WO2016190235A1 - Film polymère d'alcool polyvinylique et procédé de fabrication associé - Google Patents

Film polymère d'alcool polyvinylique et procédé de fabrication associé Download PDF

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Publication number
WO2016190235A1
WO2016190235A1 PCT/JP2016/064993 JP2016064993W WO2016190235A1 WO 2016190235 A1 WO2016190235 A1 WO 2016190235A1 JP 2016064993 W JP2016064993 W JP 2016064993W WO 2016190235 A1 WO2016190235 A1 WO 2016190235A1
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WIPO (PCT)
Prior art keywords
film
pva
drying
drying roll
roll
Prior art date
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PCT/JP2016/064993
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English (en)
Japanese (ja)
Inventor
保二郎 森
翔平 井下
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Priority to JP2017520678A priority Critical patent/JP6716553B2/ja
Priority to CN202311059168.5A priority patent/CN117001908A/zh
Priority to KR1020177033978A priority patent/KR102038212B1/ko
Priority to CN201680031048.6A priority patent/CN107614242A/zh
Publication of WO2016190235A1 publication Critical patent/WO2016190235A1/fr

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Classifications

    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/52—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
    • B29K2029/14—Polyvinylacetals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • 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 thin polyvinyl alcohol polymer film capable of producing an optical film such as a polarizing film with few optical defects (hereinafter, “polyvinyl alcohol polymer” may be abbreviated as “PVA”). And a manufacturing method thereof, an optical film such as a polarizing film manufactured from the PVA film, and a manufacturing method of the optical film.
  • PVA polyvinyl alcohol polymer
  • a polarizing plate having a light transmission and shielding function is one of important components of a liquid crystal display (LCD) together with a liquid crystal having a light switching function.
  • LCDs are used in a wide range of small devices such as calculators and watches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, tablet terminals, and measuring instruments used indoors and outdoors. It has become. Of these LCD application fields, LCD TVs and LCD monitors are becoming thinner in addition to larger screens. In recent years, tablet terminals, which have been widely used, are becoming thinner. As a means for achieving LCD thinning, it is possible to reduce the thickness of the glass used in the LCD. From the viewpoint of solving the problem of warping of the glass due to the shrinkage stress of the polarizing plate, the polarizing plate is also used. Thinning is required.
  • a polarizing plate is generally produced by dyeing and uniaxially stretching a PVA film to produce a polarizing film, and then bonding a protective film such as a cellulose triacetate (TAC) film on the surface of the polarizing film. Therefore, in order to achieve thinning of the polarizing plate, it is required to produce a thin polarizing film using a thinner PVA film, and the specific thickness of the PVA film is 55 ⁇ m or less, further 30 ⁇ m or less. It is requested to do.
  • TAC cellulose triacetate
  • Patent Document 1 describes that a PVA film having a thickness of about 75 ⁇ m and a thickness spot of about 1.6 to 3.0 ⁇ m was manufactured by the method.
  • an object of the present invention is to provide a thin PVA film capable of producing an optical film such as a polarizing film with few optical defects. Moreover, an object of this invention is to provide the optical film with few optical defects manufactured from the said PVA film.
  • the number of broken line streaks in the PVA film is set to a specific value or less.
  • a film-forming apparatus provided with a plurality of drying rolls whose rotation axes are parallel to each other is used, and a film-forming stock solution containing PVA is formed on the first drying roll located on the most upstream side of the film-forming apparatus.
  • the present invention [1] A PVA film having a thickness of 55 ⁇ m or less, and a broken line streak arranged in an approximately straight line in the flow direction of the film with a period of 0.01 to 10 mm over a length of 10 cm or more per 1 m in the width direction of the film 5 or less PVA films; [2] The PVA film of the above [1], having a width of 2 m or more; [3] A method for producing a PVA film having a thickness of 55 ⁇ m or less, wherein a film forming apparatus including a plurality of drying rolls having rotation axes parallel to each other is used, and PVA is included on the first drying roll of the film forming apparatus.
  • the film-forming stock solution discharge rate (S 0 ) is set to 2. 5 to 5.0 m / min of production method; [4] The method according to [3] above, wherein the ratio (S 1 / S 0 ) of the peripheral speed (S 1 ) of the first drying roll to the discharge speed (S 0 ) of the film-forming stock solution is 7 or less; [5] The production method of the above [3] or [4], which is a production method of a PVA film having a width of 2 m or more; [6] An optical film produced from the PVA film of [1] or [2] above; [7] The optical film according to [6], which is a polarizing film; [8] A method for producing an optical film, comprising the step of uniaxially stretching using the PVA film of [1] or [2] above; [9] The production method
  • a thin PVA film capable of producing an optical film such as a polarizing film with few optical defects, a method for producing the thin PVA film, an optical film with few optical defects produced from the PVA film, and the optical A method of manufacturing a film is provided.
