WO2016060097A1 - ポリビニルアルコール系フィルムおよびその製造方法、並びに偏光フィルム、偏光板 - Google Patents
ポリビニルアルコール系フィルムおよびその製造方法、並びに偏光フィルム、偏光板 Download PDFInfo
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- WO2016060097A1 WO2016060097A1 PCT/JP2015/078865 JP2015078865W WO2016060097A1 WO 2016060097 A1 WO2016060097 A1 WO 2016060097A1 JP 2015078865 W JP2015078865 W JP 2015078865W WO 2016060097 A1 WO2016060097 A1 WO 2016060097A1
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- Prior art keywords
- film
- polyvinyl alcohol
- aqueous solution
- stretching
- boric acid
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/46—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/02—Thermal after-treatment
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- 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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/04—PVOH, i.e. polyvinyl alcohol
Definitions
- the present invention relates to a polyvinyl alcohol film, in particular, a polyvinyl alcohol film for a polarizing film. More specifically, when producing a polarizing film, a polarizing film having excellent optical properties can be obtained without increasing the draw ratio.
- the present invention relates to a polyvinyl alcohol film that can be produced, a method for producing the same, a polarizing film, and a polarizing plate using the same.
- a polyvinyl alcohol film is prepared by dissolving a polyvinyl alcohol resin in a solvent such as water to prepare a stock solution, then forming a film by a solution casting method (casting method), and drying using a metal heating roll or the like. It is manufactured by doing.
- the polyvinyl alcohol film thus obtained is used in many applications as a film having excellent transparency, and one of its useful applications is a polarizing film.
- a polarizing film is used as a basic constituent element of a liquid crystal display, and in recent years, its use has been expanded to equipment requiring high quality and high reliability.
- the dichroic dye is oriented by dyeing and stretching the polyvinyl alcohol film, which is the raw material, with a dichroic dye such as iodine, the polarizing film is for improving the orientation, that is, the polarizing performance. It was necessary to increase the draw ratio.
- a polyvinyl alcohol film having a swelling degree (A) of 190 to 230% and a thickness of 40 ⁇ m or less A polyvinyl alcohol film having a degree of swelling (B) of 260% or more after stretching at a stretching ratio of 3 in water at 30 ° C. has been proposed (for example, Patent Document 1).
- a polyvinyl alcohol resin (X) and a polyvinyl alcohol system containing a 1,2-diol bond in the side chain for example, a polyvinyl alcohol resin (X) and a polyvinyl alcohol system containing a 1,2-diol bond in the side chain. It has been proposed to use a polyvinyl alcohol-based resin made of a resin (Y) and a polyvinyl alcohol-based film in which the weight swelling degree (W) of the polyvinyl alcohol-based film obtained from this polyvinyl alcohol-based resin is 200 to 300% by weight.
- Patent Document 2 for example, Patent Document 2,
- the present invention provides a polyvinyl alcohol film capable of obtaining a polarizing film having excellent optical characteristics without increasing the draw ratio when manufacturing a polarizing film, and a method for manufacturing the same. Furthermore, it is an object of the present invention to provide a polarizing film comprising such a polyvinyl alcohol film and a polarizing plate.
- the true stress at the time of stretching at each stretching ratio when the polyvinyl alcohol film is stretched in a boric acid aqueous solution under predetermined conditions.
- the ratio (Xc / Xa) of the true stress (Xc) at the time of 4.3 times to the true stress (Xa) at the time of 2.5 times the stretching (Xc / Xa)
- the ratio (Xc / Xa) of the true stress (Xc) at the 4.3 times stretching to the true stress (Xa) at the 2.5 times stretching is the true stress at the 2.5 times stretching.
- the film is unlikely to break even at a high draw ratio such as a draw ratio exceeding 6 times, for example, a draw ratio of 6.4 times.
- a draw ratio exceeds 6 times
- the thinner the film the greater the possibility of breakage due to stretching, and it becomes difficult to perform high stretching such that the stretching ratio exceeds 6 times.
