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WO2019244968A1 - Film d'alcool polyvinylique et son procédé de production - Google Patents

Film d'alcool polyvinylique et son procédé de production Download PDF

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Publication number
WO2019244968A1
WO2019244968A1 PCT/JP2019/024446 JP2019024446W WO2019244968A1 WO 2019244968 A1 WO2019244968 A1 WO 2019244968A1 JP 2019024446 W JP2019024446 W JP 2019024446W WO 2019244968 A1 WO2019244968 A1 WO 2019244968A1
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WIPO (PCT)
Prior art keywords
film
pva
thickness
polyvinyl alcohol
mass
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.)
Ceased
Application number
PCT/JP2019/024446
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English (en)
Japanese (ja)
Inventor
高廣 中村
遼太郎 田中
勝啓 高藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
Original Assignee
Kuraray Co Ltd
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 Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to CN201980040936.8A priority Critical patent/CN112292418B/zh
Priority to KR1020207035980A priority patent/KR102725372B1/ko
Priority to JP2020525790A priority patent/JP7301829B2/ja
Publication of WO2019244968A1 publication Critical patent/WO2019244968A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a polyvinyl alcohol film having a small film surface defect and a uniform thickness, and a method for producing the same.
  • a polarizing plate having a function of transmitting and blocking light is a fundamental component of a liquid crystal display (LCD) together with a liquid crystal that changes the polarization state of light.
  • LCDs are being 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, and measuring devices used indoors and outdoors. .
  • LCDs liquid crystal televisions and liquid crystal monitors are becoming thinner, and demand for thin film is increasing.
  • a normal polarizing plate has a configuration in which a protective film such as a cellulose triacetate (TAC) film is bonded to a polarizing film produced by uniaxially stretching and dyeing a polyvinyl alcohol film.
  • a protective film such as a cellulose triacetate (TAC) film is bonded to a polarizing film produced by uniaxially stretching and dyeing a polyvinyl alcohol film.
  • Patent Document 1 As a method for producing a polyvinyl alcohol film having a uniform thickness, for example, in Patent Document 1, after preparing a stock solution by dissolving polyvinyl alcohol in a solvent such as water, the stock solution is dripped onto a drum (roll). In the production method of forming a film and heating and drying the film on the drum, a production method in which the speed ratio between the speed of the drum and the discharge speed of the undiluted solution is 1 to 5 is described. Patent Document 1 describes that by setting such a speed ratio, a polyvinyl alcohol film having a uniform thickness and excellent smoothness can be manufactured even in a large area.
  • Patent Document 2 discloses a polyvinyl alcohol film having a thickness of 5 to 60 ⁇ m, a width of 2 m or more, and a length of 2 km or more, wherein the coefficient of variation of the thickness over the entire surface is 1% or less.
  • Patent Document 2 discloses that in order to reduce the coefficient of variation to 1% or less, a touch line in which an aqueous solution of polyvinyl alcohol is in contact with a cast drum (roll) is stabilized by an air knife to make an MD direction (film flow direction). A technique for reducing unevenness in thickness is described.
  • Patent Document 3 discloses that a polyvinyl alcohol film obtained by adding a nonionic surfactant to polyvinyl alcohol has no die line or foreign matter, has excellent long-term film forming properties, and has a thickness of 120 ⁇ m. It is described that no die line or gel was generated even when a film forming process of preparing a polyvinyl alcohol film and then biaxially stretching the film was performed continuously for 60 days.
  • the difference between the maximum thickness and the minimum thickness of the film obtained by adjusting the speed ratio between the drum speed and the stock solution discharge speed described in Patent Document 1 was 1.6 ⁇ m or more.
  • the mechanical flow direction of the PVA film hereinafter, the mechanical flow direction is referred to as MD direction.
  • Thickness did not pose a major problem.
  • Patent Document 3 does not describe that the thickness unevenness rate is particularly deteriorated when the thickness of the polyvinyl alcohol film is 35 ⁇ m or less, and neither describes nor suggests a solution thereto.