  • the PVA film of the present invention has a thickness of 55 ⁇ m or less, and a broken line streak arranged in a direction of 0.01 to 10 mm in a substantially straight line in the flow direction of the film over 10 cm or more in the width direction of the film. No more than 5 per meter.
  • the broken line streak that defines the number of the lines is formed by arranging irregularities approximately linearly in the flow direction of the film over 10 cm or more with a period of 0.01 to 10 mm as described above.
  • a broken line streak occurs along the flow direction of the film, and the length of one broken line far exceeds 10 cm.
  • the length is less than 10 cm, and it is difficult to call a broken line streak.
  • those having a length of 10 cm or more are handled as broken lines.
  • the protrusions protruding from the film surface are arranged to form unevenness as a result; the recesses recessed from the film surface are arranged, and as a result What forms the unevenness
  • the above-mentioned broken line streaks are formed by arranging irregularities with a period of 0.01 to 10 mm substantially linearly in the direction of film flow over 10 cm or more.
  • the period means the length of the film in the flow direction of one set of unevenness (a set of one concave portion and one convex portion adjacent to each other).
  • the period is in the range of 0.01 to 10 mm.
  • the period may be in the range of 0.1 to 5 mm, for example, and may be in the range of 0.2 to 1 mm.
  • the difference in thickness between the highest height and the lowest height is often in the range of 1 to 500 nm.
  • it may be within the range of 10 to 300 nm, further within the range of 20 to 100 nm, and particularly within the range of 30 to 90 nm.
  • the number of the broken line streaks is measured over the entire width direction on the straight line in the width direction passing through an arbitrary position in the flow direction.
  • the number can be obtained as the number per 1 m width.
  • the presence of the broken line streaks can be confirmed by, for example, a scanning white interference microscope.
  • the number of broken lines can be obtained by the method described later in the embodiment.
  • the number of the broken line streaks in the width direction per 1 m of the film needs to be 5 or less, preferably 3 or less, and more preferably 2 or less. Preferably, it may be 1.5 or less, and even 1 or less.
  • the number of broken lines is within the above range, an optical film with few optical defects can be easily obtained.
  • the number of broken lines is preferably 0.05 or more per 1 m in the width direction, more preferably 0.10 or more, still more preferably 0.15 or more, and 0.20 The above is most preferable.
  • PVA forming the PVA film examples include PVA (unmodified PVA) obtained by saponifying polyvinyl ester obtained by polymerizing vinyl ester, modified PVA obtained by graft copolymerization with a comonomer on the main chain of PVA, vinyl A so-called polyvinyl acetal resin in which a part of hydroxyl groups of modified PVA, unmodified PVA or modified PVA produced by saponifying a modified polyvinyl ester obtained by copolymerization of an ester and a comonomer is crosslinked with aldehydes such as formalin, butyraldehyde, and benzaldehyde And so on.
  • the amount of modification in the PVA is preferably 15 mol% or less, and more preferably 5 mol% or less.
  • vinyl ester used in the production of PVA examples include vinyl acetate, vinyl formate, vinyl laurate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl stearate, vinyl benzoate and the like. Can be mentioned. These vinyl esters can be used alone or in combination. Of these vinyl esters, vinyl acetate is preferred from the viewpoint of productivity.
  • Examples of the comonomer described above include olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene (such as ⁇ -olefin); acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, Acrylic esters such as n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
  • olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene (such as ⁇ -olefin); acrylic acid or a salt thereof; methyl acrylate, ethyl acrylate, Acrylic esters such as n-propyl acrylate,
  • acrylic acid having 1 to 18 carbon atoms of acrylic acid methacrylic acid or a salt thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i -Butyl, t-butyl methacrylate, Methacrylic acid esters such as 2-ethylhexyl crylate, dodecyl methacrylate, octadecyl methacrylate (for example, alkyl esters of 1 to 18 carbon atoms of methacrylic acid); acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N Acrylamide derivatives such as dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid or salts thereof, acrylamide propyl dimethylamine or salts thereof, N-methylol acrylamide or derivatives thereof; methacrylamide, N
  • the average degree of polymerization of PVA is preferably 1,000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more, from the viewpoint of polarization performance and durability of the polarizing film to be obtained.
  • the average degree of polymerization is preferably 8,000 or less, particularly preferably 6,000 or less, from the viewpoint of easy production of a homogeneous PVA film and stretchability.
  • the “average degree of polymerization” of PVA in the present specification refers to the average degree of polymerization measured according to JIS K6726-1994, and is the limit measured in water at 30 ° C. after re-saponifying and purifying PVA. Determined from viscosity.
  • the saponification degree of PVA is preferably 95.0 mol% or more, more preferably 98.0 mol% or more, and further preferably 99.0 mol% or more from the viewpoint of the polarizing performance and durability of the obtained polarizing film.