- the draw ratio is 6 times and 6.4 times, it is merely a difference of 0.4 on the numerical value, but even if the difference in the numerical value of the draw ratio becomes smaller as the film becomes a thin film, the industrial production This is a very big difference. From this, when the same optical characteristics are desired, it is desired that the draw ratio is as low as possible.
- the present invention based on such circumstances, as a result of repeated research on the characteristics of the polyvinyl alcohol-based film, the above-described characteristics can be obtained by changing the heat roll temperature and the like to film forming conditions suitable for thin films.
- the present invention has been found that a polyvinyl alcohol film can be obtained as a polarizing film material excellent in optical properties without having a high draw ratio as in the prior art.
- the present invention is a polyvinyl alcohol film obtained by forming a film forming material containing the polyvinyl alcohol resin (A), and the polyvinyl alcohol film is 56 ° C. in a 5% by weight boric acid aqueous solution. After being soaked for 0.5 minutes (initial state), in the boric acid aqueous solution, the true stress (Xa) when stretched 2.5 times the initial state at a stretching speed of 70 mm / sec, A polyvinyl alcohol film satisfying the following formula (1) in the true stress (Xc) when stretched 4.3 times in the initial state in an acid aqueous solution is defined as a first gist. 5.0 ⁇ Xc / Xa ⁇ 9.0 (1)
- the present invention relates to a polyvinyl alcohol film obtained by forming a film forming material containing the polyvinyl alcohol resin (A), wherein the polyvinyl alcohol film is contained in a 5% by weight boric acid aqueous solution.
- the true stress (Xa) when stretched 2.5 times in the initial state at a stretching speed of 70 mm / sec in a boric acid aqueous solution, and continuing the stretching, True stress (Xb) when stretched 3.4 times in the initial state in an aqueous boric acid solution and true stress (Xc) when stretched 4.3 times in the initial state in an aqueous boric acid solution while further stretching.
- a polyvinyl alcohol film satisfying the following formulas (1) and (2) is defined as a second gist. 5.0 ⁇ Xc / Xa ⁇ 9.0 (1) Xb / Xa ⁇ Xc / Xa (2)
- the present invention is a method for producing the polyvinyl alcohol-based film, which comprises casting an aqueous solution of a film-forming material containing the polyvinyl alcohol-based resin (A) onto a first hot roll to form a film. [I], a step [II] of peeling the film from the first hot roll, and a step [III] of alternately passing the front and back of the film through a second hot roll group having a roll surface temperature of 30 to 95 ° C.
- the third gist is a method for producing a polyvinyl alcohol film comprising the step [IV] of heat-treating the film passed through the second heat roll group in an atmosphere of 60 to 145 ° C.
- the present invention also provides a polarizing film comprising the polyvinyl alcohol film and a polarizing plate comprising a protective film provided on at least one surface of the polarizing film.
- the polyvinyl alcohol film of the present invention has the above properties, it is possible to obtain a polarizing film having excellent optical properties without increasing the stretching ratio, thereby shortening the conventional stretching time and improving productivity. In addition, there are also effects such as a reduction in the burden on the stretching apparatus due to an increase in film tension accompanying high stretching and a reduction in breakage due to high stretching.
- the polyvinyl alcohol-type film of this invention is the original film used for the original film of a polarizing film used for liquid crystal display devices, such as polarized sunglasses and a liquid crystal television, a 1/2 wavelength plate, and a 1/4 wavelength plate, It is very useful as an original film of a retardation film used in a liquid crystal display device.
- the polyvinyl alcohol film of the present invention is a polyvinyl alcohol film obtained by forming a film forming material containing a polyvinyl alcohol resin (A), and has the following characteristics.
- the polyvinyl alcohol film is immersed in a 5% by weight boric acid aqueous solution at 56 ° C. for 0.5 minutes (initial state). Thereafter, the stretching is continued in a boric acid aqueous solution at a stretching speed of 70 mm / sec, and the initial stress in the boric acid aqueous solution is maintained with the true stress (Xa) when stretched 2.5 times in the initial state and continuing the stretching. In the true stress (Xc) when the state is stretched 4.3 times, the following formula (1) is satisfied. Furthermore, the polyvinyl alcohol film is immersed in a 5% by weight boric acid aqueous solution at 56 ° C. for 0.5 minutes (initial state).