  • An object of the present invention is to provide a PVA film having a thickness of 35 ⁇ m or less and a method for producing the film, in which unevenness in the thickness in the MD direction is reduced and streak-like defects continuously occurring in the MD direction are small.
  • the width direction of the PVA film is set to the TD direction
  • the machine flow direction is set to the MD direction
  • streak defects having a height difference of 0.15 ⁇ m or more that extend linearly continuously for 1.5 m or more in the MD direction are 5 in the entire width of the film.
  • the thickness of the central portion in the TD direction is set to 0 in the MD direction.
  • a polyvinyl alcohol film having a thickness unevenness rate of 5.5% or less; Thickness unevenness rate (t MAX ⁇ t MIN ) / t AVE ⁇ 100 (%) (1)
  • the present invention even if the thickness of the film is as thin as 35 ⁇ m or less, a streak-like defect continuously occurring in the MD direction is small, and a PVA film with reduced thickness unevenness in the MD direction and a method for producing the PVA film.
  • a polarizing film in which generation of wrinkles is suppressed can be obtained. Furthermore, since the wrinkles of the polarizing film are suppressed, when the protective film is bonded to the polarizing film and processed into a polarizing plate, no entrapment of air bubbles between the polarizing film and the protective film occurs, and the resultant is obtained. The quality of the polarizing plate is improved.
  • the PVA film of the present invention is characterized in that the average thickness t AVE is 35 ⁇ m or less and the thickness unevenness ratio in the MD direction is within 5.5%.
  • the thickness unevenness rate in the present invention is defined as TD direction in the width direction of the film, MD direction in the machine flow direction of the film, and the thickness at the center of the film in the TD direction is 1.0 m at 0.5 mm intervals in the MD direction.
  • t MAX the maximum value of the film thickness
  • t MIN the minimum value of the film thickness
  • t AVE when the measurement is performed over the range, it is defined by the following equation (1).
  • Thickness unevenness rate (t MAX ⁇ t MIN ) / t AVE ⁇ 100 (%) (1)
  • the lower limit of the average value t AVE of the thickness is not particularly limited, but if it is too thin, stretching breakage is likely to occur during uniaxial stretching for producing a polarizing film. Therefore, the average value t AVE is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and particularly preferably 15 ⁇ m or more.
  • PV As the PVA constituting the PVA film of the present invention, a PVA film obtained by polymerizing a vinyl ester monomer and saponifying the vinyl ester polymer to make the vinyl ester unit a vinyl alcohol unit can be used.
  • the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl versatate.
  • vinyl is used.
  • a monomer copolymerizable with the vinyl ester monomer may be used within a range that does not impair the purpose of the present invention (preferably 15 mol based on all monomer units in PVA). %, More preferably 5 mol% or less).
  • a monomer include olefins having 3 to 30 carbon atoms such as ethylene, propylene, 1-butene, and isobutene; acrylic acid and its salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, and acryl.
  • Acrylic esters such as i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and salts thereof Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate And methacrylic acid such as octadecyl methacrylate Acid esters; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulf
  • the average degree of polymerization of PVA constituting the PVA film of the present invention is preferably at least 500 from the viewpoint of the strength of the PVA film, more preferably at least 1,000 from the viewpoint of polarization performance, still more preferably at least 2,000, particularly preferably at least 3,500. preferable.
  • the upper limit of the degree of polymerization of PVA is preferably 10,000 or less from the viewpoint of the film forming properties of the PVA film of the present invention.
  • the degree of saponification of the PVA constituting the PVA film of the present invention is preferably 95 mol% or more, more preferably 96 mol% or more, from the viewpoint of the water resistance of the polarizing film obtained by uniaxially stretching the film. More preferably, it is 98 mol% or more.
