferably 90 ° C. or higher.
- the heat treatment time can be set within the range of 24 to 120 hours, although it depends on the conditions of the chromium plating treatment and the temperature of the heat treatment.
- a film-forming stock solution obtained by dissolving a PVA-based polymer in a liquid medium or a film-forming stock solution obtained by melting a PVA polymer containing a PVA-based polymer and a liquid medium And the like in the form of a film-forming stock solution containing a PVA polymer and a liquid medium.
- the film-forming stock solution may further contain a plasticizer, a surfactant, and other components as described above, if necessary.
- liquid medium in the film-forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, Examples thereof include ethylenediamine and diethylenetriamine, and one or more of these can be used.
- water is preferable from the viewpoint of a small environmental load and recoverability. That is, as a preferable example of the PVA polymer in a solution state or a molten state, one in the form of a film forming stock solution containing a PVA polymer and water can be mentioned.
- the volatile fraction of the film-forming stock solution (the content ratio of volatile components such as a liquid medium removed by volatilization or evaporation during film-forming in the film-forming stock solution) varies depending on the film-forming method, film-forming conditions, etc. It is preferably in the range of 90% by mass, and more preferably in the range of 55-80% 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 when preparing the film-forming stock solution, and there are few foreign matters and defects. Manufacture of a polymer film becomes easy.
- the volatile fraction of the film-forming stock solution is 90% by mass or less, the concentration of the film-forming stock solution does not become too low, and the production of an industrial PVA polymer film becomes easy.
- a PVA polymer is dissolved in a liquid medium such as water, and at that time, a plasticizer, a surfactant, and other components as necessary.
- a method of adding at least one, or a PVA polymer containing a liquid medium such as water is melt-kneaded using an extruder, and at that time, a plasticizer, a surfactant, etc. And a method in which at least one of these components is melt-kneaded together.
- the above-mentioned solution or melted PVA polymer is formed on the surface of the metal support having a surface temperature of 50 ° C. or higher and 115 ° C. or lower.
- the film is cast and dried to form a film.
- the surface temperature of the metal support exceeds 115 ° C., the number of defects A increases in the resulting PVA polymer film.
- the root mean square roughness of both surfaces of the film tends to be out of the desired range.
- the surface temperature of the metal support is preferably 105 ° C. or lower, more preferably 102 ° C. or lower, further preferably 99 ° C. or lower, particularly preferably 96 ° C.
- the surface temperature of the metal support is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher.
- a heat medium such as water, oil, or water vapor is provided inside the drum. It is possible to employ a method of passing through, heating with a dielectric heater installed inside the drum, or heating with an infrared heater or hot air heater installed so as to face the surface of the drum.
- the temperature change rate when the surface temperature of the metal support is within the above range before the start of film formation for example, as described in Patent Document 5, it can be 3 ° C./hour or less.
- the reason is unknown, but it exists on the surface of the metal support even if the temperature change rate is relatively high.
- the number of the defects A in the PVA polymer film obtained can be controlled to a low level even if the increase in the number of cracks to be suppressed can be suppressed and the productivity is improved by reducing the temperature adjustment time. I found.
- the temperature change rate when the surface temperature of the metal support is within the above range before the start of film formation is preferably 0.5 ° C./hour or more, and preferably 1 ° C./hour or more. More preferably, it may be 3.5 ° C./hour or more, 4 ° C./hour or more, 4.5 ° C./hour or more, and further 5 ° C./hour or more.
- the temperature change rate is preferably 10 ° C./hour or less, more preferably 7 ° C./hour or less, from the viewpoint of reducing the number of cracks.
- the surface temperature of the metal support is set within the above range before the start of film formation, it is preferable to reduce the temperature difference in the width direction of the metal support from the viewpoint of reducing cracks.
- the absolute value of the slope is the maximum.
- the value is preferably 10 ° C./m or less, more preferably 5 ° C./m or less, further preferably 4 ° C./m or less, and particularly preferably 3 ° C./m or less.
- the area of the crack means the product of the maximum width of the crack and the maximum distance between the end portions.
- cracks such as cracks in the chromium plating layer exist on the surface of the metal support before the start of film formation. During film formation, it is considered that a foreign substance that seems to be a resin deposit gradually adheres to such a crack to form a convex shape, which is transferred to the film and a defect A is formed on the film.
- PVA-based polymers have high hydrophilicity compared to other polymers and have a good affinity with the metal, so it is considered that they easily enter into cracks existing on the surface of the metal support and adhere as resin deposits. It is considered that it is easy to form and grow a convex shape when the dried film is peeled off from the metal support.
- the surface of the metal support has a chromium plating layer
- the metal support having the above surface hardness is used, the reason is unclear, but by a general treatment applied to the surface of the metal support before starting film formation such as buffing, the metal support The number of cracks existing on the surface can be easily reduced, and the number of the above-mentioned defects A in the obtained PVA polymer film can be reduced as compared with the conventional case. Moreover, the PVA polymer film is continuously used for a long time.
- the fluctuation of the number of the defects A can be kept at a lower level than before.
- the number of the cracks on the surface of the metal support exceeds 0.7 / mm 2 , the number of defects A increases in the obtained PVA polymer film.
- the number of cracks on the surface of the metal support is 0. 0 immediately before casting the solution or molten PVA polymer.
- the number is preferably 3 pieces / mm 2 or less, and more preferably 0.15 pieces / mm 2 or less.
- the number is 0.005 pieces / mm 2 or more, and further 0.01. It is preferable that it is at least pieces / mm 2 .
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface of the metal support is defined as 25 arbitrary positions on the surface of the metal support, and each is in a range of 2 mm ⁇ 2 mm (4 mm 2 ) using a microscope.
- area identifies the 200 [mu] m 2 or more cracks ", determine the number of" area 200 [mu] m 2 or more cracks "in the range ⁇ 25 locations of the 4 mm 2, can be determined by calculating the number per 1 mm 2 now .
- the area of the crack means the product of the maximum width and the maximum end-to-end distance in each crack, and the maximum end-to-end distance is the distance between those ends when there are only two crack ends.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface of the metal support can be determined by the method described later in Examples.
- the width of the metal support can be appropriately set according to the width of the target PVA polymer film.
- the specific width of the metal support depends on the width of the target PVA polymer film, it is, for example, 0.5 m or more, and a wide PVA-based weight capable of producing a wide polarizing film. From the viewpoint of efficiently producing the combined film, it is preferably 4.5 m or more, more preferably 5.0 m or more, and further preferably 5.5 m or more.
- the width of the metal support is preferably 7.5 m or less, preferably 7.0 m or less, and 6.5 m or less. It is more preferable that
- the temperature of the molten or solution PVA polymer is preferably in the range of 50 ° C. or more and 105 ° C. or less.
- Drying after casting can be performed by a known method, and can be performed by drying with heat applied from a metal support or applying hot air. Further, a desired PVA polymer film may be produced only by drying on the surface of the metal support, but after partially drying on the surface of the metal support by a known method, the One or two or more drying rolls arranged on the downstream side of the metal support and whose rotation axes are parallel to each other, or a PVA polymer film desired by further drying with a hot air dryer Can also be manufactured.
- the PVA polymer film thus obtained can be subjected to heat treatment, or both ends (ear portions) in the width direction can be cut as necessary. Moreover, it is good also as a film roll by winding up continuously as mentioned above.
- PVA polymer film of the present invention PVA polymer film (1) and (2)
- PVA polymer film unwound from the film roll of the present invention film roll (1) and (2)
- it is preferably used as an original film for producing an optical film such as a polarizing film or a retardation film, and more preferably used as an original film for producing a polarizing film.
- Dyeing may be performed at any stage before uniaxial stretching, during uniaxial stretching, or after uniaxial stretching.
- dyes used for dyeing iodine-potassium iodide; direct black 17, 19, 154; direct brown 44, 106, 195, 210, 223; direct red 2, 23, 28, 31, 37, 39, 79, 81 240, 242, 247; Direct Blue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; Direct Violet 9, 12, 51, 98; Direct Green 1, 85; Direct One or two or more of dichroic dyes such as yellow 8, 12, 44, 86, 87; direct orange 26, 39, 106, 107 can be used.
- Dyeing can be performed by immersing the PVA polymer film in a solution (dye bath) containing the dye. In addition, when forming a PVA-type polymer film, you may contain said dye previously.
- Uniaxial stretching may be performed by either a wet stretching method or a dry heat stretching method, and may be performed in warm water (including the above-described dyeing bath and a fixed treatment bath described later), or a PVA polymer after water absorption. It can also be carried out in air using a film.
- the temperature at the time of uniaxial stretching is not particularly limited, but when the PVA polymer film is uniaxially stretched (wet stretching) in warm water, it is preferably within a range of 30 ° C. or more and 90 ° C. or less, and dry heat stretching. When it does, it is preferable that it exists in the range of 50 to 180 degreeC.
- the stretching ratio of uniaxial stretching is preferably 4 times or more and more preferably 5 times or more from the viewpoint of polarization performance.
- the thickness of the film after uniaxial stretching depends on the thickness of the PVA polymer film to be used, it is preferably in the range of 3 ⁇ m to 75 ⁇ m, and more preferably in the range of 5 ⁇ m to 50 ⁇ m.
- Fixing treatment is often performed for the purpose of strengthening the adsorption of the dye to the PVA polymer film.
- an aqueous solution containing one or more of boron compounds such as boric acid and borax can be used.
- An iodine compound may be added to the fixed treatment bath as necessary.
- washing is preferably performed in order to remove the treatment bath liquid and foreign matters attached to the film surface before drying.
- Pure water may be used for the cleaning liquid used for cleaning, or water containing a small amount of these chemicals may be used in order to suppress the outflow of dyes and boron compounds due to cleaning.