  • the “degree of saponification” of PVA in the present specification refers to the vinyl in relation to the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification. The ratio (mol%) occupied by the number of moles of alcohol units.
  • the degree of saponification of PVA can be measured according to the description of JIS K6726-1994.
  • the PVA constituting the PVA film may be one type of PVA, or may be one or more of two or more types of PVA that are different from each other in average polymerization degree, saponification degree, modification degree, and the like. Good.
  • the PVA content in the PVA film is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and in the range of 85 to 100% by mass. Further preferred.
  • the PVA film preferably contains a plasticizer because it can improve mechanical properties such as impact strength, process passability during secondary processing, and stretchability.
  • Preferred plasticizers include polyhydric alcohols, and specific examples include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like.
  • the PVA film can contain one or more of these plasticizers.
  • these plasticizers one or more of glycerin, diglycerin, and ethylene glycol are preferably used from the viewpoint of stretchability improvement effect when the PVA film is stretched and used, and glycerin is more preferable. Preferably used.
  • the content of the plasticizer in the PVA film is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of PVA contained in the PVA film. Is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.
  • the content is 1 part by mass or more, the stretchability of the PVA film can be further improved.
  • the content is 30 parts by mass or less, it is possible to prevent the PVA film from becoming too flexible and handling properties from being lowered.
  • the PVA film preferably contains a surfactant from the viewpoints of handleability and improvement of peelability from the film forming apparatus when the PVA film is produced.
  • a surfactant from the viewpoints of handleability and improvement of peelability from the film forming apparatus when the PVA film is produced.
  • anionic surfactant examples 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 alkyl ether types such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; alkyl phenyl ether types such as polyoxyethylene octyl phenyl ether; alkyl ester types such as polyoxyethylene laurate.
  • Alkylamine type such as polyoxyethylene lauryl amino ether
  • alkylamide type such as polyoxyethylene lauric acid amide
  • polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether
  • alkanolamide type alkanolamide type
  • allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether.
  • the PVA film can contain one or more of these surfactants.
  • these surfactants nonionic surfactants are preferred because of their excellent effect of reducing film surface abnormalities during film formation, and alkanolamide type surfactants are particularly preferred, and aliphatic carboxylic acids (for example, More preferred are dialkanolamides (for example, diethanolamide) of C8-30 saturated or unsaturated aliphatic carboxylic acid.
  • the content of the surfactant in the PVA film is such that the handleability of the PVA film and the peelability from the film forming apparatus when producing the PVA film can be further improved, and the occurrence of blocking can be reduced. It is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, still more preferably 0.05 parts by mass or more, and 1 part by mass with respect to 100 parts by mass of PVA. It is preferable that the amount be 0.5 parts by mass or less, more preferably 0.3 parts by mass or less.
  • the PVA film further contains other components such as antioxidants, ultraviolet absorbers, lubricants, colorants, antiseptics, antifungal agents, other polymer compounds other than those described above, and moisture as necessary. May be.
  • the PVA film can contain one or more of these other components.
  • the thickness of the PVA film needs to be 55 ⁇ m or less, preferably 40 ⁇ m or less, 30 ⁇ m or less, and further 20 ⁇ m or less. It may be. Broken line streaks are more likely to be a problem in thinner PVA films, and the effects of the present invention are particularly prominent in PVA films having such thickness.
  • the lower limit of the thickness of the PVA film is not particularly limited, but considering the handleability of the PVA film, the process passability during the production of the optical film, the optical performance of the resulting optical film (such as the polarizing performance of the polarizing film),
  • the thickness is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and further preferably 10 ⁇ m or more.
  • the thickness of the PVA film can be obtained as an average value obtained by measuring the thicknesses at arbitrary five locations.
  • the shape of the PVA film is not particularly limited, but a more uniform PVA film can be continuously and smoothly manufactured, and is also used continuously when an optical film such as a polarizing film is manufactured using the PVA film. It is preferable that the film is a long film.
  • the long film is preferably in the form of a film roll by winding it around a cylindrical core.
  • the length of the PVA film (the length in the flow direction) is not particularly limited, and can be set as appropriate according to the use, etc., but is continuously unwound from the film roll and used. In some cases, the longer the length of the PVA film, the more the loss when switching the film roll can be reduced.