  • the degree of saponification of PVA refers to a structural unit (typically, a vinyl ester unit) of PVA which can be converted into a vinyl alcohol unit (—CH 2 —CH (OH) —) by saponification and a vinyl ester. It means the ratio (mol%) of the number of moles of the vinyl alcohol unit to the total number of moles with the alcohol unit.
  • a polyhydric alcohol as a plasticizer to PVA.
  • the polyhydric alcohol include ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like. One of these can be used alone, or two or more can be used in combination. it can. Among them, ethylene glycol or glycerin is preferably used because of its effect of improving the stretchability.
  • the amount of the polyhydric alcohol to be added is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and still more preferably 5 to 20 parts by mass, per 100 parts by mass of PVA. If the amount is less than 1 part by mass, the dyeing properties and the stretchability may be reduced. If the amount is more than 30 parts by mass, the PVA film may be too flexible and the handleability may be reduced.
  • the surfactant is not particularly limited, but an anionic or nonionic surfactant is preferable.
  • the anionic surfactant include a carboxylic acid type such as potassium laurate, a sulfate type such as octyl sulfate, and a sulfonic acid type such as dodecylbenzenesulfonate.
  • Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether, alkyl phenyl ether types such as polyoxyethylene octyl phenyl ether, alkyl ester types such as polyoxyethylene laurate, and polyoxyethylene lauryl amino.
  • Alkylamine type such as ether, alkylamide type such as polyoxyethylene lauric amide, polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether, alkanolamide type such as lauric acid diethanolamide and oleic acid diethanolamide, polyoxy Nonionic surfactants such as allyl phenyl ether type such as alkylene allyl phenyl ether are exemplified.
  • the nonionic surfactant an alkanolamide type nonionic surfactant is preferable, and lauric acid diethanolamide is more preferable. These surfactants can be used alone or in combination of two or more.
  • the addition amount is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.5 part by mass, and more preferably 0.05 to 0.3 part by mass with respect to 100 parts by mass of PVA. Parts are particularly preferred.
  • the addition amount is less than 0.01 part by mass, the effect of improving stretchability and dyeability is difficult to appear, and when it is more than 1 part by mass, the surfactant is eluted on the surface of the PVA film and blocking of the PVA films is prevented. This may cause a decrease in handleability.
  • the thickness unevenness rate defined by the above formula (1) is 5.5% or less. If the thickness unevenness ratio of the PVA film is larger than this, wrinkles are generated in the obtained polarizing film.
  • the thickness unevenness rate is more preferably 4% or less.
  • the temperature of the drying roll needs to be further increased. However, when the temperature of the drying roll is set to, for example, 96 ° C. or higher, cracks easily occur in the plating layer on the roll surface. Further, even if the thickness unevenness is less than 3%, the streak-like defect is not significantly improved, so the thickness unevenness is preferably 3% or more.
  • streak defects having a height difference of 0.15 ⁇ m or more extending linearly continuously for 1.5 m or more in the MD direction are 5 or less in the entire width of the PVA film, and are continuously 1.5 m or more in the MD direction. It is necessary that linear defects extending in a straight line and having a height difference of 0.50 ⁇ m or more do not exist in the entire width of the PVA film.
  • the streak-like defect is a defect that appears as a continuous single line of 1.5 m or more extending in the MD direction, and is caused by a difference in thickness from the periphery.
  • the height difference When the height difference is 0.15 ⁇ m or more, the color spot after dyeing becomes deep, and when the number of such streak-like defects having the height difference exceeds 5 in the entire width of the film, a practical problem occurs. Further, when the height difference is 0.5 ⁇ m or more, the color spot after dyeing becomes further dark, and even if there is even one streak-like defect having such a height difference, a practical problem occurs. Streak-like defects are evaluated by the method described in Examples.
  • the width of the PVA film of the present invention is not particularly limited, and may be, for example, 0.5 m or more. In recent years, since a wide polarizing film has been required, the width is preferably at least 2.0 m, more preferably at least 2.5 m, even more preferably at least 3.5 m. On the other hand, a PVA film having an excessively large width may increase the manufacturing cost of a film forming apparatus, or may make it difficult to stretch uniformly when an optical film is manufactured using a practically used manufacturing apparatus. For this reason, the width of the PVA film is preferably 7.0 m or less, and more preferably 6.5 m or less.