- the cleaning liquid may be performed by spraying the surface of the film that has undergone each treatment in a shower or the like, or by immersing the film that has undergone each treatment in a washing bath.
- Drying or heat treatment is preferably performed within a range of 30 ° C. or higher and 150 ° C. or lower, and more preferably performed within a range of 50 ° C. or higher and 150 ° C. or lower.
- the PVA polymer film (2) and the PVA polymer film unwound from the film roll (2) as a raw film for producing a polarizing film, a dyeing process, a uniaxial stretching process, a fixing process, and drying.
- the liquid level of the processing bath and the film surface The angle formed (angle on the acute angle side) was 30 ° or more and 85 ° or less, and the upper surface of the film had the smaller root mean square roughness in the PVA polymer film used as the raw film. It is preferable to have a surface because a polarizing film with few foreign substances can be easily obtained.
- the reason why the above effect is achieved is not necessarily clear, but the production of the polarizing film as described above reduces the adhesion of the PVA polymer precipitated in each treatment bath and the treatment liquid used in each treatment. It is thought to be done.
- the angle formed between the liquid surface of the treatment bath and the film surface when exiting the last treatment bath before entering the drying process is not too large or too small. In order to facilitate, the angle is preferably 35 ° or more, more preferably 40 ° or more, further preferably 50 ° or more, and preferably 80 ° or less, and 75 ° or less. It is more preferable that it is 70 ° or less.
- the polarizing film obtained as described above is usually used as a polarizing plate by laminating a protective film having optical transparency and mechanical strength on both sides or one side.
- a protective film a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like is used.
- TAC cellulose triacetate
- CAB acetic acid / cellulose butyrate
- acrylic film a polyester film, or the like
- polyester film or the like
- the adhesive for bonding include PVA adhesives and urethane adhesives, among which PVA adhesives are suitable.
- each crack seen on the photo (if there are only two ends, it means the end-to-end distance, and if there are more than one end-to-end distance, The maximum distance among them is calculated in units of ⁇ m, and these products are calculated.
- a crack having the product of 200 ⁇ m 2 or more is defined as “a crack having an area of 200 ⁇ m 2 or more”. In this way, the number of “cracks having an area of 200 ⁇ m 2 or more” in the 4 mm 2 range ⁇ 25 locations was determined, and the number per 1 mm 2 was calculated therefrom.
- the temperature of each of the three points (total 12 points) at a position of 20 cm from the center in the width direction and from both ends toward the center is obtained for each straight line.
- the average value was defined as the surface temperature of the film-forming drum at that time.
- the obtained temperature distribution data for each straight line is made into four graphs with the position in the width direction as the horizontal axis and the temperature as the vertical axis, and the maximum value of the absolute value of the slope is obtained.
- the maximum temperature gradient of the film forming drum was used.
- the defect of the film was found from the distortion of the image of the fluorescent lamp when the fluorescent lamp placed behind the PVA film was unwound from the film roll, and the circumference was circled with an oil-based magic pen.
- the found defect is observed using a non-contact surface shape measuring instrument “NewView” 6300 (manufactured by Zygo), and is a defect that is recessed from the film surface and has an area (opening area) of 400 ⁇ m 2 or more and a depth. Is a defect (defect A) of 0.3 ⁇ m or more.
- the above operation is started from the winding end portion of the manufactured film roll (still excluding the portion up to 10 m from the end in the length direction of the film in order to reduce the error), and the number of defects A is 10
- the area of the PVA film up to the time (the length from the start of operation to the tenth defect A ⁇ the width of the film; the unit is m 2 ), and dividing 10 (pieces) by that area.
- the number of defects A (unit: pieces / m 2 ) at the end of winding was calculated. Further, among the ten defects A, it is substantially equal to an integral multiple of the entire circumference of the film-forming drum that is located at substantially the same position in the width direction of the film and in which the distance in the length direction of the film is used.
- Rotational cycle defects Two or more defects that are in a coincident relationship. Such defects, including parts other than the part subjected to measurement, are observed in the length direction of the film.
- the number of substantially the same (it can be considered that three or more are arranged at an interval of an integral multiple of the entire circumference of the film-forming drum) is obtained, and this is the above-mentioned area (unit is m 2 ).
- the number of rotation cycle defects at the end of winding (unit: pieces / m 2 ) was calculated. Then, after manufacturing a polarizing film (a polarizing film manufactured from the PVA film on the winding end portion side) as described later using the remaining film roll, the remaining PVA film in an unused state is used.
- the PVA film was unwound from the film roll and re-wound onto the film roll so that the initial winding start portion of the film roll was positioned outside the new film roll. Using this new film roll, the same operation as described above was performed to determine the number of defects A and the number of rotation period defects (both in units / m 2 ) at the initial winding start portion of the film roll, and the remaining film.
- a polarizing film (a polarizing film manufactured from the PVA film on the winding start portion side) was manufactured using a roll as described later.
- the PVA film unwound from the film roll was continuously processed in the order of pre-swelling / dying / uniaxial stretching / fixing / drying / heat treatment to prepare a polarizing film. That is, the PVA film was immersed in 30 ° C. water for 30 seconds to be pre-swelled, and then immersed in an aqueous solution (dyeing bath) having a iodine concentration of 0.4 g / L and a potassium iodide concentration of 40 g / L for 3 minutes. And stained.
- aqueous solution having a boric acid concentration of 4% at a stretching ratio of 5 times in the length direction, and further potassium iodide concentration 40 g / L, boric acid concentration 40 g / L and chloride.
- the fixing treatment was performed by immersing in a 30 ° C. aqueous solution (fixing treatment bath) having a zinc concentration of 10 g / L for 5 minutes. Thereafter, the film was dried with hot air at 40 ° C., and further heat-treated at 100 ° C. for 5 minutes. Twenty test pieces of 50 cm in the length direction and 25 cm in the width direction were collected from arbitrary positions of the obtained polarizing film.
- a polarizing plate of 50 cm ⁇ 50 cm with few defects is prepared, and the above-mentioned test pieces are stacked on this polarizing plate so that the orientation axis is vertical, and placed on the Schaukasen for X-ray photography observation.
- the defect in each test piece was confirmed.
- the stacked polarizing plate / test piece looks black, but when the test piece has a defect, light leaks from that portion and can be recognized as a spot-like bright defect.
- the test piece in which two or more of these bright defects were observed was rejected, and the pass rate among the 20 test pieces was calculated.
- Preparation Example 1 ⁇ Preparation of drum 1 >> After buffing the surface (circumferential surface) of a carbon steel film-forming drum having a width of 1.0 m and performing a base treatment such as a degreasing treatment, a chrome plating bath is used on the drum surface under the following conditions. Chrome plating was performed. In addition, what dissolved these chemical
- Chromium plating bath temperature 55 °C
- Current density 20 A / dm 2 -Chrome plating layer thickness (after polishing): 50 ⁇ m
- finish of chromium plating process the said drum for film forming was heat-processed at 102 degreeC for 50 hours, and stood to cool.
- the surface hardness of the film-forming drum having the chromium plating layer formed on the surface (circumferential surface) by the above chromium plating treatment and heat treatment was measured according to the method described above, and was 760 HV.
- this film-forming drum is referred to as “drum 1”.
- Preparation Example 2 ⁇ Preparation of drum 2 >> A chrome plating treatment and heat treatment were performed in the same manner as in Preparation Example 1 except that the chrome plating bath temperature was changed to 52 ° C. to prepare a film-forming drum having a chrome plating layer formed on the surface (peripheral surface). With respect to this film-forming drum, its surface hardness was measured according to the method described above, and it was 840 HV. Hereinafter, this film-forming drum is referred to as “drum 2”.
- Preparation Example 3 ⁇ Preparation of drum 3 >> A chrome plating treatment and heat treatment were performed in the same manner as in Preparation Example 1 except that the chrome plating bath temperature was changed to 48 ° C., and a film-forming drum having a chrome plating layer formed on the surface (circumferential surface) was prepared. With respect to this film-forming drum, its surface hardness was measured according to the method described above, and it was 950 HV. Hereinafter, this film-forming drum is referred to as “drum 3”.
- Preparation Example 4 ⁇ Preparation of drum 4 >> Except that the chrome plating bath temperature was changed to 67 ° C., a chrome plating treatment and a heat treatment were performed in the same manner as in Preparation Example 1 to prepare a film-forming drum in which a chrome plating layer was formed on the surface (circumferential surface). With respect to this film-forming drum, its surface hardness was 525 HV as measured according to the method described above. Hereinafter, this film-forming drum is referred to as “drum 4”.
- Example 1 The drum 1 was attached to a cast film forming facility and connected to a hot water circulation device. Next, the peripheral surface of the drum 1 was buffed. When the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above-described method, it was 0.10 / mm 2 . Thereafter, the surface temperature of the drum 1 was increased at a temperature change rate of 1 ° C./hour by a hot water circulation device and maintained at a surface temperature of 90 ° C. The maximum temperature gradient at this time was 3.8 ° C./m at the maximum.
- the elongate PVA film of width 0.7m was continuously manufactured by cutting the width direction both ends (ear part).
- the film forming speed was 8 m / min.
- the PVA film (thickness 60 ⁇ m, length 8,000 m) after the film formation was stabilized was continuously wound around an aluminum cylindrical core having a diameter of 6 inches to form a film roll.
- the number of defects of the PVA film was measured and the polarizing film was evaluated by the above-described method (20 sheets test). As a result, the number of defects A in the winding start portion was 0.102.
- the passing rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 100%, the defect on the winding end part
- the number of A is 0.098 pieces / m 2 (of which the rotation period defect is 0.029 pieces / m 2 ), and the pass rate in the 20 sheet test of the polarizing film produced from the PVA film on the winding start side is 100. %Met.
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 0.96 times.