  • the length is preferably 500 m or more, more preferably 1,000 m or more. Is more preferably 8,000 m or more, particularly preferably 8,000 m or more. Although there is no restriction
  • thermoplastic resin film Even if it is a single layer form (single layer film), or in the form of a laminated body like the PVA film formed by the coating method etc. on the thermoplastic resin film, for example
  • a single-layered form is preferred from the viewpoints of the effects of the present invention being more prominent, the complexity of laminating (coating and the like) work, and the cost of the thermoplastic resin film.
  • the width of the PVA film is not particularly limited, and can be set as appropriate according to the use of the PVA film or an optical film such as a polarizing film produced from the PVA film. From the point of progress, it is suitable for these uses when the width of the PVA film is 2 m or more, more preferably 3 m or more, and even more preferably 4 m or more. On the other hand, if the width of the PVA film is too large, it is likely to be difficult to perform uniaxial stretching uniformly when an optical film is produced by a device that has been put to practical use. Therefore, the width of the PVA film may be 7 m or less. preferable.
  • the manufacturing method of the PVA film of this invention is not specifically limited, According to the manufacturing method of the following this invention, the PVA film of this invention can be manufactured smoothly continuously.
  • the manufacturing method of the present invention for manufacturing a PVA film having a thickness of 55 ⁇ m or less includes a plurality of drying rolls whose rotation axes are parallel to each other (in order from the most upstream side to the downstream side, the first drying roll, 2), a film-forming stock solution containing PVA is discharged in the form of a film on the first drying roll of the film-forming apparatus and dried, followed by second drying.
  • This is a production method in which when the PVA film is formed by further drying with a drying roll after the roll, the discharge rate (S 0 ) of the raw film forming solution is set to 2.5 to 5.0 m / min.
  • a film-forming apparatus including a plurality of drying rolls whose rotation axes are parallel to each other is used, and a film-forming stock solution containing PVA is discharged into a film on the first drying roll of the film-forming apparatus. It dries, and it further dries with the drying roll after the 2nd drying roll following the downstream of the said 1st drying roll, and forms a PVA film.
  • the number of drying rolls is preferably 3 or more, more preferably 4 or more, and further preferably 5 to 30.
  • the plurality of drying rolls are preferably formed from a metal such as nickel, chromium, copper, iron, stainless steel, and the like, and in particular, the surface of the drying roll is formed from a metal material that is resistant to corrosion and has a specular gloss. More preferably. In order to increase the durability of the drying roll, it is more preferable to use a drying roll plated with a single layer or a combination of two or more layers such as a nickel layer, a chromium layer, and a nickel / chromium alloy layer.
  • first drying roll contact surface a film surface that does not contact the first drying roll
  • first drying roll non-contact surface a film surface that does not contact the first drying roll
  • a film-forming stock solution containing PVA may be discharged (cast) into a film form on the first drying roll using (film-form casting apparatus).
  • the discharge rate (S 0 ) of the film-forming stock solution needs to be 2.5 to 5.0 m / min.
  • the peripheral speed of the first drying roll against the discharge rate of the film-forming solution (S 0) the ratio of (S 1) (S 1 / S 0) Increasing or conversely increasing the film-forming stock solution discharge speed (S 0 ), while the film-forming stock solution discharge speed (S 0 ) has a peripheral speed (S 1 ) of the first drying roll.
  • the PVA film having the same thickness can be produced at a specific production rate by reducing the ratio (S 1 / S 0 ) of the present invention
  • the present inventors have developed a thin PVA film having a thickness of 55 ⁇ m or less.
  • the discharge speed (S 0 ) of the film-forming stock solution is preferably 2.6 m / min or more, and preferably 2.7 m / min or more, for the reason that the number of broken lines can be further reduced. Is more preferable, and it is still more preferable that it is 2.8 m / min or more. On the other hand, if the discharge rate (S 0 ) of the film-forming stock solution is too high, it tends to be difficult to stably produce the PVA film.
  • the discharge rate (S 0 ) of the film-forming stock solution is It is preferably 4.8 m / min or less, more preferably 4.5 m / min or less, still more preferably 4.2 m / min or less, and particularly preferably 4.0 m / min or less. preferable.
  • the discharge rate (S 0 ) of the film-forming stock solution means the linear velocity in the flow direction of the film-forming stock solution, and the volume per unit time of the film-forming stock solution discharged from the film-like discharge device is the film-like discharge rate. It can be determined by dividing by the opening area of the slit portion of the device (product of the slit width of the film-like discharge device and the average value of the slit opening).
  • a film-forming stock solution containing a PVA film can be prepared by mixing PVA with a liquid medium to form a solution, or by melting PVA pellets containing the liquid medium or the like to form a melt.
