WO2017033552A1 - Polyvinyl alcohol resin for production of polarizing film, method for producing same, polyvinyl alcohol film, method for producing polyvinyl alcohol film, polarizing film and polyvinyl alcohol resin - Google Patents
Polyvinyl alcohol resin for production of polarizing film, method for producing same, polyvinyl alcohol film, method for producing polyvinyl alcohol film, polarizing film and polyvinyl alcohol resin Download PDFInfo
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- WO2017033552A1 WO2017033552A1 PCT/JP2016/068597 JP2016068597W WO2017033552A1 WO 2017033552 A1 WO2017033552 A1 WO 2017033552A1 JP 2016068597 W JP2016068597 W JP 2016068597W WO 2017033552 A1 WO2017033552 A1 WO 2017033552A1
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- Prior art keywords
- polyvinyl alcohol
- film
- resin
- weight
- polarizing film
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and 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
- C08F16/02—Homopolymers and 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 by an alcohol radical
- C08F16/04—Acyclic compounds
- C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/06—Conditioning or physical treatment of the material to be shaped by drying
- B29B13/065—Conditioning or physical treatment of the material to be shaped by drying of powder or pellets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to a polyvinyl alcohol resin for manufacturing a polarizing film. More specifically, the present invention relates to a polyvinyl alcohol resin capable of producing a polyvinyl alcohol film excellent in transparency and dyeability with high productivity, a method for producing the same, a polyvinyl alcohol film using the polyvinyl alcohol resin, and a method thereof. The present invention relates to a manufacturing method and a polarizing film using the polyvinyl alcohol film and having excellent uniformity of polarization degree.
- a polyvinyl alcohol film has been produced by dissolving a polyvinyl alcohol resin in water to prepare an aqueous solution (film forming stock solution), and then forming and drying the film by a solution casting method (cast method). .
- the polyvinyl alcohol film thus obtained is used in many applications as a film excellent in transparency and dyeability, and one of its useful applications is a polarizing film.
- a polarizing film is used as a basic component of a liquid crystal display, and in recent years, its use has been expanded to high-luminance and high-definition equipment.
- a polyvinyl alcohol film that is excellent in transparency and dyeability necessary for producing a polarizing film free from display defects and polarization unevenness can be produced with high productivity.
- resin Provide resin.
- the present inventors have focused on the degree of weight swelling of the polyvinyl alcohol resin used as a raw material for the polyvinyl alcohol film, and a polyvinyl alcohol resin having a specific degree of weight swelling is obtained. Because it can suppress the generation of undissolved substances and aggregates in water, and can prevent the adhesion and blockage of these pipes, it can produce polyvinyl alcohol film with high productivity, and can also suppress the generation of clusters.
- the present inventors have found that a polarizing film free from display defects and uneven polarization can be produced.
- the gist of the present invention is a polyvinyl alcohol-based resin for producing a polarizing film, wherein the weight swelling degree calculated by the following formula (1) is 1.4 to 1.65.
- Degree of swelling of weight (weight when immersed in water at 15 ° C. for 1 hour and then centrifuged at 2,000 G for 1 minute) / (weight when dried at 105 ° C. for 2 hours after centrifugation) (1) )
- the present invention also provides a method for producing the above-mentioned polyvinyl alcohol resin for producing a polarizing film, which comprises a step of drying at 120 to 150 ° C. for 1 to 4 hours, A polyvinyl alcohol film obtained by using a polyvinyl alcohol resin for producing a polarizing film, a method for producing a polyvinyl alcohol film comprising the following steps (A) to (D), a polarizing film comprising the film, A polyvinyl alcohol resin having a weight swelling degree calculated by the above formula (1) of 1.4 to 1.65 is also provided.
- B A step of dewatering the polyvinyl alcohol resin after washing with water by centrifugation.
- C The process of preparing the aqueous solution of polyvinyl alcohol-type resin in a dissolution tank.
- D The process of forming into a film the polyvinyl alcohol-type resin aqueous solution by the casting method.
- the polyvinyl alcohol-based resin for producing a polarizing film of the present invention suppresses the generation of undissolved substances and aggregates in water, and prevents the adhesion to these pipes and the pipe clogging. Can be manufactured. Furthermore, since the generation of clusters can be suppressed, it is suitable for producing a polarizing film free from display defects and uneven polarization.
- the present invention is described in detail below.
- an unmodified polyvinyl alcohol resin that is, a resin produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate is used.
- a resin obtained by saponifying a copolymer of vinyl acetate and a small amount (usually 10 mol% or less, preferably 5 mol% or less) of a copolymerizable component with vinyl acetate may be used. it can.
- components copolymerizable with vinyl acetate include unsaturated carboxylic acids (including salts, esters, amides, nitriles, etc.), and olefins having 2 to 30 carbon atoms (eg, ethylene, propylene, n-butene). , Isobutene, etc.), vinyl ethers, unsaturated sulfonates and the like.
- the modified polyvinyl alcohol-type resin obtained by chemically modifying the hydroxyl group after saponification can also be used.
- a polyvinyl alcohol resin having a 1,2-diol structure in the side chain can be used as the polyvinyl alcohol resin.
- a polyvinyl alcohol resin having a 1,2-diol structure in the side chain includes, for example, (i) a method of saponifying a copolymer of vinyl acetate and 3,4-diacetoxy-1-butene, and (ii) acetic acid.
- the weight average molecular weight of the polyvinyl alcohol-based resin is preferably 100,000 to 200,000, particularly preferably 111 to 180,000, and more preferably 120,000 to 160,000. If the weight average molecular weight is too small, sufficient optical performance tends not to be obtained when the polyvinyl alcohol resin is used as an optical film, and if it is too large, stretching becomes difficult when the film is used as a polarizing film. Tend to be difficult.
- the weight average molecular weight of the polyvinyl alcohol resin in the present invention is a weight average molecular weight measured by a GPC-MALS method.
- the average saponification degree of the polyvinyl alcohol resin is preferably 99.0 mol% or more, particularly preferably 99.3 mol% or more, more preferably 99.5 mol% or more, and particularly preferably 99.7 mol% or more. It is. If the average saponification degree is too low, sufficient optical performance cannot be obtained when a polyvinyl alcohol-based resin is used as an optical film.
- the average saponification degree in the present invention is measured according to JIS K 6726.
- the polyvinyl alcohol resin preferably has a weight average molecular weight of 120,000 or more and an average saponification degree of 99.5 mol% or more.
- the greatest feature of the present invention is that a polyvinyl alcohol resin having a weight swelling degree of 1.4 to 1.65 is used.