- Example 2 A PVA film was continuously produced as a film roll in the same manner as in Example 1 except that the length of the PVA film was changed from 8,000 m to 3,000 m.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above method, it was 0.11 / mm 2 .
- the number of defects of the PVA film was measured and the polarizing film was evaluated by the above-described method using the obtained film roll (20 sheets test), the number of defects A in the winding start portion was 0.110.
- the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start part side is 100%, and the defect in the winding end part
- the number of A is 0.121 pieces / m 2 (of which the rotation period defect is 0.036 pieces / m 2 ), and the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start portion side is 100. %Met.
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.10 times.
- Example 1 A PVA film was continuously produced as a film roll in the same manner as in Example 1 except that the length of the PVA film was changed from 8,000 m to 15,000 m.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the method described above and found to be 0.10 / mm 2 .
- the number of defects of the PVA film was measured by the above-described method using the obtained film roll, the number of defects A in the winding start portion was 0.108 / m 2 (of which the rotation period defects were 0.032 pieces / m 2 ), and the number of defects A at the end of winding was 0.160 pieces / m 2 (of which the rotation period defects were 0.096 pieces / m 2 ).
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated as 1.48 times.
- Example 3 The PVA film was continuously changed in the same manner as in Example 1 except that the polymerization degree of PVA was changed from 2,400 to 3,300 and the length of the PVA film was changed from 8,000 m to 15,000 m.
- the film roll was manufactured.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the method described above and found to be 0.10 / mm 2 .
- the number of defects in the PVA film was measured and the polarizing film was evaluated (100 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.088.
- the pass rate in the 100-sheet test of the polarizing film manufactured from the PVA film on the winding start portion side is 98%, and the defects in the winding end portion
- the number of A is 0.118 pieces / m 2 (of which the rotation period defect is 0.024 pieces / m 2 ), and the pass rate in the 100 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 95. %Met.
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.34 times.
- Example 4 The PVA film was continuously changed in the same manner as in Example 1 except that the polymerization degree of PVA was changed from 2,400 to 6,000 and the length of the PVA film was changed from 8,000 m to 15,000 m.
- the film roll was manufactured. When the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above method, it was 0.13 / mm 2 . Using the obtained film roll, the number of defects of the PVA film was measured and the polarizing film was evaluated (100 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.067.
- the pass rate in the 100 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 99%, the defect in the winding end part
- the number of A is 0.074 pieces / m 2 (of which the rotation cycle defect is 0.007 pieces / m 2 ), and the pass rate in the 100 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 99. %Met.
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.10 times.
- Example 5 While using the drum 2 instead of the drum 1 and changing the length of the PVA film from 8,000 m to 3,000 m, the PVA film was continuously produced as a film roll in the same manner as in Example 1. .
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 2 after buffing was measured by the method described above, it was 0.39 / mm 2 .
- the number of defects in the PVA film was measured and the polarizing film was evaluated (20 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.172.
- the polarizing film manufactured from the PVA film on the winding start part side has a pass rate of 90% in the 20-sheet test, and the defect at the winding end part
- the number of A is 0.224 pieces / m 2 (of which the rotation period defect is 0.134 pieces / m 2 ), and the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start portion side is 85. %Met.
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.30 times.
- Example 6 The PVA film was continuously produced in the same manner as in Example 1 except that the surface temperature of the drum 1 was changed from 90 ° C. to 110 ° C. and the length of the PVA film was changed from 8,000 m to 3,000 m. And a film roll.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above method, it was 0.13 / mm 2 .
- the number of defects in the PVA film was measured and the polarizing film was evaluated by the above-described method (20 sheets test). As a result, the number of defects A in the winding start portion was 0.132.
- the passing rate in the 20 sheet test of the polarizing film produced from the PVA film on the winding start part side is 95%
- the defect in the winding end part The number of A is 0.180 pieces / m 2 (of which the rotation period defect is 0.090 pieces / m 2 )
- the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 90. %Met.
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.36 times.
- Example 7 A PVA film was continuously produced as a film roll in the same manner as in Example 1 except that the temperature change rate was changed from 1 ° C./hour to 5 ° C./hour.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the method described above and found to be 0.10 / mm 2 .
- the number of defects of the PVA film was measured by the above-described method using the obtained film roll, the number of defects A in the winding start portion was 0.110 / m 2 (of which the rotation period defects were 0.044 pieces / m 2 ), and the number of defects A at the end of winding was 0.122 pieces / m 2 (of which the rotation period defects were 0.049 pieces / m 2 ).
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.11 times.
- Example 1 A PVA film was continuously produced as a film roll in the same manner as in Example 1 except that the drum 3 was used instead of the drum 1.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 3 after buffing was measured by the above method, it was 0.73 / mm 2 .
- the number of defects of the PVA film was measured and the polarizing film was evaluated (20 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.291.
- the pass rate in the 20-sheet test of the polarizing film produced from the PVA film on the winding start side is 80%, and the defects on the winding end portion
- the number of A is 0.938 pieces / m 2 (of which 0.750 pieces / m 2 is the rotation period defect), and the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start portion side is 50. %Met.
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 3.22 times.
- Example 2 The PVA film was continuously produced in the same manner as in Example 1 except that the surface temperature of the drum 1 was changed from 90 ° C. to 120 ° C. and the length of the PVA film was changed from 8,000 m to 3,000 m. And a film roll.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above method, it was 0.11 / mm 2 .
- the number of defects of the PVA film was measured and the polarizing film was evaluated (20 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.252.
- the passing rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start part side is 80%
- the defect in the winding end part The number of A is 0.358 pieces / m 2 (of which the rotational period defect is 0.251 pieces / m 2 )
- the pass rate in the 20-sheet test of the polarizing film produced from the PVA film on the winding start portion side is 65. %Met.
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.42 times.
- Example 3 In Example 1, an attempt was made to produce a PVA film by changing the surface temperature of the drum 1 from 90 ° C. to 40 ° C., but the drying on the drum was insufficient and it was difficult to peel the film from the drum. As a result, each evaluation was not performed.
- Comparative Example 4 A PVA film was continuously produced as a film roll in the same manner as in Comparative Example 1 except that the temperature change rate was changed from 1 ° C./hour to 5 ° C./hour. When the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 3 after buffing was measured by the above method, it was 0.73 / mm 2 .
- the number of defects of the PVA film was measured by the above-described method using the obtained film roll, the number of defects A in the winding start portion was 0.332 pieces / m 2 (of which the rotation period defects were 0.166 pieces / m 2), and a number of drawbacks a in the winding termination portion 1.349 pieces / m 2 (of which, the rotation cycle drawback 1.214 pieces / m 2).
- the number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 4.06 times.
- Example 8 The drum 1 was attached to a cast film forming facility and connected to a hot water circulation device. Next, the peripheral surface of the drum 1 was buffed. When the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above-described method, it was 0.10 / mm 2 . Thereafter, the surface temperature of the drum 1 was raised by a hot water circulation device and maintained at a surface temperature of 90 ° C.
- the elongate PVA film of width 0.7m was continuously manufactured by cutting the width direction both ends (ear part).
- the film forming speed was 8 m / min.
- the PVA film (thickness 60 ⁇ m, length 12,000 m) after the film formation was stabilized was continuously wound around an aluminum cylindrical core having a diameter of 6 inches to form a film roll. It was A rank when the above-mentioned method evaluated the wrinkle of the obtained film roll (wrinkle produced when winding up a PVA film).
- the mean square roughness of the PVA film was measured by the above-described method using the PVA film unwound from the obtained film roll, the mean square roughness on the surface in contact with the surface of the drum 1 was 4 The mean square roughness on the other surface was 1.9 nm. The difference between the two was calculated to be 2.2 nm.
- the PVA film unwound from the film roll was continuously processed in the order of pre-swelling / dying / fixing / uniaxial stretching / washing / drying to prepare a polarizing film. That is, the PVA film was immersed in water at 30 ° C.
- aqueous solution for 60 seconds to be pre-swelled, and then immersed in an aqueous solution (dye bath) having an iodine concentration of 0.4 g / L and a potassium iodide concentration of 40 g / L for 110 seconds. Stained. Subsequently, the substrate was immersed for 90 seconds in a 30 ° C. aqueous solution (fixing treatment bath) having a boric acid concentration of 30 g / L, and further fixed in a 50% aqueous solution (stretching bath) having a boric acid concentration of 4%. Uniaxial stretching was performed in the direction at a stretching ratio of 5 times. Thereafter, the film was immersed in a 30 ° C.
- aqueous solution having a boric acid concentration of 15 g / L for 10 seconds for cleaning, and dried with hot air at 55 ° C. to obtain a polarizing film.
- the angle between the liquid surface of the cleaning bath and the film surface when leaving the cleaning bath, which is the last treatment bath before entering the drying process, is set to 60 ° by changing the position of the guide roll, and at that time
- the upper surface of the film was the surface having the smaller root mean square roughness of the PVA film used. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method, it was A rank.
- Example 9 A PVA film was continuously produced as a film roll in the same manner as in Example 8 except that the drum 2 was used instead of the drum 1.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 2 after buffing was measured by the above method, it was 0.37 / mm 2 . It was B rank when the above-mentioned method evaluated the wrinkle (wrinkle produced when winding up a PVA film) of the obtained film roll.
- the mean square roughness of the PVA film was measured by the above-described method using the PVA film unwound from the obtained film roll, the mean square roughness on the surface in contact with the surface of the drum 2 was 6 0.72 and the root mean square roughness on the other surface was 2.0 nm. The difference between the two was calculated to be 4.7 nm.
- a polarizing film was produced in the same manner as in Example 8 for the PVA film unwound from the film roll. It was B rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method, it was B rank.
- Example 5 A PVA film was continuously produced as a film roll in the same manner as in Example 8 except that the drum 3 was used instead of the drum 1.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 3 after buffing was measured by the above method, it was 0.73 / mm 2 . It was A rank when the above-mentioned method evaluated the wrinkle of the obtained film roll (wrinkle produced when winding up a PVA film).