  • the liquid medium used in this case include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylenediamine, and diethylenetriamine. These liquid media are used alone. Or two or more of them may be used in combination. Among these, water, dimethyl sulfoxide, or a mixture of both are preferably used, and water is more preferably used.
  • the film-forming stock solution is preferably blended with one or more of the plasticizers, surfactants, and other components as described above in the description of the PVA film in the above-mentioned amounts.
  • the volatile fraction of the film-forming stock solution used for the production of the PVA film is preferably in the range of 50 to 90% by mass, more preferably in the range of 55 to 80% by mass, and 60 to 75% by mass. More preferably within the range. If the volatile fraction of the film-forming stock solution is too low, the viscosity of the film-forming stock solution may become too high, making filtration and defoaming difficult, or making the film itself difficult. On the other hand, if the volatile fraction of the film-forming stock solution is too high, the viscosity becomes too low and the thickness uniformity of the PVA film may be impaired.
  • the volatile fraction of the film-forming stock solution in this specification refers to the volatile fraction obtained by the following formula [I].
  • Volatile fraction (% by mass) of the film-forming stock solution ⁇ (Wa ⁇ Wb) / Wa ⁇ ⁇ 100 [I] (In the formula, Wa represents the mass (g) of the film-forming stock solution, and Wb represents the mass (g) when the film-forming stock solution of Wa (g) was dried in an electrothermal dryer at 105 ° C. for 16 hours.)
  • the surface temperature of the first drying roll is not particularly limited, but it is preferably in the range of 70 to 120 ° C., and in the range of 80 to 105 ° C., from the viewpoint of film drying uniformity and productivity. Is more preferable, and it is still more preferable to be in the range of 85 to 95 ° C.
  • the film-forming stock solution discharged in the form of a film may be dried on the first drying roll only by heating from the first drying roll, the first drying roll non-contact surface is simultaneously heated with the first drying roll. It is preferable from the viewpoints of uniform drying property, drying speed, and the like to dry by blowing hot air onto the film and applying heat from both sides of the film.
  • the temperature of the hot air blown on the non-contact surface of the first drying roll of the film is preferably 50 to 150 ° C., more preferably 70 to 120 ° C. from the viewpoint of drying efficiency, drying uniformity, and the like. More preferably, it is -95 ° C. Further, the dew point temperature of the hot air blown on the non-contact surface of the first drying roll of the film is preferably 5 to 20 ° C., and more preferably 10 to 15 ° C.
  • the method for blowing hot air to the non-contact surface of the first drying roll of the film is not particularly limited, and the hot air having a uniform wind speed and uniform temperature is uniformly applied to the non-contact surface of the first drying roll, preferably the entire surface thereof. Any of the methods that can be sprayed can be employed, and among them, the nozzle method, the current plate method, or a combination thereof is preferably employed.
  • the blowing direction of the hot air to the first drying roll non-contact surface of the film was substantially along the circumferential shape of the first drying roll non-contact surface of the film, even in the direction facing the first drying roll non-contact surface.
  • the direction may be the direction (direction substantially along the circumference of the roll surface of the first drying roll) or the other direction.
  • the film when the film is dried on the first drying roll, it is preferable to exhaust the volatile matter generated from the film by drying and the hot air after spraying.
  • the exhaust method is not particularly limited, but it is preferable to employ an exhaust method that does not cause wind speed spots and temperature spots of hot air sprayed on the non-contact surface of the first drying roll of the film.
  • the peripheral speed (S 1 ) of the first drying roll can be within the range of 12 to 35 m / min because the number of broken lines can be further reduced and the stability during production is excellent.
  • the peripheral speed (S 1 ) of the first drying roll is more preferably 15 m / min or more, more preferably 30 m / min or less, and still more preferably 28 m / min or less. 26 m / min or less is particularly preferable.
  • the ratio (S 1 / S 0 ) of the peripheral speed (S 1 ) of the first drying roll to the discharge speed (S 0 ) of the film-forming stock solution can further reduce the number of broken lines and can be stable during production. From the viewpoint of excellent properties, it is preferably 7 or less, more preferably 6.8 or less, still more preferably 6.5 or less, particularly preferably 6.3 or less, It is preferably more than 3, more preferably more than 5, still more preferably more than 5.2, particularly preferably more than 5.5, and most preferably more than 6.
  • the film-forming stock solution discharged in the form of a film on the first drying roll is dried on the first drying roll, and the volatile content rate of the film (the volatile content rate of the film at the time of peeling from the first drying roll) is preferable. Is peeled from the first drying roll when it is 5 to 30% by mass, more preferably 7 to 20% by mass, and still more preferably 8 to 15% by mass. When the volatile content of the film at the time of peeling from the first drying roll is 5% by mass or more, the difference in drying speed between the first drying roll contact surface and the first drying roll non-contact surface becomes large. It can suppress that a film becomes easy to curl.