- the polyvinyl alcohol film of the present invention is immersed in a 5 wt% boric acid aqueous solution at 56 ° C. for 0.5 minutes (initial state), and then in the boric acid aqueous solution.
- (Xb) what satisfies the following formula (3) is preferable. 1.9 ⁇ Xb / Xa ⁇ 3.0 (3)
- the polyvinyl alcohol film of the present invention is continuously stretched after being immersed in a 5% by weight boric acid aqueous solution at 56 ° C. for 0.5 minutes (initial state).
- stress (Xc) it is preferable to satisfy
- the true stresses Xa, Xb and Xc in the above formulas (1), (2), (3) and (4) are 0.5% at 56 ° C. in a 5% by weight boric acid aqueous solution, respectively.
- initial state After soaking for a minute (this is referred to as “initial state”), while continuing stretching at a stretching speed of 70 mm / sec in an aqueous boric acid solution, 2.5 times the initial state, 3.4 times the initial state, And each true stress (MPa) when extending
- the stress is generally an engineering (nominal) stress, which is a value obtained by dividing the tension by the cross-sectional area before stretching.
- the true stress cannot be calculated even if the tension at each stretching ratio is divided by the cross-sectional area before stretching. . Therefore, in the present invention, the true stress is used as the stress, the measurement is performed by the following measurement method, and the calculated stress is used as the true stress. Further, the above “while continuing stretching” refers to a state in which stretching is continued continuously (not intermittently) without interrupting the stretching process.
- the true stress (MPa) is measured as follows. That is, a polyvinyl alcohol-based film was prepared, and the film was cut in the center with respect to the width direction so that the width (TD) direction was 2 cm ⁇ the machine (MD) direction was 12.5 cm, and both long sides were oily markers. After coloring, the thickness is measured with a micrometer at five points.
- stretching in a 5% by weight boric acid aqueous solution is performed by fixing the cut out film to a predetermined jig so that both ends on the short side are 96 mm, and a 5% by weight boric acid aqueous solution at 56 ° C. Soak in for 0.5 minutes (this is referred to as “initial state”).
- the grip interval is widened to the extent that no force is applied to remove the slack in the film.
- tensile_strength with respect to a draw ratio is measured continuously, continuously uniaxially extending in a machine (MD) direction at a drawing speed of 70 mm / sec. And the tension
- MD machine
- a tensile tester is used to measure the tension.
- An example of such a tensile testing machine is a testing machine having a configuration in which a gate-type chuck is attached to a water tank having a glass window on the bottom so that the film can be stretched in water.
- a gate-type chuck is attached to a water tank having a glass window on the bottom so that the film can be stretched in water.
- one end of the film is fixed in a 5% by weight boric acid aqueous solution, and the opposite side can be operated.
- boric acid aqueous solution In order to calculate the true stress, it is necessary to measure the width of the film sample being stretched, and a video camera for measuring the film sample width is installed in the water tank.
- the center of the film in the MD direction moves with stretching, so a video camera for measuring the film sample width is also installed so that it moves in synchronization with the stretching speed, and the width at the center of the film can always be measured. It is like that.
- the tension measured with such a testing machine is taken as the true stress (MPa).
- the same measurement is performed three times, and the average value is adopted.
- Cross-sectional area during stretching (S) Sample cross-sectional area before stretching (S0) x Rate of change in width (W / W0)
- W is a sample (film) width during stretching
- W0 is a sample (film) width before stretching.
- Xc / Xa is required to be 5.0 to 9.0, preferably 5.2 to 8.5, particularly preferably 5.4 to 8.0. It is. If this value is less than the above range, the orientation of the molecular chain in the film at the time of stretching will be poor and the polarizing performance will be reduced. If it exceeds the above range, the film will break at the time of stretching.