- the mean square roughness of the PVA film was measured by the above-described method using the PVA film unwound from the obtained film roll, the mean square roughness on the surface in contact with the surface of the drum 3 was 28.
- a polarizing film was produced in the same manner as in Example 8 for the PVA film unwound from the film roll. It was C rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, it was C rank when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method.
- Example 6 A PVA film was continuously produced as a film roll in the same manner as in Example 8 except that the drum 4 was used instead of the drum 1.
- the number of cracks having an area of 200 ⁇ m 2 or more on the surface (circumferential surface) of the drum 4 after buffing was measured by the method described above, it was 0.15 / mm 2 . It was C rank when the above-mentioned method evaluated the wrinkle of the obtained film roll (wrinkle produced when winding up a PVA film).
- Example 10 Using the film roll obtained in Example 8, polarized light in the same manner as in Example 8 except that the angle formed between the liquid surface of the cleaning bath and the film surface when leaving the cleaning bath was changed from 60 ° to 45 °. A film was prepared. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method, it was B rank.
- Example 7 Using the film roll obtained in Example 8, the upper surface of the film when leaving the washing bath was changed to be the surface having the larger root mean square roughness in the PVA film used A polarizing film was produced in the same manner as Example 8 except for the above. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, it was C rank when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method.
- Example 8 Using the film roll obtained in Example 8, polarized light in the same manner as in Example 8 except that the angle formed between the liquid surface of the cleaning bath and the film surface when leaving the cleaning bath was changed from 60 ° to 25 °. A film was prepared. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, it was C rank when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method.
- Example 9 Using the film roll obtained in Example 8, polarized light in the same manner as in Example 8 except that the angle formed between the liquid surface of the cleaning bath and the film surface when leaving the cleaning bath was changed from 60 ° to 88 °. A film was prepared. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, it was C rank when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method.
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Abstract
Description
本発明者らはこのような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]フィルム表面から窪んだ欠点であって面積が400μm2以上で深さが0.3μm以上の欠点の数が0.25個/m2以下であるPVA系重合体フィルム(以下、このPVA系重合体フィルムを「PVA系重合体フィルム(1)」と称することがある);
[2]前記欠点の数が0.15個/m2以下である、上記[1]のPVA系重合体フィルム;
[3]PVA系重合体フィルムに含まれるPVA系重合体の重合度が3,000以上10,000以下である、上記[1]または[2]のPVA系重合体フィルム;
[4]長尺のPVA系重合体フィルムである、上記[1]~[3]のいずれか1つのPVA系重合体フィルム;
[5]長さが6,000m以上である、上記[4]のPVA系重合体フィルム;
[6]前記欠点が、フィルムの長さ方向に実質的に一定の間隔でフィルムの幅方向に実質的に同一の位置に存在する欠点を含む、上記[4]または[5]のPVA系重合体フィルム;
[8]前記欠点の数が0.25個/m2以下である、上記[7]のフィルムロール;
[9]前記欠点の数が0.15個/m2以下である、上記[7]のフィルムロール;
[10]PVA系重合体フィルムに含まれるPVA系重合体の重合度が3,000以上10,000以下である、上記[7]~[9]のいずれか1つのフィルムロール;
[11]PVA系重合体フィルムの長さが6,000m以上である、上記[7]~[10]のいずれか1つのフィルムロール;
[12]前記欠点が、フィルムの長さ方向に実質的に一定の間隔でフィルムの幅方向に実質的に同一の位置に存在する欠点を含む、上記[7]~[11]のいずれか1つのフィルムロール;
[14]大きい方の二乗平均粗さが1nm以上20nm以下である、上記[13]のPVA系重合体フィルム;
[15]長尺のPVA系重合体フィルムである、上記[13]または[14]のPVA系重合体フィルム;
[16]上記[15]のPVA系重合体フィルムが連続的に巻き取られてなるフィルムロール(以下、このフィルムロールを「フィルムロール(2)」と称することがある);
[17]上記[13]~[15]のいずれか1つのPVA系重合体フィルムを原反フィルムとして用いる偏光フィルムの製造方法であって、染色工程、一軸延伸工程、固定処理工程および乾燥工程を有し、乾燥工程に入る前の最後の処理浴を出るときに、処理浴の液面とフィルム面とのなす角度が30°以上85°以下であると共に、フィルムの上方側の面がポリビニルアルコール系重合体フィルムにおいて小さい方の二乗平均粗さを有していた面である、製造方法;
[18]上記[17]の製造方法によって製造される偏光フィルム;
[20]溶液状態または溶融状態のPVA系重合体がPVA系重合体と水を含む製膜原液の形態である、上記[19]の製造方法;
[21]前記PVA系重合体の重合度が3,000以上10,000以下である、上記[19]または[20]の製造方法;
[22]前記金属支持体の表面硬度がビッカース硬さで600HV以上800HV未満である、上記[19]~[21]のいずれか1つの製造方法;
[23]表面にクロムメッキ層を有し、表面硬度がビッカース硬さで550HV以上900HV未満である金属支持体の表面温度を0.5℃/時間以上の変温速度で50℃以上115℃以下にする工程を有する、上記[19]~[22]のいずれか1つの製造方法;
[24]上記[1]~[6]および[13]~[15]のいずれか1つのPVA系重合体フィルムを製造する、[19]~[23]のいずれか1つの製造方法;
に関する。
[PVA系重合体フィルム(1)]
本発明のPVA系重合体フィルム(PVA系重合体フィルム(1))は、フィルム表面から窪んだ欠点であって面積が400μm2以上で深さが0.3μm以上の欠点(以下、この欠点を「欠点A」と称することがある)の数が0.25個/m2以下である。プラスチックフィルムに存在する欠点としては、フィルム中のボイド(気泡);異物の混入・付着によるいわゆるフィッシュアイ;フィルムのハンドリング中に生じる傷(多くは溝状の凹み);製膜装置上の凸形状が転写されることによる欠点などが挙げられるが、本発明者らは、上記欠点Aの数を特に制御することによって欠陥の少ない偏光フィルムや偏光板を収率よく製造することができるなどの優れた効果が奏されることを見出した。この欠点Aは上記した製膜装置上の凸形状の転写が原因の1つであると考えられ、特に、後述するようにドラムやベルトといった金属支持体を用いてPVA系重合体フィルムを製膜した場合に、金属支持体上に付着した樹脂堆積物と思われる異物による凸形状がフィルムに転写されることが原因の1つであると考えられる。このような原因によって長尺のPVA系重合体フィルムに欠点Aが生じる場合には、欠点Aのうちの少なくとも一部が、フィルムの長さ方向に実質的に一定の間隔で且つフィルムの幅方向に実質的に同一の位置に複数(例えば3個以上)配列する傾向がある。ここで上記の実質的に一定の間隔は、典型的には、ドラムやベルトといった金属支持体の1周分の長さ(全周長さ)に対応するが、場合によっては、1周分の長さの整数倍に対応することもある。また、異物による凸形状は金属支持体上に複数形成され得るため、上記のように配列した欠点Aの群も複数存在し得る。
一方、欠点Aの数の下限については必ずしも限定されないが、欠点Aの数を極度に少なくするためには、製膜設備を設置するためのコストが極度に高くなるなどのおそれがあることから、欠点Aの数は0.001個/m2以上であることが好ましく、0.003個/m2以上であることがより好ましく、0.005個/m2以上であることがさらに好ましい。
欠点Aの数(単位は個/m2)は、対象となるPVA系重合体フィルムの一方の端から欠点Aを探していき、10個の欠点Aを見つけるまでに検査したPVA系重合体フィルムの面積(単位はm2)で10(個)を除すことにより求めることができ、具体的には実施例において後述する方法によって求めることができる。ここで、個々の欠点が欠点Aであるか否かの判定は、非接触表面形状測定機を用いて行うことができる。