  • the volatile fraction of the film in the present specification refers to the volatile fraction determined by the following formula [II].
  • Film volatile content (mass%) ⁇ (Wc ⁇ Wd) / Wc ⁇ ⁇ 100 [II]
  • Wc represents the mass (g) of the sample collected from the film
  • Wd is the sample of Wc (g) placed in a vacuum dryer at a temperature of 50 ° C. and a pressure of 0.1 kPa or less and dried for 4 hours.
  • It represents mass (g) at the time.
  • the film dried to a volatile content of preferably 5 to 30% by mass on the first drying roll is peeled off from the first drying roll, and this time, the non-contact surface of the first drying roll is opposed to the second drying roll.
  • the film is preferably dried with a second drying roll.
  • the film dried by the second drying roll is peeled off from the second drying roll, and the third drying roll, the fourth drying roll, the fifth drying roll, etc., depending on the number of drying rolls provided in the film forming apparatus, etc. * What is necessary is just to dry sequentially by several drying rolls, such as.
  • each drying roll from the second drying roll to the final drying roll is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, from the viewpoint of uniform drying properties, drying speed, etc. More preferably, it is preferably less than 100 ° C, more preferably less than 90 ° C, still more preferably less than 85 ° C, and particularly preferably less than 80 ° C.
  • the heat treatment can be performed using a heat treatment roll or other known heat treatment apparatus.
  • the heat treatment roll there may be one heat treatment roll or a plurality of heat treatment rolls.
  • the surface temperature of the heat treatment roll is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and more preferably 110 ° C. or higher, because a PVA film having a moderately advanced crystallization and excellent hot water resistance can be obtained. More preferably it is.
  • the surface temperature of the heat treatment roll is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and further preferably 130 ° C. or lower.
  • the heat treatment time it is preferably in the range of 3 to 60 seconds, more preferably in the range of 5 to 30 seconds, because the target PVA film can be produced more smoothly. preferable.
  • the film forming apparatus described above may have a hot air drying device, a humidity control device, or the like as necessary.
  • the film obtained as described above is further subjected to humidity conditioning treatment, cutting of both end portions (ear portions) of the film, if necessary, and finally wound into a roll with a predetermined length. It can be set as the PVA film of invention.
  • the volatile content of the PVA film finally obtained by the above-described series of treatments is preferably in the range of 1 to 5% by mass, and more preferably in the range of 2 to 4% by mass.
  • the PVA film of this invention is a polarizing film and retardation. It is preferably used as an original film for producing an optical film such as a film. Such an optical film can be produced, for example, by applying a treatment such as uniaxial stretching using the PVA film of the present invention.
  • the method for producing a polarizing film using the PVA film of the present invention as a raw film is not particularly limited, and any conventionally employed method may be employed. Examples of such a method include a method of dyeing and uniaxially stretching a PVA film or uniaxially stretching a PVA film containing a dye.
  • a method of subjecting the PVA film of the present invention to dyeing, uniaxial stretching, fixing treatment, drying treatment, and heat treatment as necessary can be mentioned.
  • the order of dyeing and uniaxial stretching is not particularly limited, and dyeing may be performed before uniaxial stretching, dyeing may be performed simultaneously with uniaxial stretching, or dyeing may be performed after uniaxial stretching.
  • steps such as uniaxial stretching and dyeing may be repeated a plurality of times.
  • the rupture at the time of uniaxial stretching is performed by performing uniaxial stretching in a state where the thermoplastic resin film is laminated. It can be further reduced.
  • Examples of the dye used for dyeing the PVA film include iodine or a dichroic organic dye (for example, DirectBlack 17, 19, 154; DirectBrown 44, 106, 195, 210, 223; DirectRed 2, 23, 28, 31, 37, 39. 79, 81, 240, 242, 247; DirectBlue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; DirectViolet 9, 12, 51, 98; DirectGreen 1, 85; Direct Yellow 8, 12, 44, 86, 87; dichroic dyes such as Direct Orange 26, 39, 106, 107) can be used. These dyes can be used alone or in combination of two or more. Dyeing can usually be performed by immersing the PVA film in a solution containing the dye, but the treatment conditions and treatment method are not particularly limited.
  • the uniaxial stretching of the PVA film may be performed by either a wet stretching method or a dry heat stretching method, but the wet stretching method is preferred from the viewpoint of the performance and quality stability of the obtained polarizing film.
  • the wet stretching method include a method of stretching a PVA film in pure water, an aqueous solution containing various components such as an additive and an aqueous medium, or an aqueous dispersion in which various components are dispersed.
  • Uniaxial stretching by a wet stretching method Specific examples of the method include a method of uniaxially stretching in warm water containing boric acid, a method of uniaxially stretching in a solution containing the above-described dye or a fixing treatment bath described later, and the like.