  • a roll film forming machine equipped with one or more rotating rolls, a drying device, a humidity control device and a winding device is used.
  • a motor, a transmission, or the like is used to drive each device, and the transport speed is adjusted.
  • the drying temperature of the PVA film is generally from 50 to 150 ° C.
  • the film forming method for example, a cast film forming method using a film forming stock solution in which PVA is dissolved in a solvent, or a roll film forming method in which a film forming stock solution made of water-containing polyvinyl alcohol is extruded and dripped onto a roll is adopted. In particular, the latter is preferred.
  • the film forming stock solution comprising the hydrated polyvinyl alcohol may contain an organic solvent.
  • the PVA-containing stock solution supplied on the roll is preferably at 94 to 98 ° C. at the die inlet, more preferably at 94.5 to 96.5 ° C. preferable.
  • the temperature of the film forming solution is less than 94 ° C., the leveling property of the film forming solution supplied on the roll is reduced, and the thickness unevenness tends to increase.
  • the temperature is higher than 98 ° C., the viscosity of the film-forming stock solution decreases, and the lip tip and the discharged film-forming stock solution interfere with each other.
  • the volatile matter content of the PVA-containing stock solution used for producing the PVA film is preferably 50 to 90% by mass, more preferably 55 to 80% by mass. If the volatile content is less than 50% by mass, the viscosity may be high, so that film formation may be difficult. When the volatile content is more than 90% by mass, the viscosity becomes too low, and the thickness uniformity of the PVA film may be impaired.
  • a die made of a flexible lip When producing a PVA film, it is preferable to use a die made of a flexible lip, and to supply a film forming stock solution from the die onto a roll of a roll film forming machine.
  • the die include a T-die, an I-die, and a lip coater die. Next, volatile components such as water and an organic solvent contained in the stock solution are evaporated on the roll.
  • the temperature of the roll to which the stock solution is supplied is preferably from 88 ° C. to 92 ° C., more preferably from 89 ° C. to 90 ° C.
  • the temperature is lower than 88 ° C.
  • the peeling property from the roll is deteriorated due to poor drying, and the thickness unevenness may be increased.
  • the temperature exceeds 92 ° C.
  • crystallization of PVA proceeds on the surface in contact with the roll of the film, and a difference in crystallinity from the other surface may occur. If there is a difference in crystallinity between one surface and the other surface of the film, a difference occurs in water absorption characteristics, so that the film is easily curled in a processing step of immersion in water, and the processability deteriorates.
  • the peripheral speed of the roll is preferably in the range of 10.0 to 50.0 m / min.
  • productivity is poor.
  • the peripheral speed exceeds the above upper limit, the time of contact with the roll is shortened, so that drying of the PVA film tends to be insufficient.
  • the PVA film After drying and adjusting the humidity of the PVA film peeled from the roll to adjust the PVA film to an appropriate PVA film, the PVA film is wound up.
  • the PVA film is dyed, uniaxially stretched, fixed, dried, and, if necessary, heat-treated.
  • the order of each step is not particularly limited, and two steps such as dyeing and uniaxial stretching may be performed simultaneously. Further, each step may be repeated a plurality of times.
  • the dyeing can be performed before, during, or after the uniaxial stretching. However, since the degree of crystallinity of PVA tends to increase due to the uniaxial stretching and the dyeing property may decrease, the uniaxial stretching may be performed. It is preferable to carry out in an optional step prior to stretching or during uniaxial stretching.
  • Dyes used for dyeing include 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.
  • Direct Blue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; Direct Violet 9, 12, 51, 98; Direct Green 1, 85; Dichroic dyes such as Yellow 8, 12, 44, 86, 87; Direct Orange 26, 39, 106, 107 and the like can be used alone or as a mixture of two or more.