当該長尺のPVA系重合体フィルムの長さは特に制限されず、PVA系重合体フィルム(1)の用途などに応じて適宜設定することができ、具体的には当該長さは1,000m以上であることが好ましく、4,000m以上であることがより好ましく、6,000m以上であることがさらに好ましく、7,000m以上であることが特に好ましく、8,000m以上であることが最も好ましい。特に後述するPVA系重合体フィルムの製造方法によれば、PVA系重合体フィルムの欠点Aの数を低減できるとともに、PVA系重合体フィルムを長時間にわたり連続して製膜しても欠点Aの数の変動を低いレベルに保つことができるため、上記長さがより長い場合(例えば6,000m以上)であっても欠点Aの数が低減されたPVA系重合体フィルムを簡便に得ることができる。そしてこのようなより長いPVA系重合体フィルムによれば、偏光フィルムを連続的に製造する場合に欠陥が少なくて近年要求される品質レベルを満足する製品を長時間にわたり収率よく安定して製造することが可能となり、また、フィルムロールの切り替えに伴う煩雑さや時間ロスを低減することもできる。長尺のPVA系重合体フィルムの長さの上限に特に制限はないが、あまりに長いとフィルムロールとした際に重量やロール径が過度に大きくなるなどしてハンドリング性が低下し保管や輸送が困難になる場合があることなどから、当該長さは30,000m以下であることが好ましく、25,000m以下であることがより好ましく、20,000m以下であることがさらに好ましい。
重合度 = ([η]×103/8.29)(1/0.62)
PVA系重合体フィルム(1)における可塑剤の含有量は、PVA系重合体100質量部に対して1~30質量部の範囲内であることが好ましく、3~25質量部の範囲内であることがより好ましく、5~20質量部の範囲内であることがさらに好ましい。
アニオン性界面活性剤としては、例えば、ラウリン酸カリウム等のカルボン酸型、オクチルサルフェート等の硫酸エステル型、ドデシルベンゼンスルホネート等のスルホン酸型などが挙げられる。
ノニオン性界面活性剤としては、例えば、ポリオキシエチレンオレイルエーテル等のアルキルエーテル型、ポリオキシエチレンオクチルフェニルエーテル等のアルキルフェニルエーテル型、ポリオキシエチレンラウレート等のアルキルエステル型、ポリオキシエチレンラウリルアミノエーテル等のアルキルアミン型、ポリオキシエチレンラウリン酸アミド等のアルキルアミド型、ポリオキシエチレンポリオキシプロピレンエーテル等のポリプロピレングリコールエーテル型、ラウリン酸ジエタノールアミド、オレイン酸ジエタノールアミド等のアルカノールアミド型、ポリオキシアルキレンアリルフェニルエーテル等のアリルフェニルエーテル型などが挙げられる。
これらの界面活性剤は1種を単独で使用しても、2種以上を併用してもよい。
本発明のフィルムロール(フィルムロール(1))は、長尺のPVA系重合体フィルムが連続的に巻き取られてなるフィルムロールであって、PVA系重合体フィルムの巻き取り開始部分(PVA系重合体フィルムをフィルムロールとして巻き取り始めたときのフィルム部分)における上記欠点Aの数に対する、PVA系重合体フィルムの巻き取り終了部分(PVA系重合体フィルムをフィルムロールとして巻き取り終わったときのフィルム部分)における上記欠点Aの数が1.4倍以下である。このようなフィルムロールではPVA系重合体フィルムの巻き取り開始部分から巻き取り終了部分までの表面特性の差が小さいため、当該フィルムロールによれば品質の安定した偏光フィルムひいては偏光板を製造することが可能となる。このような観点から、PVA系重合体フィルムの巻き取り開始部分における上記欠点Aの数に対するPVA系重合体フィルムの巻き取り終了部分における上記欠点Aの数は、1.3倍以下であることが好ましく、1.2倍以下であることがより好ましく、1.1倍以下であることがさらに好ましい。また、長尺のPVA系重合体フィルムの製膜において欠点Aの数は概ね経時的に増加する傾向があるため、PVA系重合体フィルムの巻き取り開始部分における上記欠点Aの数に対するPVA系重合体フィルムの巻き取り終了部分における上記欠点Aの数は通常0.6倍以上となることが多く、また、品質の安定した偏光フィルムひいては偏光板を製造するなどの観点からPVA系重合体フィルムの巻き取り開始部分における上記欠点Aの数に対するPVA系重合体フィルムの巻き取り終了部分における上記欠点Aの数は0.7倍以上であることが好ましく、0.75倍以上であることがより好ましく、0.8倍以上であることがさらに好ましく、0.9倍以上であることが特に好ましい。
本発明のPVA系重合体フィルム(PVA系重合体フィルム(2))は、フィルムの両面のそれぞれにおいて二乗平均粗さを測定した際に、得られた2つの二乗平均粗さの差が0.3nm以上10nm以下であり、小さい方の二乗平均粗さが10nm以下である。PVA系重合体フィルムが連続的に巻き取られてなる従来のフィルムロールではフィルム間のスリップ性不良などによりフィルムに皺が生じやすいが、本発明のPVA系重合体フィルム(2)によれば、当該皺の発生を低減することができる。なおフィルムロールの皺には、PVA系重合体フィルムを巻き取る際に生じるものと、一旦フィルムロールとした後これを倉庫等で保管しているときにPVA系重合体フィルムに残存していた応力による巻き絞まりが生じてこの際にフィルム間のスリップ性が不良であることにより生じるものとがあり、本発明のPVA系重合体フィルム(2)によれば、前者の皺の発生を効果的に低減することができるが、後者の皺の発生も低減することもできる。これに加えて本発明のPVA系重合体フィルム(2)によれば、上記した欠陥とは異なる染色斑が低減された偏光フィルムを容易に製造することができる。
当該長尺のPVA系重合体フィルムの長さは特に制限されず、PVA系重合体フィルム(2)の用途などに応じて適宜設定することができ、具体的には当該長さは1,000m以上であることが好ましく、4,000m以上であることがより好ましく、6,000m以上であることがさらに好ましく、7,000m以上であることが特に好ましく、8,000m以上であることが最も好ましい。このようなより長いPVA系重合体フィルムによれば、フィルムロールの切り替えに伴う煩雑さや時間ロスを低減することができる。長尺のPVA系重合体フィルムの長さの上限に特に制限はないが、あまりに長いとフィルムロールとした際に重量やロール径が過度に大きくなるなどしてハンドリング性が低下し保管や輸送が困難になる場合があることなどから、当該長さは30,000m以下であることが好ましく、25,000m以下であることがより好ましく、20,000m以下であることがさらに好ましい。なお、フィルムロールを保管しているときに発生する皺の原因の1つとしてはPVA系重合体フィルムに残存していた応力による巻き絞まりが挙げられるが、この巻き絞まりはより長くより幅の広いPVA系重合体フィルムにおいて強く現れやすいため、より長いPVA系重合体フィルムにおいて本発明の効果がより顕著に奏される。
本発明のフィルムロール(フィルムロール(2))は、上記のPVA系重合体フィルム(2)であって長尺のPVA系重合体フィルムが連続的に巻き取られてなり、例えば、円筒状のコアにPVA系重合体フィルム(2)であって長尺のPVA系重合体フィルムが連続的に巻き取られてなる。円筒状のコアが使用される場合には、当該コアの両端部はフィルムロールの端面から突出する突出部を形成していることが好ましい。当該コアとしては、フィルムロール(1)の説明として上記したものを用いることができ、ここでは重複する説明を省略する。
PVA系重合体フィルムを製造するための本発明の製造方法は、表面にクロムメッキ層を有し、表面硬度がビッカース硬さで550HV以上900HV未満であり、表面温度が50℃以上115℃以下である金属支持体の表面上に、溶液状態または溶融状態のPVA系重合体を流延して乾燥させて製膜する工程を有する。そして、溶液状態または溶融状態のPVA系重合体を流延し始める直前において金属支持体の表面における面積(最大幅と最大端部間距離との積)が200μm2以上のクラックの数が0.7個/mm2以下である。当該製造方法によれば、上記した本発明のPVA系重合体フィルム(PVA系重合体フィルム(1)および(2))や、本発明のフィルムロール(フィルムロール(1)および(2))において連続的に巻き取られる長尺のPVA系重合体フィルムを簡便に製造することができる。
<サージエント浴の組成>
無水クロム酸:100~300g/L(使用薬品基準の濃度)
硫酸:使用される無水クロム酸の1/50~1/150(質量割合)
<クロムメッキ処理の条件>
電流密度 10~60A/dm2
本発明のPVA系重合体フィルム(PVA系重合体フィルム(1)および(2))や、本発明のフィルムロール(フィルムロール(1)および(2))から巻き出されたPVA系重合体フィルムは、欠点Aの数が少ない;品質が安定している;皺が発生しにくい;などの利点を活かして各種用途に使用することができるが、本発明の効果がより顕著に奏されることから、偏光フィルムや位相差フィルムなどの光学フィルム製造用の原反フィルムとして使用するのが好ましく、偏光フィルム製造用の原反フィルムとして使用するのがより好ましい。
一軸延伸する際の温度は特に制限されないが、PVA系重合体フィルムを温水中で一軸延伸(湿式延伸)する場合には30℃以上90℃以下の範囲内であることが好ましく、また乾熱延伸する場合には50℃以上180℃以下の範囲内であることが好ましい。
一軸延伸の延伸倍率(多段で一軸延伸する場合には合計の延伸倍率)は、偏光性能の点から4倍以上であることが好ましく、5倍以上であることがより好ましい。延伸倍率の上限に特に制限はないが、8倍以下であると一軸延伸を安定して行い易いため好ましい。一軸延伸後のフィルムの厚みは、用いるPVA系重合体フィルムの厚みにもよるが、3μm以上75μm以下の範囲内であることが好ましく、5μm以上50μm以下の範囲内であることがより好ましい。
製膜用ドラムの表面(周面)において、両端からそれぞれ5mm内側に入りこんだ線上で、製膜用ドラムの全周長さを4等分するように各端部4点ずつ合計8点を定めた。そして各点において、UCI式硬さ計 MIC10(GEセンシング&インスペクション・テクノロジーズ株式会社製;プローブはMIC-2101-Aを使用)にてクロムメッキ層表面のビッカース硬度を測定し、それらの平均値を製膜用ドラムの表面硬度とした。
製膜用ドラムの表面(周面)上で任意の25箇所を定め、それぞれにおいて、デジタルビデオマイクロスコープ VHX-900(キーエンス社製)を用いて1000倍の倍率で2mm×2mm(4mm2)の範囲内にあるクラック(クロムメッキ層上のひび割れ)の写真を撮影した。そして写真上に見られる各クラックの最大幅と最大端部間距離(端部が2つのみの場合にはそれらの端部間距離を意味し、複数ある場合には複数の端部間距離のうちの最大の距離を意味する)をμm単位で求めてこれらの積を算出し、その積が200μm2以上となるクラックを「面積が200μm2以上のクラック」とした。このようにして上記4mm2の範囲×25箇所において「面積が200μm2以上のクラック」の数を求めて、これから1mm2あたりの数を算出した。
製膜用ドラムの表面(周面)上の任意の1点を通過する幅方向の1直線と、この1直線に平行でこの1直線と共に周面を4等分するようなその他の3直線(すなわち製膜用ドラムが1/4周する毎に同一直線上に位置する直線)を定め、これらの4直線上における温度分布を、サーモトレーサ TH9100MR(NEC Avio赤外線テクノロジー株式会社製)を用いて測定した。次いで、得られた温度分布データから、各直線につき幅方向中央部と両端部から中央部に向けて20cmの位置の各3点(合計12点)の温度を得て、これら12点の温度を平均した値をそのときの製膜用ドラムの表面温度とした。また、得られた各直線毎の温度分布データを、幅方向の位置を横軸とし温度を縦軸とする4本のグラフにし、その傾きの絶対値の最大値を求め、これをそのときの製膜用ドラムの最大温度勾配とした。