- the true stress (Xa) in the above formula (1) that is, in the initial state, while continuously uniaxially stretching the polyvinyl alcohol film in a 5 wt% boric acid aqueous solution at a stretching rate of 70 mm / sec.
- the true stress (Xa) (MPa) when stretched 5 times is preferably 4.0 to 7.0 MPa, particularly 4.4 to 6.9 MPa, more preferably 4.6 to 6.8 MPa. Preferably there is. If the range is too small, swelling at the film end tends to progress and workability tends to be reduced. If it is too large, shrinkage in the width (TD) direction of the film increases and the yield tends to decrease. .
- the true stress (Xc) in the above formula (1) that is, the polyvinyl alcohol film was continuously uniaxially stretched in a 5% by weight boric acid aqueous solution at a stretching speed of 70 mm / sec, while the initial state was 4.
- the true stress (Xc) (MPa) when stretched 3 times is preferably 35.0 to 45.0 MPa, particularly 36.0 to 44.0 MPa, more preferably 37.0 to 43.0 MPa. Preferably there is.
- the range is too small, the performance of the polarizing film tends to be lowered due to the decrease in the orientation of molecular chains in the film, and when it is too large, the film tends to break.
- the true stress (Xb) in the above formula (1) that is, the initial state of the polyvinyl alcohol film, while continuously uniaxially stretching in a 5 wt% boric acid aqueous solution at a stretching speed of 70 mm / sec
- the true stress (Xb) (MPa) when stretched 4 times is preferably 11.0 to 15.0 MPa, particularly 11.5 to 14.8 MPa, more preferably 12.0 to 14.5 MPa. Preferably there is.
- this range is too small, there is a tendency that uneven polarization of the polarizing film is caused by stretching unevenness, and when it is too large, stretchability tends to be lowered (cannot be stretched to a predetermined stretching ratio).
- the value of Xc / Xa is preferably not less than the value of Xb / Xa, more preferably 2.0 to 3.5 times the value of Xb / Xa, particularly 2. 5 to 3.3 times is preferable.
- Xc / Xa is smaller than Xb / Xa, there is a tendency that the polarizing performance of the polarizing film is remarkably lowered or it is difficult to obtain the polarizing film.
- Xb / Xa is preferably 1.9 to 3.0, more preferably 2.0 to 2.8, particularly 2.1 to 2.7. Is preferred. When this value is too small, there is a tendency to cause uneven coloring of the polarizing film due to stretching unevenness during film stretching, and when it is too large, there is a tendency for stretchability to decrease.
- Xc / Xb is preferably 2.0 to 3.5, more preferably 2.3 to 3.4, and particularly 2.5 to 3.3. Is preferred. If this value is too small, the performance of the polarizing film tends to deteriorate due to insufficient film stretching. If the value is too large, the polarizing film tends to break.
- the polyvinyl alcohol film of the present invention having the above properties is cast using a film forming material containing the polyvinyl alcohol resin (A).
- polyvinyl alcohol resin (A) As the polyvinyl alcohol resin (A), an unmodified polyvinyl alcohol resin, that is, a resin produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate is usually used. If necessary, a resin obtained by saponifying a copolymer of vinyl acetate and a small amount (for example, 10 mol% or less, preferably 5 mol% or less) of vinyl acetate and a copolymerizable component may be used. it can.
- a resin obtained by saponifying a copolymer of vinyl acetate and a small amount (for example, 10 mol% or less, preferably 5 mol% or less) of vinyl acetate and a copolymerizable component may be used. it can.
- components copolymerizable with vinyl acetate include unsaturated carboxylic acids (including salts, esters, amides, nitriles, etc.), olefins having 2 to 30 carbon atoms (ethylene, propylene, n-butene, isobutene, etc.) Vinyl ethers, unsaturated sulfonates, and the like.
- a polyvinyl alcohol resin having a 1,2-glycol bond in the side chain can also be used.
- Such a polyvinyl alcohol resin having a 1,2-glycol bond 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.