  • Dyeing is generally performed by immersing a PVA film in a solution containing the dye, but the processing conditions and processing methods, such as mixing the dye with a PVA-containing stock solution to form a film, are described below. There is no particular limitation.
  • the uniaxial stretching method performed in the length direction of the PVA film a wet stretching method in which the film is stretched while immersed in a solution, or a dry heat stretching method in which the PVA film is absorbed and then stretched in air can be adopted.
  • the uniaxial stretching of the PVA film may be performed in a solution containing the dye or in a fixing bath described later.
  • the stretching is preferably performed at a stretch ratio as high as possible within a range in which the PVA film is not cut, and specifically, preferably 4 times or more, more preferably 5 times or more, and particularly preferably 6 times or more. When the stretching ratio is smaller than 4 times, it is difficult to obtain practically sufficient polarization performance and durability performance.
  • the stretching temperature is not particularly limited, but is preferably from 30 to 90 ° C. when the PVA film is stretched in water (wet stretching), and preferably from 50 to 180 ° C. when stretching by dry heat.
  • the thickness of the stretched film is preferably 2 to 25 ⁇ m, more preferably 5 to 20 ⁇ m.
  • a fixing treatment can be performed for the purpose of strengthening the adsorption of the dye to the PVA film.
  • boric acid and a boron compound are added to the treatment bath used for the fixing treatment.
  • an iodine compound may be added to the treatment bath as needed.
  • the drying treatment (heat treatment) of the PVA film is preferably performed at 30 to 150 ° C, more preferably at 50 to 150 ° C.
  • the polarizing film obtained as described above is usually used as a polarizing plate by laminating a protective film having optical strength and mechanical strength on both sides or one side thereof.
  • a protective film usually, a cellulose acetate film, an acrylic film, a polyester film, or the like is used.
  • the streak-like defect is a defect that is observed as a continuous single line of 1.5 m or more extending in the machine flow direction (MD direction) at the time of film formation.
  • the film is irradiated with light using a light source, and the light transmitted through the film is irradiated with light. When projected on a white wall, it is recognized as a continuous bright or dark pattern extending in the MD direction.
  • the film having the streak-like defect has a height difference of 0.15 ⁇ m or more between the concave portion and the convex portion on the surface, and can be observed as the light pattern or the dark pattern.
  • a sample piece cut out by 1.5 m in the MD direction from the PVA film obtained in the following example or comparative example in the MD direction was suspended so that the MD direction was up and down, and was 350 cm away from the film surface.
  • a halogen lamp light source manufactured by S1 Co., Ltd. having a luminous intensity of about 550 Lux was installed at the position, and light was projected perpendicularly to the film surface.
  • a streak-like bright or dark pattern observed when the light transmitted through the film was projected on a white wall 10 cm away from the film was judged as a streak-like defect.
  • the difference in height in the film thickness direction between the defective portion and the surrounding portion is measured for each portion of the film corresponding to the streak-like defect with a contact type thickness meter “KG601A” manufactured by Anritsu Corporation for the total number of streak-like defects. did.
  • the number of streak-like defects extending linearly and continuously in the MD direction for 1.5 m or more in the MD direction in the entire width of the PVA film is in the range of 0.15 to 0.50 ⁇ m and 1.5 m or more in the MD direction.
  • the presence or absence of streak-like defects having a height difference of 0.5 ⁇ m or more extending linearly was determined and evaluated according to the following criteria. If the height difference exceeds 0.50 ⁇ m, even one streak-like defect poses a practical problem.
  • A Five or less streak defects having a height difference of 0.15 to 0.50 ⁇ m in the entire width of the PVA film, and no streak defects having a height difference of 0.5 ⁇ m or more
  • B There are more than 5 streak defects having a height difference in the range of 0.15 to 0.50 ⁇ m, or there are streak defects having a height difference of 0.5 ⁇ m or more.