- the weight swelling degree in this invention is computed by following formula (1).
- Weight swell degree (weight when immersed in water at 15 ° C. for 1 hour and then centrifuged at 2,000 G for 1 minute) / (weight when dried at 105 ° C. for 2 hours after centrifugation) (1) )
- the weight swelling degree is preferably 1.43 to 1.62, particularly preferably 1.45 to 1.60, and further preferably 1.47 to 1.58.
- the weight swelling degree exceeds the upper limit, the particles of the polyvinyl alcohol-based resin easily aggregate in water or in a state of containing moisture, and the aggregate easily adheres in the pipe, thereby achieving the object of the present invention. Can not. Moreover, it becomes difficult to dissolve in water due to agglomeration, and the clusters tend to remain in the aqueous solution, and the object of the present invention cannot be achieved. On the other hand, even if the degree of weight swelling is less than the lower limit, it becomes difficult to dissolve in water, and the clusters tend to remain in the aqueous solution, and the object of the present invention cannot be achieved.
- Examples of a method for controlling the weight swelling degree include a technique for controlling the molecular weight and the degree of saponification, a technique for drying the polyvinyl alcohol resin under specific conditions, and a technique for controlling the particle diameter by sieving.
- the method of drying polyvinyl alcohol-type resin on specific conditions as mentioned later is preferable.
- a film called a skin layer
- the degree of weight swelling can be controlled.
- the synthesized polyvinyl alcohol resin is subjected to solvent washing, drying, and, if necessary, subsequent processes such as pulverization and sieving to be used for forming a polyvinyl alcohol film.
- the drying process is important for controlling the degree of weight swelling, and in the present invention, the drying process is preferably performed at 120 to 150 ° C. for 1 to 4 hours.
- the drying temperature is particularly preferably 121 to 145 ° C., more preferably 122 to 140 ° C., and particularly preferably 123 to 135 ° C. If the drying temperature is too high, the degree of weight swelling tends to decrease and the polyvinyl alcohol resin tends to yellow. Conversely, if it is too low, drying tends to be insufficient and the degree of weight swelling tends to increase.
- the drying time is particularly preferably 1.3 to 3.7 hours, more preferably 1.5 to 3.5 hours. If the drying time is too long, the degree of weight swelling tends to decrease and the polyvinyl alcohol resin tends to yellow. On the other hand, if it is too short, drying tends to be insufficient and the degree of weight swelling tends to increase.
- Such a drying step may be performed by a known dry drying technique such as a rotary dryer or a stirring drying tank, but as a preferred embodiment of the present invention, performing the wet drying before the dry drying step, It is preferable for forming an appropriate skin layer.
- the wet drying is performed by spraying water vapor while flowing the resin powder in a heated jacket or a vented extruder. In wet drying, it is impossible to completely remove moisture from the resin, but it is possible to reduce the water content of the resin to the order of several percent.
- the polyvinyl alcohol resin for producing a polarizing film of the present invention is obtained.
- the polyvinyl alcohol film is produced by the following steps (A) to (D) using the polyvinyl alcohol resin of the present invention.
- a step of washing the polyvinyl alcohol resin with water (B) A step of dewatering the polyvinyl alcohol resin after washing with water by centrifugation.
- C The process of preparing the aqueous solution of polyvinyl alcohol-type resin in a dissolution tank.
- D The process of forming into a film the polyvinyl alcohol-type resin aqueous solution by the casting method.
- the polyvinyl alcohol resin described above is washed with water in order to remove the remaining sodium acetate.
- the water used as the cleaning liquid may contain a small amount of auxiliary components such as alcohol and surfactant.
- the polyvinyl alcohol resin in a slurry state is dehydrated with a centrifugal separator to obtain a wet cake having a water content of 50% by weight or less. If the water content is too high, it tends to be difficult to prepare a desired aqueous solution concentration in the step (C).
- the weight swelling degree of the polyvinyl alcohol-based resin is excessively large or excessively small, adhesion or deposition of the resin to the pipe occurs. Such a defect is most likely to occur in a wet cake state. Specifically, it occurs in SUS piping from the centrifuge outlet to the dissolution tank.
- step (C) water, the obtained polyvinyl alcohol-based resin wet cake, and, if necessary, a plasticizer such as glycerin or a surfactant are charged into the dissolving tank, and dissolved by heating and stirring.
- a plasticizer such as glycerin or a surfactant
- Such dissolution is preferably carried out by blowing water vapor in a dissolution tank equipped with a vertical circulation flow generation type stirring blade in view of solubility. In such a case, it is preferable from the viewpoint that uniform stirring can be performed when steam is blown into the dissolution tank and the temperature in the tank reaches 40 to 80 ° C.
- the dissolution temperature is too low, sufficient dissolution of the polyvinyl alcohol-based resin cannot be obtained, and the transparency of the polyvinyl alcohol-based film tends to decrease. If it is too high, the decomposition product of the polyvinyl alcohol-based resin or the surfactant is present. And the hue of the polyvinyl alcohol film tends to decrease.
- the concentration of the aqueous polyvinyl alcohol-based resin solution is preferably 15 to 60% by weight, particularly preferably 18 to 55% by weight, More preferably, it is 20 to 50% by weight. If the resin concentration is too low, the drying load of the film becomes large. Conversely, if the resin concentration is too high, the viscosity becomes too high and film formation tends to be difficult.
- the aqueous polyvinyl alcohol resin solution used in the present invention is obtained, but the obtained aqueous polyvinyl alcohol resin solution is preferably defoamed.
- the defoaming method include stationary defoaming and defoaming with a multi-screw extruder having a vent.
- a twin-screw extruder having a vent is usually used as the multi-screw extruder having the vent.
- step (D) the polyvinyl alcohol-based resin aqueous solution is filtered, and then discharged and fluted from a T-type slit die to a cast mold such as a cast drum or an endless belt to form a film.
- a cast mold such as a cast drum or an endless belt to form a film.
- the polyvinyl alcohol film of the present invention is obtained.
- the polyvinyl alcohol film of the present invention preferably has a thickness of 60 ⁇ m or less, particularly preferably 30 ⁇ m or less. If the thickness is too large, it is difficult to reduce the thickness of the polarizing film.
- the polyvinyl alcohol film of the present invention preferably has a width of 4 m or more from the viewpoint of productivity, and more preferably 4 km or more from the viewpoint of productivity.
- the polyvinyl alcohol film of the present invention preferably has a haze of 0.3% or less, particularly preferably 0.2% or less, and more preferably 0.1% or less. If the haze is too high, the light transmittance of the polarizing film tends to decrease.