- a method of saponifying and decarboxylating a copolymer of vinyl and vinyl ethylene carbonate; and (iii) saponifying and decarboxylating a copolymer of vinyl acetate and 2,2-dialkyl-4-vinyl-1,3-dioxolane It is obtained by a method of ketalization, (iv) a method of saponifying a copolymer of vinyl acetate and glyceryl monoallyl ether, or the like.
- the average saponification degree of the polyvinyl alcohol resin (A) used in the present invention is usually preferably 90 mol% or more, particularly preferably 95 mol% or more, more preferably 98 mol% or more, and particularly preferably 99 mol%.
- the mol% or more more preferably 99.5 mol% or more.
- the saponification degree in the present invention is obtained by analyzing the alkali consumption required for hydrolysis of residual vinyl acetate.
- the viscosity of the polyvinyl alcohol resin (A) is preferably 8 to 500 mPa ⁇ s, particularly 20 to 400 mPa ⁇ s, more preferably 40 to 400 mPa ⁇ s, as a 4 wt% aqueous solution viscosity at 20 ° C. -S is preferable. If the viscosity of the 4% by weight aqueous solution is too small, the stretchability at the time of forming the polarizing film tends to decrease, and if too large, the flatness and transparency of the film tend to decrease.
- polyvinyl alcohol resin (A) used in the present invention in the above polyvinyl alcohol resin, two or more kinds having different modified species, average saponification degree, viscosity and the like may be used in combination.
- a polyvinyl alcohol film is produced using a film forming material containing the polyvinyl alcohol resin (A).
- a known compounding agent such as a plasticizer (B) or a surfactant (C) is blended and manufactured.
- the plasticizer (B) generally contributes effectively to stretchability when producing a polarizing film.
- glycerins such as glycerin, diglycerin, triglycerin, ethylene glycol, diethylene glycol, triglycerin.
- alkylene glycols or polyalkylene glycols such as ethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol and polypropylene glycol, and trimethylolpropane.
- These plasticizers (B) can be used alone or in combination of two or more.
- glycerin alone glycerin and diglycerin, or a combination of glycerin and trimethylolpropane.
- glycerin / diglycerin weight ratio
- glycerin / trimethylolpropane weight ratio
- the content of the plasticizer (B) is preferably 1 to 35 parts by weight, particularly 3 to 30 parts by weight, and more preferably 7 to 25 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin (A). Part.
- the content of the plasticizer (B) is preferably 1 to 35 parts by weight, particularly 3 to 30 parts by weight, and more preferably 7 to 25 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin (A). Part.
- the surfactant (C) generally has a function of suppressing film surface smoothness and adhesion between films when wound into a roll.
- an anionic surfactant or a nonionic interface An active agent can be used individually or in combination of 2 or more types.
- the combined use of an anionic surfactant and a nonionic surfactant is preferable from the viewpoint of the transparency of the film.
- anionic surfactants include aliphatic alkyl sulfonates, alkyl sulfate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, higher fatty acid alkanolamide sulfates, and the like.
- sulfate esters such as sulfated oils, higher alcohol ethoxy sulfates and monoglycolates, fatty acid soaps, N-acyl amino acids and salts thereof, polyoxyethylene alkyls Carboxylate types such as ester carboxylates and acylated peptides, alkylbenzene sulfonates, alkylnaphthalene sulfonates, naphthalene sulfonic acid salt formalin polycondensates, melamine sulfonic acid salt formalin condensates, dialkyl sulfosuccinates Sulfonic acids such as ester salts, alkyl disulphates of sulfosuccinic acid, polyoxyethylene alkyl sulfosuccinic acid disalts, alkyl sulfoacetates, ⁇ -olefin sulfonates, N-acylmethyl taurates, di
- nonionic surfactant for example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid mono- or dialkanolamide, higher fatty acid amide, polyoxyethylene alkylamine, polyoxyethylene higher fatty acid amide, And amine oxides.