フィルムロールよりPVAフィルムを巻き出しながらフィルムを通してその後ろに置かれた蛍光灯を見たときの蛍光灯の像のゆがみからフィルムの欠点を見つけ、その回りを油性マジックペンで丸く囲った。次に、見つけた欠点を非接触表面形状測定機「NewView」6300(ザイゴ社製)を用いて観察し、フィルム表面から窪んだ欠点であって面積(開口部面積)が400μm2以上で深さが0.3μm以上の欠点(欠点A)であるか否かを判定した。上記の操作を、製造されたフィルムロールにおける巻き取り終了部分(なお誤差を低減するためフィルムの長さ方向の端部より10mまでの部分は除外した)から始め、欠点Aの数が10個になったときまでのPVAフィルムの面積(操作を始めてから10個目の欠点Aまでの長さ×フィルムの幅;単位はm2)を求め、その面積で10(個)を除すことにより、巻き取り終了部分における欠点Aの数(単位は個/m2)を算出した。また10個の欠点Aのうち、フィルムの幅方向に実質的に同一の位置にあり且つフィルムの長さ方向の間隔が使用された製膜用ドラムの全周長さの整数倍に実質的に一致する関係にある2個以上の欠点(以下、「回転周期欠点」と称することがある。なおこのような欠点は、測定に供された部分以外の部分も含めて、フィルムの長さ方向に実質的に一定(製膜用ドラムの全周長さの整数倍)の間隔で3個以上配列していると考えることができる。)の数を求め、これを上記面積(単位はm2)で除すことにより、巻き取り終了部分における回転周期欠点の数(単位は個/m2)を算出した。
続いて、残りのフィルムロールを用いて後述するように偏光フィルム(巻き取り終了部分側のPVAフィルムから製造された偏光フィルム)を製造後、大部分のPVAフィルムが未使用の状態にある残りのフィルムロールからPVAフィルムを巻き出して新たにフィルムロールに巻き直すことにより、当初のフィルムロールの巻き取り開始部分が新たなフィルムロールの外側に位置するようにした。この新たなフィルムロールを用いて上記と同様の操作を行い、当初のフィルムロールの巻き取り開始部分における欠点Aおよび回転周期欠点の数(いずれも単位は個/m2)を求め、残りのフィルムロールを用いて後述するように偏光フィルム(巻き取り開始部分側のPVAフィルムから製造された偏光フィルム)を製造した。
フィルムロールを目視で観察し、以下の基準で皺を評価した。
Aランク:皺が認められない
Bランク:皺が僅かに存在するが、実用上問題ないレベル
Cランク:実用上問題となるレベルの皺がある
PVAフィルムの一方の面の任意の10箇所の二乗平均粗さを白色干渉顕微鏡 NV6300(ザイゴ社製)を用いて測定し、それらの平均値をその面の二乗平均粗さとした。次いで、PVAフィルムの他方の面についても同様にして二乗平均粗さを得た。
上記のフィルムロールから巻き出されたPVAフィルムを予備膨潤・染色・一軸延伸・固定処理・乾燥・熱処理の順番で連続的に処理して偏光フィルムを作製した。
すなわち、PVAフィルムを30℃の水中に30秒間浸漬して予備膨潤し、次いでヨウ素濃度0.4g/Lおよびヨウ化カリウム濃度40g/Lの35℃の水溶液(染色浴)中に3分間浸漬して染色した。続いて、ホウ酸濃度4%の50℃の水溶液(延伸浴)中で長さ方向に延伸倍率5倍で一軸延伸を行い、さらにヨウ化カリウム濃度40g/L、ホウ酸濃度40g/Lおよび塩化亜鉛濃度10g/Lの30℃の水溶液(固定処理浴)中に5分間浸漬して固定処理を行った。その後、フィルムを40℃で熱風乾燥し、さらに100℃で5分間熱処理を行った。
得られた偏光フィルムの任意の位置から、長さ方向に50cm、幅方向に25cmの試験片を20枚採取した。一方、欠陥の少ない50cm×50cmの偏光板を準備して、この偏光板上に上記の各試験片を配向軸が垂直になるように重ね、それをレントゲン写真観察用のシャウカッセンの上に置いて、それぞれの試験片における欠陥を確認した。なお、試験片に欠陥がない場合、重ねた偏光板/試験片は真っ黒に見えるが、試験片に欠陥がある場合、その部分から光が漏れて点状の明るい欠陥として認識することができる。この明るい欠陥が2個以上観察された試験片は不合格として、20枚の試験片中の合格率を算出した。
試験片の数を20枚から100枚に変更するとともに、明るい欠陥が1個以上観察された試験片を不合格としたこと以外は上記の20枚試験と同様にして、100枚の試験片中の合格率を算出した。
得られた偏光フィルムの任意の位置から、長さ方向に50cm、幅方向に25cmの試験片を採取した。一方、染色斑や異物の少ない50cm×50cmの偏光板を準備して、この偏光板上に上記の試験片を配向軸が垂直になるように重ね、それをレントゲン写真観察用のシャウカッセンの上に置いて、試験片における染色斑および異物を以下の基準で評価した。
・染色斑
Aランク:染色斑が認められない
Bランク:染色斑が僅かに存在するが、実用上問題ないレベル
Cランク:実用上問題となるレベルの染色斑がある
・異物
Aランク:異物が認められない
Bランク:異物が僅かに存在するが、実用上問題ないレベル
Cランク:実用上問題となるレベルの異物がある
《ドラム1の調製》
幅1.0mの炭素鋼製の製膜用ドラムのドラム表面(周面)をバフ研磨して脱脂処理などの下地処理を行った後、当該ドラム表面にクロムメッキ浴を用いて以下の条件でクロムメッキ処理を実施した。なお、使用薬品基準の濃度で無水クロム酸200g/Lおよび硫酸2g/Lとなるようにこれらの薬品を蒸留水に溶解したものをクロムメッキ浴とした。
・クロムメッキ浴温度:55℃
・電流密度:20A/dm2
・クロムメッキ層厚み(研磨後):50μm
そして、クロムメッキ処理の終了後、当該製膜用ドラムを102℃で50時間熱処理し、放冷した。
上記のクロムメッキ処理と熱処理により表面(周面)にクロムメッキ層が形成された製膜用ドラムについて、その表面硬度を上記した方法に従って測定したところ760HVであった。以下、この製膜用ドラムを「ドラム1」と称する。
《ドラム2の調製》
クロムメッキ浴温度を52℃に変更したこと以外は調製例1と同様にしてクロムメッキ処理と熱処理を行い、表面(周面)にクロムメッキ層が形成された製膜用ドラムを調製した。この製膜用ドラムについて、その表面硬度を上記した方法に従って測定したところ840HVであった。以下、この製膜用ドラムを「ドラム2」と称する。
《ドラム3の調製》
クロムメッキ浴温度を48℃に変更したこと以外は調製例1と同様にしてクロムメッキ処理と熱処理を行い、表面(周面)にクロムメッキ層が形成された製膜用ドラムを調製した。この製膜用ドラムについて、その表面硬度を上記した方法に従って測定したところ950HVであった。以下、この製膜用ドラムを「ドラム3」と称する。
《ドラム4の調製》
クロムメッキ浴温度を67℃に変更したこと以外は調製例1と同様にしてクロムメッキ処理と熱処理を行い、表面(周面)にクロムメッキ層が形成された製膜用ドラムを調製した。この製膜用ドラムについて、その表面硬度を上記した方法に従って測定したところ525HVであった。以下、この製膜用ドラムを「ドラム4」と称する。
ドラム1をキャスト製膜設備に取り付け、温水循環装置と接続した。次いで、ドラム1の周面をバフ研磨した。バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.10個/mm2であった。その後、ドラム1の表面温度を温水循環装置により1℃/時間の変温速度で上昇させ、表面温度90℃で維持した。この際の最大温度勾配は最大で3.8℃/mであった。
一方、けん化度99.9モル%、重合度2,400のPVA(酢酸ビニルの単独重合体のけん化物)のチップ100質量部を35℃の蒸留水2,500質量部に24時間浸漬した後、遠心脱水を行い、PVA含水チップを得た。PVA含水チップ中の揮発分率は70質量%であった。そのPVA含水チップ333質量部(乾燥状態PVA換算で100質量部)に対して、グリセリン12質量部および界面活性剤(ラウリン酸ジエタノールアミド95質量%含有)0.3質量部を添加した後、よく混合して混合物とし、これを最高温度130℃のベント付き二軸押出機で加熱溶融した。得られた溶融状態のPVAを熱交換機で100℃に冷却した後、900mm幅のコートハンガーダイから表面温度を90℃にした前記ドラム1上に押出製膜して、さらに熱風乾燥炉内を通して乾燥して、幅方向両端部(耳部)をカットすることにより幅0.7mの長尺のPVAフィルムを連続的に製造した。なお、製膜速度は8m/分とした。製膜が安定した後のPVAフィルム(厚み60μm、長さ8,000m)は直径6インチのアルミニウム製の円筒状のコアに連続的に巻き取ってフィルムロールとした。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定と偏光フィルムの評価(20枚試験)を行ったところ、巻き取り開始部分における欠点Aの数は0.102個/m2(うち、回転周期欠点は0.031個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は100%、巻き取り終了部分における欠点Aの数は0.098個/m2(うち、回転周期欠点は0.029個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は100%であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は0.96倍と計算された。
PVAフィルムの長さを8,000mから3,000mに変更したこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.11個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定と偏光フィルムの評価(20枚試験)を行ったところ、巻き取り開始部分における欠点Aの数は0.110個/m2(うち、回転周期欠点は0.044個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は100%、巻き取り終了部分における欠点Aの数は0.121個/m2(うち、回転周期欠点は0.036個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は100%であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は1.10倍と計算された。
PVAフィルムの長さを8,000mから15,000mに変更したこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.10個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定を行ったところ、巻き取り開始部分における欠点Aの数は0.108個/m2(うち、回転周期欠点は0.032個/m2)、巻き取り終了部分における欠点Aの数は0.160個/m2(うち、回転周期欠点は0.096個/m2)であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は1.48倍と計算された。
PVAの重合度を2,400から3,300に変更するとともに、PVAフィルムの長さを8,000mから15,000mに変更したこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.10個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定と偏光フィルムの評価(100枚試験)を行ったところ、巻き取り開始部分における欠点Aの数は0.088個/m2(うち、回転周期欠点は0.018個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの100枚試験における合格率は98%、巻き取り終了部分における欠点Aの数は0.118個/m2(うち、回転周期欠点は0.024個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの100枚試験における合格率は95%であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は1.34倍と計算された。