- a method for reducing such haze a method for controlling the weight swelling degree of the polyvinyl alcohol resin described above, a method for improving the solubility by adding a surfactant to the polyvinyl alcohol resin aqueous solution, a cast type surface smoothness The technique etc. which improve are mentioned.
- the polyvinyl alcohol film of the present invention has few defects, is excellent in transparency and dyeability, and is preferably used as a raw material for a polarizing film.
- the polarizing film of the present invention is produced through steps such as swelling, dyeing, boric acid crosslinking, stretching, washing, and drying by unwinding the polyvinyl alcohol film from a roll and transferring it in the horizontal direction.
- the swelling process is performed before the dyeing process.
- water is usually used as the treatment liquid.
- the treatment solution may contain a small amount of an iodide compound, an additive such as a surfactant, alcohol, or the like.
- the temperature of the swelling bath is usually about 10 to 45 ° C., and the immersion time in the swelling bath is usually about 0.1 to 10 minutes. Moreover, you may perform extending
- the dyeing step is performed by bringing the film into contact with a liquid containing iodine or a dichroic dye.
- a liquid containing iodine or a dichroic dye usually, an iodine-potassium iodide aqueous solution is used.
- the iodine concentration is suitably 0.1-2 g / L, and the potassium iodide concentration is 1-100 g / L.
- the dyeing time is practically about 30 to 500 seconds.
- the temperature of the treatment bath is preferably 5 to 50 ° C.
- the aqueous solution may contain a small amount of an organic solvent compatible with water in addition to the aqueous solvent. Moreover, you may perform extending
- the boric acid crosslinking step is performed using a boron compound such as boric acid or borax.
- the boron compound is used in the form of an aqueous solution or a water-organic solvent mixture at a concentration of about 10 to 100 g / L, and it is preferable that potassium iodide coexists in the solution from the viewpoint of stabilizing the polarization performance.
- the temperature during the treatment is preferably about 30 to 70 ° C., and the treatment time is preferably about 0.1 to 20 minutes. If necessary, the stretching operation may be performed during the treatment.
- the stretching step it is preferable to stretch 3 to 10 times, preferably 3.5 to 6 times in a uniaxial direction.
- a slight stretching may be performed in a direction perpendicular to the stretching direction.
- the temperature during stretching is preferably 30 to 170 ° C.
- the draw ratio may be finally set within the above range, and the drawing operation may be performed not only in one stage but also in any stage of the manufacturing process.
- the washing step is performed, for example, by immersing a polyvinyl alcohol film in an aqueous solution of iodide such as water or potassium iodide, thereby removing deposits generated on the surface of the film.
- iodide such as water or potassium iodide
- the concentration of potassium iodide may be about 1 to 80 g / L.
- the temperature during the washing treatment is usually 5 to 50 ° C., preferably 10 to 45 ° C.
- the treatment time is usually 1 to 300 seconds, preferably 10 to 240 seconds.
- the drying process may be performed in the atmosphere at 40 to 80 ° C. for 1 to 10 minutes.
- the polarization degree of the polarizing film of the present invention is preferably 99.5% or more, more preferably 99.8% or more. If the degree of polarization is too low, there is a tendency that the contrast in the liquid crystal display cannot be secured.
- the degree of polarization is generally the light transmittance (H 11 ) measured at the wavelength ⁇ in the state where two polarizing films are overlapped so that their orientation directions are the same direction, and the two polarizing films. It is calculated according to the following equation from the light transmittance (H 1 ) measured at the wavelength ⁇ in a state where the films are superposed so that the orientation directions are orthogonal to each other. [(H 11 ⁇ H 1 ) / (H 11 + H 1 )] 1/2
- the single transmittance of the polarizing film of the present invention is preferably 43% or more. If the single transmittance is too low, it tends to be impossible to achieve high brightness of the liquid crystal display.
- the single transmittance is a value obtained by measuring the light transmittance of a single polarizing film using a spectrophotometer.
- the polarizing film of the present invention is obtained, the polarizing film of the present invention is suitable for producing a polarizing plate with little polarization unevenness.
- the manufacturing method of this polarizing plate is demonstrated.
- the polarizing film is bonded to one or both surfaces of the polarizing film through an adhesive as an optically isotropic resin film as a protective film to form a polarizing plate.
- protective films include films of cellulose triacetate, cellulose diacetate, polycarbonate, polymethyl methacrylate, cycloolefin polymer, cycloolefin copolymer, polystyrene, polyethersulfone, polyarylene ester, poly-4-methylpentene, polyphenylene oxide, and the like. Or a sheet.
- the bonding method is performed by a known method. For example, after a liquid adhesive composition is uniformly applied to a polarizing film, a protective film, or both, the two are bonded and pressure-bonded, and heated or activated. This is done by irradiating energy rays.
- a curable resin such as urethane resin, acrylic resin, urea resin, etc. is applied on one side or both sides and cured and laminated. You can also.
- the polarizing film and polarizing plate obtained by the present invention are free from display defects and uneven polarization, and have excellent in-plane polarization performance, such as portable information terminals, personal computers, televisions, projectors, signage, electronic desk calculators, electronic Watches, word processors, electronic paper, game consoles, videos, cameras, photo albums, thermometers, audio, liquid crystal display devices such as cars and machinery instruments, sunglasses, anti-glare glasses, stereoscopic glasses, wearable displays, display elements ( CRT, LCD, organic EL, electronic paper, etc.) for use in antireflection layers, optical communication equipment, medical equipment, building materials, toys and the like.
- portable information terminals personal computers, televisions, projectors, signage, electronic desk calculators, electronic Watches, word processors, electronic paper, game consoles, videos, cameras, photo albums, thermometers, audio, liquid crystal display devices such as cars and machinery instruments, sunglasses, anti-glare glasses, stereoscopic glasses, wearable displays, display elements ( CRT, LCD, organic EL
- Polarization unevenness A test piece having a length of 30 cm and a width of 30 cm was cut out from the obtained polarizing film, and two polarizing plates in a crossed Nicol state (single transmittance 43.5%, polarization degree 99.9%) were obtained. After being sandwiched at an angle of 45 °, optical color unevenness was observed in a transmission mode using a light box having a surface illuminance of 14,000 lx and evaluated according to the following criteria. (Evaluation criteria) ⁇ : No color unevenness. ⁇ ... There is uneven color.
- a test piece having a length of 30 cm and a width of 13 cm was cut out from the obtained polarizing film, visually inspected in an environment of 15000 lx, and the number of display defects (pieces) of 100 ⁇ m or more was measured.