- ethylene oxide derivatives of alkylphenol formalin condensates polyoxyethylene polyoxypropylene block polymers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene castor oil and hydrogenated castor oil, poly Ether-type surfactants such as oxyethylene sorbitan fatty acid esters and polyoxyethylene sorbitol fatty acid esters, and ester-type surfactants such as polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides, propylene glycol fatty acid esters, and sucrose fatty acid esters , Etc.
- the content of the surfactant (C) is preferably 0.01 to 1 part by weight, particularly preferably 0.02 to 0.5 part by weight based on 100 parts by weight of the polyvinyl alcohol resin (A). Part, more preferably 0.03 to 0.2 part by weight. If the content of the surfactant (C) is too small, the anti-blocking effect tends to be difficult to obtain, and if it is too large, the transparency of the film tends to decrease.
- the anionic surfactant is used in an amount of 0.01 to 1 part by weight, particularly 100 parts by weight of the polyvinyl alcohol resin (A).
- the amount is preferably 0.02 to 0.2 parts by weight, more preferably 0.03 to 0.1 parts by weight, and the nonionic surfactant is 0.01 to 1 part by weight, particularly 0.02 to 0.2 parts by weight. It is preferable that the amount is 0.03 to 0.1 parts by weight.
- the amount of the anionic surfactant is too small, the dispersibility of the dye at the time of preparing the polarizing film tends to decrease, and the dyeing spots tend to increase. If the amount is too large, foaming occurs when the polyvinyl alcohol resin is dissolved, and bubbles are generated in the film. It tends to be mixed and cannot be used as an optical film. If the nonionic surfactant is too small, it is difficult to obtain an anti-blocking effect, and if it is too much, the transparency and flatness of the film tend to be lowered.
- an antioxidant in order to prevent yellowing of the film.
- examples of the antioxidant include phenolic antioxidants and the like. -T-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol) and the like are preferable.
- the antioxidant is preferably used in the range of about 2 to 100 ppm relative to the polyvinyl alcohol resin (A).
- a film-forming material is prepared using the polyvinyl alcohol-based resin (A).
- the polyvinyl alcohol-based resin (A) further includes at least a plasticizer (B) and a surfactant (C).
- a film-forming material is formed into a film and a polyvinyl alcohol-type film is obtained.
- a film-forming material is prepared using at least one of a polyvinyl alcohol-based resin (A), preferably a plasticizer (B) and a surfactant (C), and an aqueous solution of the film-forming material is used as a drum-type roll.
- a polyvinyl alcohol-based resin A
- B plasticizer
- C surfactant
- an aqueous solution of the film-forming material is used as a drum-type roll.
- it is cast on an endless belt, preferably a drum-type roll, formed into a film, dried, and then heat-treated to produce a polyvinyl alcohol film.
- the polyvinyl alcohol resin (A) powder is first washed to remove sodium acetate usually contained in the resin.
- washing methanol or water is used for washing.
- the method of washing with methanol requires solvent recovery and therefore, the method of washing with water is more preferable.
- the water-containing polyvinyl alcohol-based resin (A) wet cake after washing is dissolved to prepare a polyvinyl alcohol-based resin (A) aqueous solution.
- a water-containing polyvinyl alcohol-based resin (A) wet cake is dissolved in water as it is, Since a desired high-concentration aqueous solution cannot be obtained, it is preferable to perform dehydration once.
- the dehydration method is not particularly limited, but a method using centrifugal force is common.
- a wet polyvinyl alcohol resin (A) wet cake having a water content of 50% by weight or less, preferably 30 to 45% by weight, by the washing and dehydration. If the water content is too high, it tends to be difficult to obtain a desired aqueous solution concentration.
- an aqueous solution of a film forming material used for forming a polyvinyl alcohol film is prepared by adding water, water-containing polyvinyl alcohol resin (A) wet cake after dehydration, plasticizer (B), and surfactant in a dissolution tank. (C) and the like are prepared, heated, stirred and dissolved.
- water-containing polyvinyl alcohol resin (A) wet cake is dissolved by blowing water vapor in a dissolution tank equipped with a vertical circulation flow generation type stirring blade. .