PVAの重合度を2,400から6,000に変更するとともに、PVAフィルムの長さを8,000mから15,000mに変更したこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.13個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定と偏光フィルムの評価(100枚試験)を行ったところ、巻き取り開始部分における欠点Aの数は0.067個/m2(うち、回転周期欠点は0.007個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの100枚試験における合格率は99%、巻き取り終了部分における欠点Aの数は0.074個/m2(うち、回転周期欠点は0.007個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの100枚試験における合格率は99%であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は1.10倍と計算された。
ドラム1に代えてドラム2を用いるとともに、PVAフィルムの長さを8,000mから3,000mに変更したこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム2の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.39個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定と偏光フィルムの評価(20枚試験)を行ったところ、巻き取り開始部分における欠点Aの数は0.172個/m2(うち、回転周期欠点は0.052個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は90%、巻き取り終了部分における欠点Aの数は0.224個/m2(うち、回転周期欠点は0.134個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は85%であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は1.30倍と計算された。
ドラム1の表面温度を90℃から110℃に変更するとともに、PVAフィルムの長さを8,000mから3,000mに変更したこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.13個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定と偏光フィルムの評価(20枚試験)を行ったところ、巻き取り開始部分における欠点Aの数は0.132個/m2(うち、回転周期欠点は0.053個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は95%、巻き取り終了部分における欠点Aの数は0.180個/m2(うち、回転周期欠点は0.090個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は90%であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は1.36倍と計算された。
変温速度を1℃/時間から5℃/時間に変更したこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.10個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定を行ったところ、巻き取り開始部分における欠点Aの数は0.110個/m2(うち、回転周期欠点は0.044個/m2)、巻き取り終了部分における欠点Aの数は0.122個/m2(うち、回転周期欠点は0.049個/m2)であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は1.11倍と計算された。
ドラム1に代えてドラム3を用いたこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム3の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.73個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定と偏光フィルムの評価(20枚試験)を行ったところ、巻き取り開始部分における欠点Aの数は0.291個/m2(うち、回転周期欠点は0.175個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は80%、巻き取り終了部分における欠点Aの数は0.938個/m2(うち、回転周期欠点は0.750個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は50%であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は3.22倍と計算された。
ドラム1の表面温度を90℃から120℃に変更するとともに、PVAフィルムの長さを8,000mから3,000mに変更したこと以外は実施例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.11個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定と偏光フィルムの評価(20枚試験)を行ったところ、巻き取り開始部分における欠点Aの数は0.252個/m2(うち、回転周期欠点は0.101個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は80%、巻き取り終了部分における欠点Aの数は0.358個/m2(うち、回転周期欠点は0.251個/m2)、巻き取り開始部分側のPVAフィルムから製造された偏光フィルムの20枚試験における合格率は65%であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は1.42倍と計算された。
実施例1において、ドラム1の表面温度を90℃から40℃に変更してPVAフィルムの製造を試みたが、ドラム上での乾燥が不十分であってフィルムをドラムから剥離することが困難であったため、各評価は行わなかった。
変温速度を1℃/時間から5℃/時間に変更したこと以外は比較例1と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム3の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.73個/mm2であった。
得られたフィルムロールを用いて、上記した方法によりPVAフィルムの欠点の数の測定を行ったところ、巻き取り開始部分における欠点Aの数は0.332個/m2(うち、回転周期欠点は0.166個/m2)、巻き取り終了部分における欠点Aの数は1.349個/m2(うち、回転周期欠点は1.214個/m2)であった。巻き取り開始部分における欠点Aの数に対する巻き取り終了部分における欠点Aの数は4.06倍と計算された。
ドラム1をキャスト製膜設備に取り付け、温水循環装置と接続した。次いで、ドラム1の周面をバフ研磨した。バフ研磨後のドラム1の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.10個/mm2であった。その後、ドラム1の表面温度を温水循環装置により上昇させ、表面温度90℃で維持した。
一方、けん化度99.9モル%、重合度2,400のPVA(酢酸ビニルの単独重合体のけん化物)のチップ100質量部を35℃の蒸留水2,500質量部に24時間浸漬した後、遠心脱水を行い、PVA含水チップを得た。PVA含水チップ中の揮発分率は70質量%であった。そのPVA含水チップ333質量部(乾燥状態PVA換算で100質量部)に対して、グリセリン12質量部および界面活性剤(ラウリン酸ジエタノールアミド95質量%含有)0.3質量部を添加した後、よく混合して混合物とし、これを最高温度130℃のベント付き二軸押出機で加熱溶融した。得られた溶融状態のPVAを熱交換機で100℃に冷却した後、900mm幅のコートハンガーダイから表面温度を90℃にした前記ドラム1上に押出製膜して、さらに熱風乾燥炉内を通して乾燥して、幅方向両端部(耳部)をカットすることにより幅0.7mの長尺のPVAフィルムを連続的に製造した。なお、製膜速度は8m/分とした。製膜が安定した後のPVAフィルム(厚み60μm、長さ12,000m)は直径6インチのアルミニウム製の円筒状のコアに連続的に巻き取ってフィルムロールとした。
得られたフィルムロールの皺(PVAフィルムを巻き取る際に生じる皺)を上記した方法により評価したところAランクであった。また、得られたフィルムロールから巻き出したPVAフィルムを用いて、上記した方法によりPVAフィルムの二乗平均粗さを測定したところ、ドラム1の表面に接した側の面における二乗平均粗さは4.1nmであり、他方の面における二乗平均粗さは1.9nmであった。両者の差は2.2nmと計算された。
上記のフィルムロールから巻き出されたPVAフィルムを予備膨潤・染色・固定処理・一軸延伸・洗浄・乾燥の順番で連続的に処理して偏光フィルムを作製した。すなわち、PVAフィルムを30℃の水中に60秒間浸して予備膨潤し、次いでヨウ素濃度0.4g/Lおよびヨウ化カリウム濃度40g/Lの35℃の水溶液(染色浴)中に110秒間浸漬して染色した。続いて、ホウ酸濃度30g/Lの30℃の水溶液(固定処理浴)中に90秒間浸漬して固定処理を行い、さらにホウ酸濃度4%の50℃の水溶液(延伸浴)中で長さ方向に延伸倍率5倍で一軸延伸を行った。その後、ホウ酸濃度15g/Lの30℃の水溶液(洗浄浴)中に10秒間浸漬して洗浄を行い、55℃で熱風乾燥して偏光フィルムとした。なお乾燥工程に入る前の最後の処理浴である洗浄浴を出るときの洗浄浴の液面とフィルム面とのなす角度をガイドロールの位置を変更することにより60°に設定すると共に、そのときのフィルムの上方側の面が使用したPVAフィルムにおいて小さい方の二乗平均粗さを有していた面となるようにした。
得られた偏光フィルムの染色斑を上記した方法により評価したところAランクであった。また、得られた偏光フィルムの異物を上記した方法により評価したところAランクであった。
ドラム1に代えてドラム2を用いたこと以外は実施例8と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム2の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.37個/mm2であった。
得られたフィルムロールの皺(PVAフィルムを巻き取る際に生じる皺)を上記した方法により評価したところBランクであった。また、得られたフィルムロールから巻き出したPVAフィルムを用いて、上記した方法によりPVAフィルムの二乗平均粗さを測定したところ、ドラム2の表面に接した側の面における二乗平均粗さは6.7nmであり、他方の面における二乗平均粗さは2.0nmであった。両者の差は4.7nmと計算された。
上記のフィルムロールから巻き出されたPVAフィルムに対して、実施例8と同様にして偏光フィルムを作製した。得られた偏光フィルムの染色斑を上記した方法により評価したところBランクであった。また、得られた偏光フィルムの異物を上記した方法により評価したところBランクであった。
ドラム1に代えてドラム3を用いたこと以外は実施例8と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム3の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.73個/mm2であった。