  • Example 1 Using a roll film forming machine, 100 parts by mass of PVA having a degree of saponification of 99.9 mol% and an average degree of polymerization of 2400, 12 parts by mass of glycerin, 0.1 part by mass of lauric acid diethanolamide, and a volatile matter content of 70% The mass-forming stock solution of mass% is discharged from a T-die at 96 ° C. to a first drying roll (surface temperature: 91.7 ° C., peripheral speed: 24.8 m / min), and then peeled off by a second drying roll, and then to a second drying roll. Thereafter, drying was performed at an average of 85 ° C.
  • a PVA film (thickness t AVE: 21.1 ⁇ m, width: 3000 mm) was obtained by winding with a winding device.
  • the obtained film had a thickness unevenness ratio of 3.79%, a number of streak-like defects having a height difference in the range of 0.15 to 0.50 ⁇ m was two in the entire width, and a stripe having a height difference of 0.5 ⁇ m or more. No shape defects were present. Also, after stretching 2.6 times in the MD direction, no wrinkles lined up in the TD direction occurred.
  • Example 2 Using a roll film forming machine, 100 parts by mass of PVA having a degree of saponification of 99.9 mol% and an average degree of polymerization of 2400, 12 parts by mass of glycerin, 0.1 part by mass of lauric acid diethanolamide, and a volatile matter content of 70% Mass% of the stock solution was discharged from a T-die at 94 ° C. to a first drying roll (surface temperature: 89.7 ° C., peripheral speed: 24.8 m / min), and then peeled off by a second drying roll, followed by a second drying roll. Thereafter, drying was performed at an average of 85 ° C.
  • a first drying roll surface temperature: 89.7 ° C., peripheral speed: 24.8 m / min
  • a PVA film (thickness t AVE 20.7 ⁇ m, film width 3000 mm) was obtained by winding up with a winding device.
  • the obtained film had a thickness unevenness ratio of 4.55%, a number of streak-like defects having a height difference in the range of 0.15 to 0.50 ⁇ m was one in the entire width, and a stripe having a height difference of 0.5 ⁇ m or more. No shape defects were present. Also, after stretching 2.6 times in the MD direction, very slight wrinkles arranged in the TD direction occurred.
  • Example 3 Using a roll film forming machine, 100 parts by mass of PVA having a degree of saponification of 99.9 mol% and an average degree of polymerization of 2400, 12 parts by mass of glycerin, 0.1 part by mass of lauric acid diethanolamide, and a volatile matter content of 70% The mass-forming stock solution of mass% is discharged from a T-die at 97 ° C. to a first drying roll (surface temperature: 89.7 ° C., peripheral speed: 24.8 m / min), and then peeled off by a second drying roll to form a second drying roll. Thereafter, drying was performed at an average of 85 ° C.
  • a PVA film (thickness t AVE 20.4 ⁇ m, film width 3000 mm) was obtained by winding with a winding device.
  • the obtained film had a thickness unevenness rate of 5.11%, and no streak-like defects were generated over the entire width. Also, after stretching 2.6 times in the MD direction, very slight wrinkles arranged in the TD direction occurred.
  • Example 4 Using a roll film forming machine, 100 parts by mass of PVA having a degree of saponification of 99.9 mol% and an average degree of polymerization of 2400, 12 parts by mass of glycerin, 0.1 part by mass of lauric acid diethanolamide, and a volatile matter content of 70% The mass-forming stock solution of mass% is discharged from a T-die at 96 ° C. to a first drying roll (surface temperature: 88.0 ° C., peripheral speed: 24.8 m / min), and then peeled off by a second drying roll to form a second drying roll. Thereafter, drying was performed at an average of 85 ° C.
  • a PVA film (thickness t AVE 20.1 ⁇ m, film width 3000 mm) was obtained by winding with a winding device.
  • the obtained film had a thickness unevenness rate of 5.22%, and no streak-like defects were generated over the entire width. Also, after stretching 2.6 times in the MD direction, very slight wrinkles arranged in the TD direction occurred.