- Example 1 Manufacture of polyvinyl alcohol resin
- peroxyester as an initiator, vinyl acetate was polymerized in methanol to obtain polyvinyl acetate.
- the polyvinyl alcohol-type resin composition was obtained by saponifying using 2% NaOH aqueous solution.
- the obtained polyvinyl alcohol-based resin composition was washed with water and dehydrated with a centrifugal separator to obtain a polyvinyl alcohol-based resin wet cake.
- the obtained wet cake was put into a jacket, wet-dried with steam, and then dried at 125 ° C. for 2 hours using a rotary dryer.
- the weight swelling degree of the obtained polyvinyl alcohol-based resin was 1.58, the weight average molecular weight was 128,000, and the average saponification degree was 99.8 mol%.
- the polyvinyl alcohol-based resin aqueous solution was supplied to a twin-screw extruder having a vent and defoamed, and then the aqueous solution temperature was set to 95 ° C. and cast into a cast drum from a T-type slit die to form a film. . Finally, the obtained film is dried using a metal heating roll, both ends are cut off with a slit, and wound to form a roll-like polyvinyl alcohol film (thickness 30 ⁇ m, width 5 m, length 5 km). Obtained. Table 2 shows the characteristics of the obtained polyvinyl alcohol film.
- Examples 2 to 4 A polyvinyl alcohol resin, a polyvinyl alcohol film, and a polarizing film were obtained in the same manner as in Example 1 except that the drying conditions in the production process of the polyvinyl alcohol resin were the drying conditions shown in Table 1. The respective characteristics are shown in Table 1 and Table 2.
- Example 1 A polyvinyl alcohol resin was obtained in the same manner as in Example 1 except that the drying conditions in the production process of the polyvinyl alcohol resin were the drying conditions shown in Table 1. The obtained polyvinyl alcohol-based resin had reduced water solubility. Furthermore, in the same manner as in Example 1, a polyvinyl alcohol film and a polarizing film were obtained. The respective characteristics are shown in Table 1 and Table 2.
- Example 2 A polyvinyl alcohol resin was obtained in the same manner as in Example 1 except that the drying conditions in the production process of the polyvinyl alcohol resin were the drying conditions shown in Table 1.
- the obtained polyvinyl alcohol-based resin has a large amount of adhesion to pipes during the production of the polyvinyl alcohol-based film, and it has been difficult to continuously produce a polyvinyl alcohol-based film stably. In addition, it is difficult to dissolve evenly because it is likely to become lumps when dissolved with water.
- a polyvinyl alcohol film and a polarizing film were obtained. The respective characteristics are shown in Table 1 and Table 2.
- the polyvinyl alcohol resins of Examples 1 to 4 have a degree of weight swelling within the specific range of the present invention, there is no adhesion to the piping during the production of the polyvinyl alcohol film, and the resulting polyvinyl alcohol film is transparent. It was excellent.
- the polyvinyl alcohol-based resin of Comparative Example 1 having a degree of weight swelling smaller than the specific range of the present invention is poor in transparency of the resulting polyvinyl alcohol-based film due to a decrease in water solubility, and the weight swelling.
- the polyvinyl alcohol resin of Comparative Example 2 having a degree greater than the specific range of the present invention has a large amount of adhesion to the pipe during production and is difficult to be stably produced continuously. Therefore, the polyvinyl alcohol film that is difficult to dissolve uniformly is poor in transparency. It can be seen that the polarizing characteristics and quality of the polarizing films obtained from the respective polyvinyl alcohol films are superior to those of Comparative Examples 1 and 2 in Examples 1 to 4.
- the polyvinyl alcohol-based film obtained from the polyvinyl alcohol-based resin for producing the polarizing film of the present invention is excellent in transparency, and the polarizing film obtained from the polyvinyl alcohol-based film is free from display defects and uneven polarization, and is excellent in quality.
- Personal digital assistants personal computers, TVs, projectors, signage, electronic desk calculators, electronic clocks, word processors, electronic paper, game machines, videos, cameras, photo albums, thermometers, audio, automobile and machinery instruments, etc.
- liquid crystal display devices sunglasses, anti-glare glasses, stereoscopic glasses, wearable displays, antireflection reducing layers for display elements (CRT, LCD, organic EL, electronic paper, etc.), optical communication equipment, medical equipment, building materials, toys, etc. Used.
- display elements CRT, LCD, organic EL, electronic paper, etc.
- optical communication equipment medical equipment, building materials, toys, etc. Used.
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Abstract
Description
重量膨潤度=(15℃の水に1時間浸漬後、2,000Gで1分間遠心分離した時の重量)/(遠心分離後に105℃で2時間乾燥させた時の重量) ・・・(1) That is, the gist of the present invention is a polyvinyl alcohol-based resin for producing a polarizing film, wherein the weight swelling degree calculated by the following formula (1) is 1.4 to 1.65.
Degree of swelling of weight = (weight when immersed in water at 15 ° C. for 1 hour and then centrifuged at 2,000 G for 1 minute) / (weight when dried at 105 ° C. for 2 hours after centrifugation) (1) )
(A)ポリビニルアルコール系樹脂を水洗浄する工程。
(B)水洗浄後のポリビニルアルコール系樹脂を遠心分離で脱水する工程。
(C)溶解槽でポリビニルアルコール系樹脂の水溶液を調液する工程。
(D)ポリビニルアルコール系樹脂水溶液をキャスト法により製膜する工程。 The present invention also provides a method for producing the above-mentioned polyvinyl alcohol resin for producing a polarizing film, which comprises a step of drying at 120 to 150 ° C. for 1 to 4 hours, A polyvinyl alcohol film obtained by using a polyvinyl alcohol resin for producing a polarizing film, a method for producing a polyvinyl alcohol film comprising the following steps (A) to (D), a polarizing film comprising the film, A polyvinyl alcohol resin having a weight swelling degree calculated by the above formula (1) of 1.4 to 1.65 is also provided.
(A) A step of washing the polyvinyl alcohol resin with water.
(B) A step of dewatering the polyvinyl alcohol resin after washing with water by centrifugation.
(C) The process of preparing the aqueous solution of polyvinyl alcohol-type resin in a dissolution tank.
(D) The process of forming into a film the polyvinyl alcohol-type resin aqueous solution by the casting method.