  • Uniaxial stretching is preferably performed in the flow direction of the PVA film.
  • the stretching temperature for uniaxial stretching is not particularly limited, but in the case of wet stretching, a temperature in the range of preferably 20 to 90 ° C, more preferably 25 to 70 ° C, and even more preferably 30 to 65 ° C is adopted. In the case of hot stretching, a temperature within the range of 50 to 180 ° C. is preferably employed.
  • the stretching ratio of uniaxial stretching (the total stretching ratio in the case of performing uniaxial stretching in multiple stages) is preferably stretched as much as possible from the point of polarization performance until just before the film is cut, and specifically 4 times or more. It is preferably 5 times or more, more preferably 5.5 times or more.
  • the upper limit of the stretching ratio is not particularly limited as long as the film is not broken, but is preferably 8.0 times or less in order to perform uniform stretching.
  • the thickness of the uniaxially stretched film is preferably 1 to 30 ⁇ m, particularly 3 to 25 ⁇ m.
  • the said thickness can measure
  • fixing treatment is often performed in order to strengthen the adsorption of the dye to the uniaxially stretched film.
  • a method of immersing the film in a fixing treatment bath to which boric acid and / or boron compound is added is generally widely adopted. In that case, you may add an iodine compound in a processing bath as needed.
  • the film subjected to the uniaxial stretching treatment or the uniaxial stretching treatment and the fixing treatment is then subjected to a drying treatment (heat treatment).
  • the temperature of the drying treatment (heat treatment) is preferably 30 to 150 ° C., particularly 50 to 140 ° C. If the temperature of the drying treatment (heat treatment) is too low, the dimensional stability of the obtained polarizing film tends to be lowered, while if too high, the polarizing performance is likely to deteriorate due to the decomposition of the dye.
  • a polarizing film can be obtained by bonding optically transparent protective films having mechanical strength to both surfaces or one surface of the polarizing film obtained as described above.
  • a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like is used.
  • a PVA adhesive or a urethane adhesive is generally used, and among them, a PVA adhesive is preferably used.
  • the polarizing plate obtained as described above can be used as a component of a liquid crystal display device after being coated with an acrylic adhesive or the like and then bonded to a glass substrate.
  • a retardation film, a viewing angle improving film, a brightness improving film, or the like may be bonded simultaneously.
  • Optical defects in polarizing film After appropriately dividing the polarizing film in the width direction, place the polarizing film in an orthogonal direction between polarizing plates for observation (two layers of parallel Nicols, polarization degree of 99.99% or more), and visually observe the degree of optical defects. The following criteria were used for evaluation. ⁇ : No or almost no optical defects can be found. ⁇ : Optical defects can be found easily. XX: Optical defects can be found very easily.
  • Example 1 [Production of PVA film] It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water.
  • a film-forming stock solution having a volatile content of 70% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.8 m / min, and a film-forming apparatus provided with a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other.
  • iodine / potassium iodide aqueous solution containing potassium iodide at a concentration of 3% by mass (2 3) and then immersed in a boric acid / potassium iodide aqueous solution at 30 ° C. containing 3% by weight of boric acid and 3% by weight of potassium iodide.
  • Boric acid / potassium iodide aqueous solution at 63 ° C.
  • Example 2 It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water.
  • a film-forming stock solution having a volatile content rate of 66 mass% was discharged from a T-shaped slit die at a discharge speed (S 0 ) of 2.8 m / min, and a film-forming apparatus comprising a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other.
  • heat treatment is performed with a heat treatment roll having a surface temperature of 115 ° C., and both end portions (ear portions) are cut and wound on a cylindrical core to finally have a thickness of 40.6 ⁇ m, a length of 2,000 m, and a width.
  • a long PVA film single layer film having 2.6 m and a volatile content (water content) of 2% by mass was produced.
  • the unevenness having a height difference of 50 to 60 nm was approximately 10 cm or more in a straight line in the film flow direction with a period of 0.3 to 0.7 mm.
  • Comparative Example 1 It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water.
  • a film-forming stock solution having a volatilization rate of 66% by mass was discharged from a T-type slit die at a discharge speed (S 0 ) of 2.4 m / min, and a film-forming apparatus comprising a plurality of drying rolls and heat treatment rolls whose rotation axes were parallel to each other.
  • Comparative Example 2 It consists of 100 parts by mass of PVA (average polymerization degree 2,400, saponification degree 99.9 mol%) obtained by saponifying polyvinyl acetate, 12 parts by mass of glycerol, 0.1 part by mass of lauric acid diethanolamide, and water.
  • a film-forming stock solution having a volatile content rate of 66% by mass is discharged from a T-shaped slit die at a discharge speed (S 0 ) of 2.0 m / min. 1 film is discharged onto a drying roll (peripheral speed (S 1 ) 15 m / min), and hot air of 90 ° C.