  • a PVA film (thickness t AVE 20.1 ⁇ m, film width 3000 mm) was obtained by winding with a winding device.
  • the obtained film had a thickness unevenness rate of 4.13%, and the number of streak-like defects having a height difference in the range of 0.15 to 0.50 ⁇ m was 12 in the entire width. Further, after stretching 2.6 times in the MD direction, remarkable wrinkles arranged in the TD direction occurred.
  • a PVA film (thickness t AVE 20.4 ⁇ m, film width 3000 mm) was obtained by winding with a winding device.
  • the obtained film had a thickness unevenness ratio of 7.13% and the number of streak-like defects having a height difference in the range of 0.15 to 0.50 ⁇ m was 50 or more in the entire width. Further, after stretching 2.6 times in the MD direction, remarkable wrinkles arranged in the TD direction occurred.
  • a PVA film (thickness t AVE: 20.3 ⁇ m, film width: 3000 mm) was obtained by winding with a winding device.
  • the obtained film had a thickness unevenness rate of 5.95%, the number of streak-like defects having a height difference in the range of 0.15 to 0.50 ⁇ m was two in the entire width, and the number of stripe-like defects was 0.5 ⁇ m or more. No shape defects were present.
  • noticeable wrinkles lined up in the TD direction occurred.
  • a PVA film (thickness t AVE 20.6 ⁇ m, film width 3000 mm) was obtained by winding up with a winding device.
  • the obtained film had a thickness unevenness ratio of 7.22%, the number of streak-like defects having a height difference in the range of 0.15 to 0.50 ⁇ m was one in the entire width, and the number of streaks having a height difference of 0.5 ⁇ m or more was obtained. No shape defects were present. Further, after stretching 2.6 times in the MD direction, remarkable wrinkles arranged in the TD direction occurred.
  • the film was taken up by a take-up device to obtain a PVA film (thickness t AVE: 44.7 ⁇ m, film width: 3000 mm).
  • the obtained film had a thickness unevenness rate of 6.71%, a number of streak-like defects having a height difference of 0.15 to 0.50 ⁇ m was one in the entire width, and a stripe having a height difference of 0.5 ⁇ m or more. No shape defects were present. Also, after stretching 2.6 times in the MD direction, no wrinkles lined up in the TD direction occurred.
  • Table 1 shows the production conditions of the PVA film in Examples, Comparative Examples, and Reference Examples and the evaluation results of the obtained PVA films.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention concerne un film d'alcool polyvinylique (PVA), le nombre de défauts de type bande ayant une différence de hauteur d'au moins 0,15 µm et s'étendant en continu au moins 1,5 m dans une ligne droite dans la direction MD (direction de flux de machine) est inférieur ou égal à 5 sur toute la largeur du film, et le nombre de défauts de type bande ayant une différence de hauteur d'au moins 0,50 µm et s'étendant en continu au moins 1,5 m dans une ligne droite dans la direction MD est nul sur toute la largeur du film. Lorsque tMAX, tMIN, et tAVE sont respectivement la valeur maximale, la valeur minimale, et la valeur moyenne de l'épaisseur de la partie centrale du film dans la direction TD (direction de la largeur du film) mesurée pour une section de 1,0 m à des intervalles de 0,5 mm dans la direction MD, tAVE est de 35 µm ou moins et l'écart d'épaisseur tel que défini par l'équation (1) ci-dessous est de 5,5 % ou moins. En dépit d'une faible épaisseur, le film présente peu de défauts de type bande et présente un écart d'épaisseur réduit dans la direction MD, et ainsi la formation de rides est supprimée lorsque le film est étiré. (1) : Écart d'épaisseur = (tMAX-tMIN)/tAVE×100(%)