本発明の(偏光膜製造用)ポリビニルアルコール系樹脂は、通常、未変性のポリビニルアルコール系樹脂、即ち、酢酸ビニルを重合して得られるポリ酢酸ビニルをケン化して製造される樹脂が用いられる。必要に応じて、酢酸ビニルと、少量(通常、10モル%以下、好ましくは5モル%以下)の酢酸ビニルと共重合可能な成分との共重合体をケン化して得られる樹脂を用いることもできる。酢酸ビニルと共重合可能な成分としては、例えば、不飽和カルボン酸(例えば、塩、エステル、アミド、ニトリル等を含む)、炭素数2~30のオレフィン類(例えば、エチレン、プロピレン、n-ブテン、イソブテン等)、ビニルエーテル類、不飽和スルホン酸塩等があげられる。また、ケン化後の水酸基を化学修飾して得られる変性ポリビニルアルコール系樹脂を用いることもできる。 The present invention is described in detail below.
As the polyvinyl alcohol resin (for producing a polarizing film) of the present invention, an unmodified polyvinyl alcohol resin, that is, a resin produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate is used. If necessary, a resin obtained by saponifying a copolymer of vinyl acetate and a small amount (usually 10 mol% or less, preferably 5 mol% or less) of a copolymerizable component with vinyl acetate may be used. it can. Examples of components copolymerizable with vinyl acetate include unsaturated carboxylic acids (including salts, esters, amides, nitriles, etc.), and olefins having 2 to 30 carbon atoms (eg, ethylene, propylene, n-butene). , Isobutene, etc.), vinyl ethers, unsaturated sulfonates and the like. Moreover, the modified polyvinyl alcohol-type resin obtained by chemically modifying the hydroxyl group after saponification can also be used.
重量平均分子量が小さすぎるとポリビニルアルコール系樹脂を光学フィルムとする場合に充分な光学性能が得られない傾向にあり、大きすぎるとフィルムを偏光膜とする場合に延伸が困難となり、工業的な生産が難しい傾向にある。なお、本発明におけるポリビニルアルコール系樹脂の重量平均分子量は、GPC-MALS法により測定される重量平均分子量である。 The weight average molecular weight of the polyvinyl alcohol-based resin is preferably 100,000 to 200,000, particularly preferably 111 to 180,000, and more preferably 120,000 to 160,000.
If the weight average molecular weight is too small, sufficient optical performance tends not to be obtained when the polyvinyl alcohol resin is used as an optical film, and if it is too large, stretching becomes difficult when the film is used as a polarizing film. Tend to be difficult. The weight average molecular weight of the polyvinyl alcohol resin in the present invention is a weight average molecular weight measured by a GPC-MALS method.
通常、合成されたポリビニルアルコール系樹脂は、溶剤洗浄、乾燥、必要に応じて、粉砕やふるいなどの後工程を経て、ポリビニルアルコール系フィルムの製膜に供される。かかる後工程の中でも乾燥工程が、重量膨潤度の制御に重要であり、本発明においては、乾燥工程が120~150℃で1~4時間行われることが好ましい。 Below, an example of the method of manufacturing a polyvinyl alcohol-type resin is demonstrated, controlling a weight swelling degree.
Usually, the synthesized polyvinyl alcohol resin is subjected to solvent washing, drying, and, if necessary, subsequent processes such as pulverization and sieving to be used for forming a polyvinyl alcohol film. Among these post-processes, the drying process is important for controlling the degree of weight swelling, and in the present invention, the drying process is preferably performed at 120 to 150 ° C. for 1 to 4 hours.
(A)ポリビニルアルコール系樹脂を水洗浄する工程。
(B)水洗浄後のポリビニルアルコール系樹脂を遠心分離で脱水する工程。
(C)溶解槽でポリビニルアルコール系樹脂の水溶液を調液する工程。
(D)ポリビニルアルコール系樹脂水溶液をキャスト法により製膜する工程。 Next, a method for producing a polyvinyl alcohol film will be described. The polyvinyl alcohol film is produced by the following steps (A) to (D) using the polyvinyl alcohol resin of the present invention.
(A) A step of washing the polyvinyl alcohol resin with water.
(B) A step of dewatering the polyvinyl alcohol resin after washing with water by centrifugation.
(C) The process of preparing the aqueous solution of polyvinyl alcohol-type resin in a dissolution tank.
(D) The process of forming into a film the polyvinyl alcohol-type resin aqueous solution by the casting method.
また、本発明のポリビニルアルコール系フィルムは、幅4m以上であることが、生産性の点で好ましく、長さ4km以上であることが、生産性の点でより好ましい。 The polyvinyl alcohol film of the present invention preferably has a thickness of 60 μm or less, particularly preferably 30 μm or less. If the thickness is too large, it is difficult to reduce the thickness of the polarizing film.
The polyvinyl alcohol film of the present invention preferably has a width of 4 m or more from the viewpoint of productivity, and more preferably 4 km or more from the viewpoint of productivity.
なお、偏光度は、一般的に2枚の偏光膜を、その配向方向が同一方向になるように重ね合わせた状態で、波長λにおいて測定した光線透過率(H11)と、2枚の偏光膜を、配向方向が互いに直交する方向になる様に重ね合わせた状態で、波長λにおいて測定した光線透過率(H1)より、下式にしたがって算出される。
〔(H11-H1)/(H11+H1)〕1/2 The polarization degree of the polarizing film of the present invention is preferably 99.5% or more, more preferably 99.8% or more. If the degree of polarization is too low, there is a tendency that the contrast in the liquid crystal display cannot be secured.
Note that the degree of polarization is generally the light transmittance (H 11 ) measured at the wavelength λ in the state where two polarizing films are overlapped so that their orientation directions are the same direction, and the two polarizing films. It is calculated according to the following equation from the light transmittance (H 1 ) measured at the wavelength λ in a state where the films are superposed so that the orientation directions are orthogonal to each other.
[(H 11 −H 1 ) / (H 11 + H 1 )] 1/2
単体透過率は、分光光度計を用いて偏光膜単体の光線透過率を測定して得られる値である。 Further, the single transmittance of the polarizing film of the present invention is preferably 43% or more. If the single transmittance is too low, it tends to be impossible to achieve high brightness of the liquid crystal display.
The single transmittance is a value obtained by measuring the light transmittance of a single polarizing film using a spectrophotometer.
以下、かかる偏光板の製造方法について説明する。 Thus, although the polarizing film of the present invention is obtained, the polarizing film of the present invention is suitable for producing a polarizing plate with little polarization unevenness.
Hereinafter, the manufacturing method of this polarizing plate is demonstrated.
なお、例中「部」、「%」とあるのは、重量基準を意味する。
各物性について、次のようにして測定を行った。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples, “parts” and “%” mean weight basis.
Each physical property was measured as follows.