得られたフィルムロールの皺(PVAフィルムを巻き取る際に生じる皺)を上記した方法により評価したところAランクであった。また、得られたフィルムロールから巻き出したPVAフィルムを用いて、上記した方法によりPVAフィルムの二乗平均粗さを測定したところ、ドラム3の表面に接した側の面における二乗平均粗さは28.3nmであり、他方の面における二乗平均粗さは2.6nmであった。両者の差は25.7nmと計算された。
上記のフィルムロールから巻き出されたPVAフィルムに対して、実施例8と同様にして偏光フィルムを作製した。得られた偏光フィルムの染色斑を上記した方法により評価したところCランクであった。また、得られた偏光フィルムの異物を上記した方法により評価したところCランクであった。
ドラム1に代えてドラム4を用いたこと以外は実施例8と同様にして、PVAフィルムを連続的に製造しフィルムロールとした。なお、バフ研磨後のドラム4の表面(周面)における面積が200μm2以上のクラックの数を上記した方法によって測定したところ0.15個/mm2であった。
得られたフィルムロールの皺(PVAフィルムを巻き取る際に生じる皺)を上記した方法により評価したところCランクであった。また、得られたフィルムロールから巻き出したPVAフィルムを用いて、上記した方法によりPVAフィルムの二乗平均粗さを測定したところ、ドラム4の表面に接した側の面における二乗平均粗さは2.8nmであり、他方の面における二乗平均粗さは2.6nmであった。両者の差は0.2nmと計算された。
上記のフィルムロールから巻き出されたPVAフィルムに対して、実施例8と同様にして偏光フィルムを作製した。得られた偏光フィルムの染色斑を上記した方法により評価したところAランクであった。また、得られた偏光フィルムの異物を上記した方法により評価したところAランクであった。
実施例8で得られたフィルムロールを用い、洗浄浴を出るときの洗浄浴の液面とフィルム面とのなす角度を60°から45°に変更したこと以外は実施例8と同様にして偏光フィルムを作製した。得られた偏光フィルムの染色斑を上記した方法により評価したところAランクであった。また、得られた偏光フィルムの異物を上記した方法により評価したところBランクであった。
実施例8で得られたフィルムロールを用い、洗浄浴を出るときのフィルムの上方側の面が使用したPVAフィルムにおいて大きい方の二乗平均粗さを有していた面となるように変更したこと以外は実施例8と同様にして偏光フィルムを作製した。得られた偏光フィルムの染色斑を上記した方法により評価したところAランクであった。また、得られた偏光フィルムの異物を上記した方法により評価したところCランクであった。
実施例8で得られたフィルムロールを用い、洗浄浴を出るときの洗浄浴の液面とフィルム面とのなす角度を60°から25°に変更したこと以外は実施例8と同様にして偏光フィルムを作製した。得られた偏光フィルムの染色斑を上記した方法により評価したところAランクであった。また、得られた偏光フィルムの異物を上記した方法により評価したところCランクであった。
実施例8で得られたフィルムロールを用い、洗浄浴を出るときの洗浄浴の液面とフィルム面とのなす角度を60°から88°に変更したこと以外は実施例8と同様にして偏光フィルムを作製した。得られた偏光フィルムの染色斑を上記した方法により評価したところAランクであった。また、得られた偏光フィルムの異物を上記した方法により評価したところCランクであった。
Claims (24)
- フィルム表面から窪んだ欠点であって面積が400μm2以上で深さが0.3μm以上の欠点の数が0.25個/m2以下であるポリビニルアルコール系重合体フィルム。
- 前記欠点の数が0.15個/m2以下である、請求項1に記載のポリビニルアルコール系重合体フィルム。
- ポリビニルアルコール系重合体フィルムに含まれるポリビニルアルコール系重合体の重合度が3,000以上10,000以下である、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。
- 長尺のポリビニルアルコール系重合体フィルムである、請求項1~3のいずれか1項に記載のポリビニルアルコール系重合体フィルム。
- 長さが6,000m以上である、請求項4に記載のポリビニルアルコール系重合体フィルム。
- 前記欠点が、フィルムの長さ方向に実質的に一定の間隔でフィルムの幅方向に実質的に同一の位置に存在する欠点を含む、請求項4または5に記載のポリビニルアルコール系重合体フィルム。
- 長尺のポリビニルアルコール系重合体フィルムが連続的に巻き取られてなるフィルムロールであって、フィルム表面から窪んだ欠点であって面積が400μm2以上で深さが0.3μm以上の欠点について、ポリビニルアルコール系重合体フィルムの巻き取り開始部分における当該欠点の数に対するポリビニルアルコール系重合体フィルムの巻き取り終了部分における当該欠点の数が1.4倍以下であるフィルムロール。
- 前記欠点の数が0.25個/m2以下である、請求項7に記載のフィルムロール。
- 前記欠点の数が0.15個/m2以下である、請求項7に記載のフィルムロール。
- ポリビニルアルコール系重合体フィルムに含まれるポリビニルアルコール系重合体の重合度が3,000以上10,000以下である、請求項7~9のいずれか1項に記載のフィルムロール。
- ポリビニルアルコール系重合体フィルムの長さが6,000m以上である、請求項7~10のいずれか1項に記載のフィルムロール。
- 前記欠点が、フィルムの長さ方向に実質的に一定の間隔でフィルムの幅方向に実質的に同一の位置に存在する欠点を含む、請求項7~11のいずれか1項に記載のフィルムロール。
- フィルムの両面のそれぞれにおいて二乗平均粗さを測定した際に、得られた2つの二乗平均粗さの差が0.3nm以上10nm以下であり、小さい方の二乗平均粗さが10nm以下である、ポリビニルアルコール系重合体フィルム。
- 大きい方の二乗平均粗さが1nm以上20nm以下である、請求項13に記載のポリビニルアルコール系重合体フィルム。
- 長尺のポリビニルアルコール系重合体フィルムである、請求項13または14に記載のポリビニルアルコール系重合体フィルム。
- 請求項15に記載のポリビニルアルコール系重合体フィルムが連続的に巻き取られてなるフィルムロール。
- 請求項13~15のいずれか1項に記載のポリビニルアルコール系重合体フィルムを原反フィルムとして用いる偏光フィルムの製造方法であって、染色工程、一軸延伸工程、固定処理工程および乾燥工程を有し、乾燥工程に入る前の最後の処理浴を出るときに、処理浴の液面とフィルム面とのなす角度が30°以上85°以下であると共に、フィルムの上方側の面がポリビニルアルコール系重合体フィルムにおいて小さい方の二乗平均粗さを有していた面である、製造方法。
- 請求項17に記載の製造方法によって製造される偏光フィルム。
- 表面にクロムメッキ層を有し、表面硬度がビッカース硬さで550HV以上900HV未満であり、表面温度が50℃以上115℃以下である金属支持体の表面上に、溶液状態または溶融状態のポリビニルアルコール系重合体を流延して乾燥させて製膜する工程を有する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、溶液状態または溶融状態のポリビニルアルコール系重合体を流延し始める直前において金属支持体の表面における面積(最大幅と最大端部間距離との積)が200μm2以上のクラックの数が0.7個/mm2以下である、製造方法。
- 溶液状態または溶融状態のポリビニルアルコール系重合体がポリビニルアルコール系重合体と水を含む製膜原液の形態である、請求項19に記載の製造方法。
- 前記ポリビニルアルコール系重合体の重合度が3,000以上10,000以下である、請求項19または20に記載の製造方法。
- 前記金属支持体の表面硬度がビッカース硬さで600HV以上800HV未満である、請求項19~21のいずれか1項に記載の製造方法。
- 表面にクロムメッキ層を有し、表面硬度がビッカース硬さで550HV以上900HV未満である金属支持体の表面温度を0.5℃/時間以上の変温速度で50℃以上115℃以下にする工程を有する、請求項19~22のいずれか1項に記載の製造方法。
- 請求項1~6および13~15のいずれか1項に記載のポリビニルアルコール系重合体フィルムを製造する、請求項19~23のいずれか1項に記載の製造方法。
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| CN109312086A (zh) * | 2016-06-13 | 2019-02-05 | 日本合成化学工业株式会社 | 聚乙烯醇系薄膜及其制造方法、以及使用该聚乙烯醇系薄膜的偏光膜 |
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| KR20170129095A (ko) * | 2015-03-17 | 2017-11-24 | 닛폰고세이가가쿠고교 가부시키가이샤 | 폴리비닐 알코올계 필름 및 이의 제조 방법, 및 편광막 |
| KR102453054B1 (ko) | 2015-03-17 | 2022-10-11 | 미쯔비시 케미컬 주식회사 | 폴리비닐 알코올계 필름 및 이의 제조 방법, 및 편광막 |
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| JP2016224410A (ja) * | 2015-05-29 | 2016-12-28 | 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及び偏光膜、ならびにポリビニルアルコール系フィルムの製造方法 |
| JP2016194726A (ja) * | 2016-07-27 | 2016-11-17 | 住友化学株式会社 | 気泡欠陥の少ない偏光子 |
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| JP2019123091A (ja) * | 2018-01-12 | 2019-07-25 | コニカミノルタ株式会社 | 支持体、支持体の製造方法および光学フィルムの製造方法 |
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| JP2016216741A (ja) | 2016-12-22 |
| CN112505818A (zh) | 2021-03-16 |
| KR102346772B1 (ko) | 2022-01-03 |
| CN104204045B (zh) | 2017-11-24 |
| JP6216848B2 (ja) | 2017-10-18 |
| CN112505818B (zh) | 2022-09-16 |
| KR102260000B1 (ko) | 2021-06-02 |
| JP6088976B2 (ja) | 2017-03-01 |
| TWI557164B (zh) | 2016-11-11 |
| TW201638169A (zh) | 2016-11-01 |
| KR20200023490A (ko) | 2020-03-04 |
| TW201638170A (zh) | 2016-11-01 |
| TW201404806A (zh) | 2014-02-01 |
| KR20140143206A (ko) | 2014-12-15 |
| KR20200110456A (ko) | 2020-09-23 |
| KR102392226B1 (ko) | 2022-04-28 |
| CN107656334A (zh) | 2018-02-02 |
| JPWO2013146459A1 (ja) | 2015-12-10 |
| CN104204045A (zh) | 2014-12-10 |
| CN107656334B (zh) | 2021-04-27 |
| TWI639636B (zh) | 2018-11-01 |
| TWI634140B (zh) | 2018-09-01 |
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