PCT/JP2019/024446 2018-06-21 2019-06-20 Film d'alcool polyvinylique et son procédé de production Ceased WO2019244968A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021187310A1 (fr) * 2020-03-17 2021-09-23

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2008111702A1 (fr) * 2007-03-15 2008-09-18 Lg Chem, Ltd. Procédé de préparation d'un film de polarisation à base d'alcool polyvinylique, et film de polarisation à base d'alcool polyvinylique préparé par ce procédé
JP2009067010A (ja) * 2007-09-18 2009-04-02 Tohcello Co Ltd ポリビニルアルコール系フィルムの製造方法及びフィルム
JP2011237580A (ja) * 2010-05-10 2011-11-24 Fujifilm Corp 偏光子およびその製造方法、偏光板およびその製造方法、並びに液晶表示装置
WO2015076169A1 (fr) * 2013-11-21 2015-05-28 株式会社クラレ Film d'alcool polyvinylique
WO2016182010A1 (fr) * 2015-05-13 2016-11-17 株式会社クラレ Film d'alcool polyvinylique
JP2016222834A (ja) * 2015-06-02 2016-12-28 株式会社クラレ ポリビニルアルコールフィルムの製造方法
WO2017204271A1 (fr) * 2016-05-27 2017-11-30 日本合成化学工業株式会社 Film à base de poly(alcool polyvinylique), procédé pour sa production et film de polarisation utilisant un film à base de poly(alcool polyvinylique)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4663842B2 (ja) 2000-03-10 2011-04-06 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その製造方法
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
JP5649820B2 (ja) * 2007-08-24 2015-01-07 株式会社クラレ ポリビニルアルコールフィルムおよびその製造法
CN103897208A (zh) * 2011-03-29 2014-07-02 可乐丽股份有限公司 偏振膜的制造方法
CN104185653B (zh) * 2012-03-30 2018-07-06 株式会社可乐丽 聚乙烯醇系聚合物膜和偏光膜
JP6750261B2 (ja) 2015-03-17 2020-09-02 三菱ケミカル株式会社 ポリビニルアルコール系フィルム、ポリビニルアルコール系フィルムの製造方法、偏光フィルム及び偏光板
WO2016148159A1 (fr) * 2015-03-17 2016-09-22 日本合成化学工業株式会社 Film de poly(alcool vinylique), procédé pour sa production et film polarisant

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2008111702A1 (fr) * 2007-03-15 2008-09-18 Lg Chem, Ltd. Procédé de préparation d'un film de polarisation à base d'alcool polyvinylique, et film de polarisation à base d'alcool polyvinylique préparé par ce procédé
JP2009067010A (ja) * 2007-09-18 2009-04-02 Tohcello Co Ltd ポリビニルアルコール系フィルムの製造方法及びフィルム
JP2011237580A (ja) * 2010-05-10 2011-11-24 Fujifilm Corp 偏光子およびその製造方法、偏光板およびその製造方法、並びに液晶表示装置
WO2015076169A1 (fr) * 2013-11-21 2015-05-28 株式会社クラレ Film d'alcool polyvinylique
WO2016182010A1 (fr) * 2015-05-13 2016-11-17 株式会社クラレ Film d'alcool polyvinylique
JP2016222834A (ja) * 2015-06-02 2016-12-28 株式会社クラレ ポリビニルアルコールフィルムの製造方法
WO2017204271A1 (fr) * 2016-05-27 2017-11-30 日本合成化学工業株式会社 Film à base de poly(alcool polyvinylique), procédé pour sa production et film de polarisation utilisant un film à base de poly(alcool polyvinylique)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021187310A1 (fr) * 2020-03-17 2021-09-23
WO2021187310A1 (fr) * 2020-03-17 2021-09-23 株式会社クラレ Procédé de production d'un film de poly(alcool vinylique)
CN115210302A (zh) * 2020-03-17 2022-10-18 株式会社可乐丽 聚乙烯醇膜的制造方法
JP7653413B2 (ja) 2020-03-17 2025-03-28 株式会社クラレ ポリビニルアルコールフィルムの製造方法

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