(1)重量膨潤度
ポリビニルアルコール系樹脂1gを、15℃の水10gに1時間浸漬して膨潤させた。得られたスラリーを遠心管に入れ、遠心分離器(コクサン社製「H-19α」)を用いて、2,000Gで1分間の遠心分離を行い、水を振り切った。得られたケーキの重量A(g)を測定した後、アルミ皿上で105℃で2時間乾燥させ、得られた粉末の重量B(g)を測定して、下記式に従い重量膨潤度を算出した。
重量膨潤度=(15℃の水に1時間浸漬後、2,000Gで1分間遠心分離した時の重量A)/(遠心分離後に105℃で2時間乾燥させた時の重量B) <Measurement conditions>
(1) Weight swelling degree 1 g of polyvinyl alcohol-based resin was immersed in 10 g of water at 15 ° C. for 1 hour to swell. The obtained slurry was put into a centrifuge tube, and centrifuged at 2,000 G for 1 minute using a centrifuge (“H-19α” manufactured by Kokusan Co., Ltd.), and the water was shaken off. After measuring the weight A (g) of the obtained cake, it was dried on an aluminum dish at 105 ° C. for 2 hours, the weight B (g) of the obtained powder was measured, and the weight swelling degree was calculated according to the following formula. did.
Weight swelling degree = (weight A when immersed in water at 15 ° C. for 1 hour and then centrifuged at 2,000 G for 1 minute) / (weight B when centrifuged at 105 ° C. for 2 hours)
得られたポリビニルアルコール系フィルムから50mm×50mmの試験片を10枚切り出し、日本電色社製ヘイズメーターNDH-2000を用いて測定し、10枚の平均値をヘイズとした。 (2) Haze (%)
Ten test pieces of 50 mm × 50 mm were cut out from the obtained polyvinyl alcohol film and measured using a Nippon Denshoku haze meter NDH-2000, and the average value of the ten sheets was taken as haze.
得られた偏光膜から、長さ30cm×幅30cmの試験片を切り出し、クロスニコル状態の2枚の偏光板(単体透過率43.5%、偏光度99.9%)の間に45°の角度で挟んだのちに、表面照度14,000lxのライトボックスを用いて、透過モードで光学的な色ムラを観察し、以下の基準で評価した。
(評価基準)
○…色ムラなし。
×…色ムラあり。 (3) Polarization unevenness A test piece having a length of 30 cm and a width of 30 cm was cut out from the obtained polarizing film, and two polarizing plates in a crossed Nicol state (single transmittance 43.5%, polarization degree 99.9%) were obtained. After being sandwiched at an angle of 45 °, optical color unevenness was observed in a transmission mode using a light box having a surface illuminance of 14,000 lx and evaluated according to the following criteria.
(Evaluation criteria)
○: No color unevenness.
×… There is uneven color.
得られた偏光膜から、長さ30cm×幅13cmの試験片を切り出し、15000lxの環境下で目視検査し、100μm以上の表示欠点数(個)を測定した。 (4) Display defects (pieces)
A test piece having a length of 30 cm and a width of 13 cm was cut out from the obtained polarizing film, visually inspected in an environment of 15000 lx, and the number of display defects (pieces) of 100 μm or more was measured.
得られた偏光膜から、長さ4cm×幅4cmのサンプルを切り出し、自動偏光フィルム測定装置(日本分光社製:VAP7070)を用いて、単体透過率を測定した。 (5) Single transmittance (%)
A sample having a length of 4 cm and a width of 4 cm was cut out from the obtained polarizing film, and the single transmittance was measured using an automatic polarizing film measuring device (manufactured by JASCO Corporation: VAP7070).
(ポリビニルアルコール系樹脂の製造)
パーオキシエステルを開始剤に用いて、メタノール中で酢酸ビニルを重合して、ポリ酢酸ビニルとした。次いで、2%NaOH水溶液を用いてケン化することにより、ポリビニルアルコール系樹脂組成物を得た。得られたポリビニルアルコール系樹脂組成物を、水洗浄し、遠心分離器で脱水してポリビニルアルコール系樹脂ウェットケーキを得た。得られたウェットケーキをジャケットに投入し、スチームで湿式乾燥した後、回転式ドライヤーを用いて、125℃で2時間乾燥した。得られたポリビニルアルコール系樹脂の重量膨潤度は表1に示される通り1.58であり、重量平均分子量は128,000、平均ケン化度99.8モル%であった。 <Example 1>
(Manufacture of polyvinyl alcohol resin)
Using peroxyester as an initiator, vinyl acetate was polymerized in methanol to obtain polyvinyl acetate. Subsequently, the polyvinyl alcohol-type resin composition was obtained by saponifying using 2% NaOH aqueous solution. The obtained polyvinyl alcohol-based resin composition was washed with water and dehydrated with a centrifugal separator to obtain a polyvinyl alcohol-based resin wet cake. The obtained wet cake was put into a jacket, wet-dried with steam, and then dried at 125 ° C. for 2 hours using a rotary dryer. As shown in Table 1, the weight swelling degree of the obtained polyvinyl alcohol-based resin was 1.58, the weight average molecular weight was 128,000, and the average saponification degree was 99.8 mol%.
得られたポリビニルアルコール系樹脂1,000kgを、水12,000kgで洗浄した後、脱水して、含水率40%のウェットケーキを得た。水洗浄後のスラリーからウェットケーキの取り出しまでに、樹脂の配管への付着は観察されなかった。次いで、ウェットケーキ1,700kg、水2,300kg、可塑剤としてグリセリン120kgを加圧溶解缶に入れ、撹拌しながら140℃まで昇温して、樹脂濃度25%に濃度調整を行い、均一に溶解したポリビニルアルコール系樹脂水溶液を得た。次いで、ポリビニルアルコール系樹脂水溶液を、ベントを有する2軸押出機に供給して脱泡した後、水溶液温度を95℃にし、T型スリットダイよりキャストドラムに流延してフィルム状に製膜した。最後に、得られたフィルムを、金属加熱ロールを用いて乾燥を行い、両端部をスリットで切り落とし、巻き取ることによりロール状のポリビニルアルコール系フィルム(厚さ30μm、幅5m、長さ5km)を得た。得られたポリビニルアルコール系フィルムの特性を表2に示す。 (Manufacture of polyvinyl alcohol film)
The obtained polyvinyl alcohol-based resin (1,000 kg) was washed with 12,000 kg of water and then dehydrated to obtain a wet cake having a water content of 40%. No adhesion of the resin to the piping was observed before the wet cake was removed from the slurry after water washing. Next, 1,700 kg of wet cake, 2,300 kg of water, and 120 kg of glycerin as a plasticizer are placed in a pressure dissolution can, heated to 140 ° C. while stirring, adjusted to a resin concentration of 25%, and uniformly dissolved A polyvinyl alcohol resin aqueous solution was obtained. Next, the polyvinyl alcohol-based resin aqueous solution was supplied to a twin-screw extruder having a vent and defoamed, and then the aqueous solution temperature was set to 95 ° C. and cast into a cast drum from a T-type slit die to form a film. . Finally, the obtained film is dried using a metal heating roll, both ends are cut off with a slit, and wound to form a roll-like polyvinyl alcohol film (thickness 30 μm, width 5 m, length 5 km). Obtained. Table 2 shows the characteristics of the obtained polyvinyl alcohol film.