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

Abstract

La présente invention se rapporte à un film de PVAL possédant une épaisseur inférieure ou égale à 55 µm, le film de PVAL ayant au plus cinq rayures en lignes pointillées, agencées de manière sensiblement linéaire sur au moins 10 cm dans le sens d'écoulement du film dont les irrégularités ont un intervalle de 0,01 à 10 mm, pour 1 m dans le sens de la largeur du film ; un procédé de fabrication d'un film de PVAL possédant une épaisseur inférieure ou égale à 55 µm. Le procédé de fabrication utilise un appareil de formation de film pourvu d'une pluralité de séchoirs à cylindres, dont les axes de rotation sont parallèles les uns aux autres, et la vitesse de déversement (SO) de la solution de formation de film est comprise entre 2,5 et 5,0 m/min lorsqu'un film de PVAL est obtenu par le déversement sous forme de film d'une solution de formation de film de PVAL contenant du PVAL sur un premier séchoir à cylindres de l'appareil de formation de film et par le séchage, puis par le séchage par les seconds séchoirs à cylindres suivants.
PCT/JP2016/064993 2015-05-28 2016-05-20 Film polymère d'alcool polyvinylique et procédé de fabrication associé WO2016190235A1 (fr)

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JP2017520678A JP6716553B2 (ja) 2015-05-28 2016-05-20 ポリビニルアルコール系重合体フィルム及びその製造方法
CN202311059168.5A CN117001908A (zh) 2015-05-28 2016-05-20 聚乙烯醇系聚合物膜和其制造方法
KR1020177033978A KR102038212B1 (ko) 2015-05-28 2016-05-20 폴리비닐알코올계 중합체 필름 및 그 제조 방법
CN201680031048.6A CN107614242A (zh) 2015-05-28 2016-05-20 聚乙烯醇系聚合物膜和其制造方法

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WO2020138438A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film soluble dans l'eau, son procédé de fabrication, et emballage
WO2020138440A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film soluble dans l'eau et emballage
WO2020138444A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film hydrosoluble et emballage
WO2020138437A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film soluble dans l'eau, procédé de fabrication de celui-ci et emballage
WO2022004343A1 (fr) * 2020-06-29 2022-01-06 株式会社クラレ Film hydrosoluble, et emballage
WO2022004536A1 (fr) * 2020-06-30 2022-01-06 株式会社クラレ Film de poly(alcool vinylique) et procédé de fabrication d'un film optique dans lequel ce film est utilisé
WO2022004535A1 (fr) * 2020-06-30 2022-01-06 株式会社クラレ Film d'alcool polyvinylique et procédé de production de film optique l'utilisant

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JP6665512B2 (ja) * 2015-12-14 2020-03-13 コニカミノルタ株式会社 光学フィルムの製造方法

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JP2000301555A (ja) * 1999-04-21 2000-10-31 Fuji Photo Film Co Ltd 溶液製膜方法
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JP2006199927A (ja) * 2004-12-21 2006-08-03 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルムおよび偏光膜

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JP3473838B2 (ja) 2000-06-28 2003-12-08 株式会社クラレ ポリビニルアルコールフィルムの製造法
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JPS52133371A (en) * 1976-04-30 1977-11-08 Toshiba Machine Co Ltd Method of forming polyvinyl alcohol film
JP2000301555A (ja) * 1999-04-21 2000-10-31 Fuji Photo Film Co Ltd 溶液製膜方法
JP2005231185A (ja) * 2004-02-19 2005-09-02 Konica Minolta Opto Inc 光学フィルムの製造方法及び光学フィルム
JP2006199927A (ja) * 2004-12-21 2006-08-03 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルムおよび偏光膜

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JPWO2020138438A1 (ja) * 2018-12-28 2021-11-11 株式会社クラレ 水溶性フィルム、その製造方法および包装体
WO2020138440A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film soluble dans l'eau et emballage
JPWO2020138440A1 (ja) * 2018-12-28 2021-11-11 株式会社クラレ 水溶性フィルムおよび包装体
WO2020138438A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film soluble dans l'eau, son procédé de fabrication, et emballage
WO2020138437A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film soluble dans l'eau, procédé de fabrication de celui-ci et emballage
CN113226941A (zh) * 2018-12-28 2021-08-06 株式会社可乐丽 水溶性膜以及包装体
JPWO2020138437A1 (ja) * 2018-12-28 2021-11-11 株式会社クラレ 水溶性フィルム、その製造方法および包装体
JPWO2020138445A1 (ja) * 2018-12-28 2021-11-11 株式会社クラレ 水圧転写用ベースフィルムおよび水圧転写用印刷フィルム
CN113226941B (zh) * 2018-12-28 2023-10-27 株式会社可乐丽 水溶性膜以及包装体
WO2020138445A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film de base de transfert hydraulique et film d'impression par transfert hydraulique
WO2020138444A1 (fr) * 2018-12-28 2020-07-02 株式会社クラレ Film hydrosoluble et emballage
JP7336464B2 (ja) 2018-12-28 2023-08-31 株式会社クラレ 水溶性フィルムおよび包装体
JP7240423B2 (ja) 2018-12-28 2023-03-15 株式会社クラレ 水圧転写用ベースフィルムおよび水圧転写用印刷フィルム
JP7240420B2 (ja) 2018-12-28 2023-03-15 株式会社クラレ 水溶性フィルム、その製造方法および包装体
JP7240421B2 (ja) 2018-12-28 2023-03-15 株式会社クラレ 水溶性フィルム、その製造方法および包装体
WO2022004343A1 (fr) * 2020-06-29 2022-01-06 株式会社クラレ Film hydrosoluble, et emballage
WO2022004535A1 (fr) * 2020-06-30 2022-01-06 株式会社クラレ Film d'alcool polyvinylique et procédé de production de film optique l'utilisant
WO2022004536A1 (fr) * 2020-06-30 2022-01-06 株式会社クラレ Film de poly(alcool vinylique) et procédé de fabrication d'un film optique dans lequel ce film est utilisé

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KR20180013908A (ko) 2018-02-07
TWI741984B (zh) 2021-10-11
JPWO2016190235A1 (ja) 2018-03-15
KR102038212B1 (ko) 2019-10-29
CN107614242A (zh) 2018-01-19

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