得られたポリビニルアルコール系フィルムを、水温25℃の水槽に浸漬して膨潤させながら、流れ方向へ1.7倍に延伸した。次いで、ヨウ素0.5g/L、ヨウ化カリウム30g/Lよりなる28℃の水溶液中に浸漬し染色しながら、流れ方向へ1.6倍に延伸した。次いで、ホウ酸40g/L、ヨウ化カリウム30g/Lの組成の水溶液(55℃)に浸漬し、ホウ酸架橋しながら、流れ方向へ2.1倍に一軸延伸した。最後に、ヨウ化カリウム水溶液で洗浄し、乾燥して、総延伸倍率5.7倍の偏光膜を得た。得られた偏光膜の特性を表2に示す。 (Manufacture of polarizing film)
The obtained polyvinyl alcohol-based film was stretched 1.7 times in the flow direction while being immersed and swollen in a water bath at a water temperature of 25 ° C. Next, the film was stretched 1.6 times in the flow direction while being immersed and dyed in an aqueous solution at 28 ° C. composed of 0.5 g / L of iodine and 30 g / L of potassium iodide. Next, the film was immersed in an aqueous solution (55 ° C.) having a composition of boric acid 40 g / L and potassium iodide 30 g / L, and uniaxially stretched 2.1 times in the flow direction while crosslinking with boric acid. Finally, it was washed with an aqueous potassium iodide solution and dried to obtain a polarizing film having a total draw ratio of 5.7 times. Table 2 shows the characteristics of the obtained polarizing film.
ポリビニルアルコール系樹脂の製造過程における乾燥条件を、表1に示される乾燥条件とすること以外は実施例1と同様にして、ポリビニルアルコール系樹脂、ポリビニルアルコール系フィルム、及び偏光膜を得た。それぞれの特性を表1および表2に示す。 <Examples 2 to 4>
A polyvinyl alcohol resin, a polyvinyl alcohol film, and a polarizing film were obtained in the same manner as in Example 1 except that the drying conditions in the production process of the polyvinyl alcohol resin were the drying conditions shown in Table 1. The respective characteristics are shown in Table 1 and Table 2.
ポリビニルアルコール系樹脂の製造過程における乾燥条件を、表1に示される乾燥条件とすること以外は実施例1と同様にしてポリビニルアルコール系樹脂を得た。得られたポリビニルアルコール系樹脂は、水への溶解性が低下していた。更に、実施例1と同様にして、ポリビニルアルコール系フィルム、及び偏光膜を得た。それぞれの特性を表1および表2に示す。 <Comparative Example 1>
A polyvinyl alcohol resin was obtained in the same manner as in Example 1 except that the drying conditions in the production process of the polyvinyl alcohol resin were the drying conditions shown in Table 1. The obtained polyvinyl alcohol-based resin had reduced water solubility. Furthermore, in the same manner as in Example 1, a polyvinyl alcohol film and a polarizing film were obtained. The respective characteristics are shown in Table 1 and Table 2.
ポリビニルアルコール系樹脂の製造過程における乾燥条件を、表1に示される乾燥条件とすること以外は実施例1と同様にしてポリビニルアルコール系樹脂を得た。得られたポリビニルアルコール系樹脂は、ポリビニルアルコール系フィルム製造時の配管への付着が多く安定的にポリビニルアルコール系フィルムを連続製造することが困難であった。また水で溶解する際にダマになりやすいため均一に溶解することが難しかった。更に、実施例1と同様にして、ポリビニルアルコール系フィルム、及び偏光膜を得た。それぞれの特性を表1および表2に示す。 <Comparative Example 2>
A polyvinyl alcohol resin was obtained in the same manner as in Example 1 except that the drying conditions in the production process of the polyvinyl alcohol resin were the drying conditions shown in Table 1. The obtained polyvinyl alcohol-based resin has a large amount of adhesion to pipes during the production of the polyvinyl alcohol-based film, and it has been difficult to continuously produce a polyvinyl alcohol-based film stably. In addition, it is difficult to dissolve evenly because it is likely to become lumps when dissolved with water. Furthermore, in the same manner as in Example 1, a polyvinyl alcohol film and a polarizing film were obtained. The respective characteristics are shown in Table 1 and Table 2.
そして、各々のポリビニルアルコール系フィルムから得られる偏光膜の偏光特性や品質は、実施例1~4が比較例1および2よりも優れるものであることがわかる。 On the other hand, the polyvinyl alcohol-based resin of Comparative Example 1 having a degree of weight swelling smaller than the specific range of the present invention is poor in transparency of the resulting polyvinyl alcohol-based film due to a decrease in water solubility, and the weight swelling. The polyvinyl alcohol resin of Comparative Example 2 having a degree greater than the specific range of the present invention has a large amount of adhesion to the pipe during production and is difficult to be stably produced continuously. Therefore, the polyvinyl alcohol film that is difficult to dissolve uniformly is poor in transparency.
It can be seen that the polarizing characteristics and quality of the polarizing films obtained from the respective polyvinyl alcohol films are superior to those of Comparative Examples 1 and 2 in Examples 1 to 4.
Claims (8)
- 下記式(1)で計算される重量膨潤度が1.4~1.65であることを特徴とする偏光膜製造用ポリビニルアルコール系樹脂。
重量膨潤度=(15℃の水に1時間浸漬後、2,000Gで1分間遠心分離した時の重量)/(遠心分離後に105℃で2時間乾燥させた時の重量) ・・・(1) A polyvinyl alcohol-based resin for producing a polarizing film, wherein the weight swelling degree calculated by the following formula (1) is 1.4 to 1.65.
Degree of swelling of weight = (weight when immersed in water at 15 ° C. for 1 hour and then centrifuged at 2,000 G for 1 minute) / (weight when dried at 105 ° C. for 2 hours after centrifugation) (1) ) - ポリビニルアルコール系樹脂の重量平均分子量が12万以上かつ平均ケン化度が99.5モル%以上であることを特徴とする請求項1記載の偏光膜製造用ポリビニルアルコール系樹脂。 The polyvinyl alcohol resin for producing a polarizing film according to claim 1, wherein the polyvinyl alcohol resin has a weight average molecular weight of 120,000 or more and an average saponification degree of 99.5 mol% or more.
- 請求項1または2記載の偏光膜製造用ポリビニルアルコール系樹脂を製造する方法であって、120~150℃で1~4時間の乾燥する工程を含むことを特徴とする偏光膜製造用ポリビニルアルコール系樹脂の製造方法。 3. A method for producing a polyvinyl alcohol resin for producing a polarizing film according to claim 1, comprising a step of drying at 120 to 150 ° C. for 1 to 4 hours. Manufacturing method of resin.
- 請求項1または2記載の偏光膜製造用ポリビニルアルコール系樹脂を用いて得られることを特徴とするポリビニルアルコール系フィルム。 A polyvinyl alcohol film obtained by using the polyvinyl alcohol resin for producing a polarizing film according to claim 1 or 2.
- 厚さが30μm以下であることを特徴とする請求項4記載のポリビニルアルコール系フィルム。 The polyvinyl alcohol film according to claim 4, wherein the thickness is 30 μm or less.
- 請求項4または5記載のポリビニルアルコール系フィルムからなることを特徴とする偏光膜。 A polarizing film comprising the polyvinyl alcohol film according to claim 4 or 5.
- 請求項4または5記載のポリビニルアルコール系フィルムを製造する方法であって、下記工程(A)~(D)を含むことを特徴とするポリビニルアルコール系フィルムの製造方法。
(A)ポリビニルアルコール系樹脂を水洗浄する工程。
(B)水洗浄後のポリビニルアルコール系樹脂を遠心分離で脱水する工程。
(C)溶解槽でポリビニルアルコール系樹脂の水溶液を調液する工程。
(D)ポリビニルアルコール系樹脂水溶液をキャスト法により製膜する工程。 6. A method for producing a polyvinyl alcohol film according to claim 4, comprising the following steps (A) to (D).
(A) A step of washing the polyvinyl alcohol resin with water.
(B) A step of dewatering the polyvinyl alcohol resin after washing with water by centrifugation.
(C) The process of preparing the aqueous solution of polyvinyl alcohol-type resin in a dissolution tank.
(D) The process of forming into a film the polyvinyl alcohol-type resin aqueous solution by the casting method. - 下記式(1)で計算される重量膨潤度が1.4~1.65であることを特徴とするポリビニルアルコール系樹脂。
重量膨潤度=(15℃の水に1時間浸漬後、2,000Gで1分間遠心分離した時の重量)/(遠心分離後に105℃で2時間乾燥させた時の重量) ・・・(1) A polyvinyl alcohol-based resin having a weight swelling degree calculated by the following formula (1) of 1.4 to 1.65.
Degree of swelling of weight = (weight when immersed in water at 15 ° C. for 1 hour and then centrifuged at 2,000 G for 1 minute) / (weight when dried at 105 ° C. for 2 hours after centrifugation) (1) )
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JP2016542782A JP6812795B2 (en) | 2015-08-26 | 2016-06-23 | Polyvinyl alcohol-based resin for manufacturing polarizing film and its manufacturing method, polyvinyl alcohol-based film and its manufacturing method, polarizing film, polyvinyl alcohol-based resin |
KR1020177029988A KR102489524B1 (en) | 2015-08-26 | 2016-06-23 | Polyvinyl alcohol-based resin for producing polarizing film and method for producing the same, polyvinyl alcohol-based film and method for producing the same, polarizing film, polyvinyl alcohol-based resin |
CN201680022651.8A CN107533176B (en) | 2015-08-26 | 2016-06-23 | Polyvinyl alcohol resin for polarizing film production, method for producing same, polyvinyl alcohol film, method for producing same, polarizing film, and polyvinyl alcohol resin |
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KR (1) | KR102489524B1 (en) |
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Cited By (11)
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JP2019194660A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing film, polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019194659A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing plate and polarizing plate roll |
JP2019194656A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing film, polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019194655A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019194661A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing film, polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019194662A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing film, polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019197206A (en) * | 2019-02-12 | 2019-11-14 | 日東電工株式会社 | Polarizing plate and polarizing plate roll |
JP2019197205A (en) * | 2019-02-12 | 2019-11-14 | 日東電工株式会社 | Polarizing plate and polarizing plate roll |
JP2019197204A (en) * | 2019-02-12 | 2019-11-14 | 日東電工株式会社 | Polarizing plate and polarizing plate roll |
JP7494267B2 (en) | 2022-08-02 | 2024-06-03 | 長春石油化學股▲分▼有限公司 | Polyvinyl alcohol film, optical film and manufacturing method |
WO2024143239A1 (en) * | 2022-12-26 | 2024-07-04 | 三菱ケミカル株式会社 | Polyvinyl alcohol-based film for polarizing film production use, method for producing same, and polarizing film using same |
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JP2019194660A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing film, polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019194659A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing plate and polarizing plate roll |
JP2019194656A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing film, polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019194655A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019194661A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing film, polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019194662A (en) * | 2017-09-13 | 2019-11-07 | 日東電工株式会社 | Polarizing film, polarizing plate, polarizing plate roll, and method of manufacturing polarizing film |
JP2019197206A (en) * | 2019-02-12 | 2019-11-14 | 日東電工株式会社 | Polarizing plate and polarizing plate roll |
JP2019197205A (en) * | 2019-02-12 | 2019-11-14 | 日東電工株式会社 | Polarizing plate and polarizing plate roll |
JP2019197204A (en) * | 2019-02-12 | 2019-11-14 | 日東電工株式会社 | Polarizing plate and polarizing plate roll |
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WO2024143239A1 (en) * | 2022-12-26 | 2024-07-04 | 三菱ケミカル株式会社 | Polyvinyl alcohol-based film for polarizing film production use, method for producing same, and polarizing film using same |
Also Published As
Publication number | Publication date |
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TW201718669A (en) | 2017-06-01 |
CN107533176B (en) | 2021-03-26 |
CN107533176A (en) | 2018-01-02 |
KR102489524B1 (en) | 2023-01-17 |
JPWO2017033552A1 (en) | 2018-06-14 |
TWI735449B (en) | 2021-08-11 |
JP6812795B2 (en) | 2021-01-13 |
KR20180044842A (en) | 2018-05-03 |
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