- the resin temperature is 40 to 80 ° C., preferably 45 It is preferable to start stirring when the temperature reaches ⁇ 70 ° C. from the viewpoint of uniform dissolution. If the resin temperature is too low, the load on the motor tends to increase. If the resin temperature is too high, the polyvinyl alcohol resin (A) tends to be hardened and cannot be uniformly dissolved.
- uniform dissolution can be achieved by injecting water vapor and pressurizing the inside of the tank when the resin temperature is usually 90 to 100 ° C., preferably 95 to 100 ° C. If the resin temperature is too low, undissolved products tend to be formed. Then, when the resin temperature reaches 130 to 150 ° C., the blowing of water vapor is terminated, and stirring is continued for 0.5 to 3 hours to perform dissolution. After dissolution, the concentration is adjusted so that the desired concentration is obtained.
- the concentration of the aqueous solution of the film-forming material thus obtained is preferably 10 to 50% by weight, more preferably 15 to 40% by weight, especially considering the above physical properties (each true stress, etc.). It is preferably 20 to 30% by weight. If the concentration is too high or too low, it is difficult to form a uniform film, and the stress during stretching may be increased or decreased due to film thickness unevenness.
- the aqueous solution of the obtained film forming material is defoamed.
- the defoaming method include stationary defoaming and defoaming with a multi-screw extruder, but in the production method of the present invention, there is a method of defoaming using a multi-screw extruder in terms of productivity. preferable.
- the aqueous solution of the film forming material discharged from the multi-screw extruder is introduced into a T-type slit die by a certain amount and cast onto a drum-type roll or an endless belt to form a film, Dry and heat treated.
- the resin temperature at the exit of the T-type slit die is usually preferably 80 to 100 ° C., more preferably 85 to 98 ° C. If the resin temperature at the exit of the T-type slit die is too low, there is a tendency to cause poor flow, and if it is too high, foaming tends to occur.
- the casting is performed with a drum-type roll or an endless belt, but it is preferably performed with a drum-type roll from the viewpoints of widening, lengthening, and film thickness uniformity.
- the rotational speed of the drum is preferably 5 to 30 m / min, and particularly preferably 6 to 20 m / min.
- the surface temperature of the drum-type roll is preferably 50 to 99 ° C., more preferably 60 to 97 ° C. If the surface temperature of the drum-type roll is too low, drying tends to be poor, and if it is too high, foaming tends to occur.
- Drying of the polyvinyl alcohol film formed by the drum-type roll is performed by alternately passing the front and back surfaces of the film through a plurality of heat roll groups.
- the surface temperature of the heat roll group is preferably set to a lower temperature than conventional, specifically 30 to 95 ° C., more preferably 40 to 85 ° C., particularly 45 to 75 ° C. It is preferable that it is ° C. If the surface temperature is too low or too high, the molecular orientation becomes random and the stress tends to decrease.
- the heat treatment is preferably performed at a relatively high temperature, such as 60 to 145 ° C., more preferably 90 to 140 ° C., and particularly preferably 100 to 135 ° C. If the heat treatment temperature is too low, the film moisture and the degree of swelling tend to increase and the stress tends to decrease too much. If too high, the film moisture and the degree of swelling tend to decrease and the stress tends to become too high.
- a relatively high temperature such as 60 to 145 ° C., more preferably 90 to 140 ° C., and particularly preferably 100 to 135 ° C.
- the heat treatment temperature is too low, the film moisture and the degree of swelling tend to increase and the stress tends to decrease too much. If too high, the film moisture and the degree of swelling tend to decrease and the stress tends to become too high.
- the heat treatment method for example, (1) a method of passing a roll having a surface of 0.2 to 2 m (1 to 30) with a hard chrome plating treatment or a mirror treatment, and (2) a floating dryer (
- a polyvinyl alcohol film can be obtained.
- the following formulas [I] to [IV] are included, and the relational expression of the true stress is a feature of the present invention. It is preferable in that it can be satisfied.
- the first heat roll is a drum-type roll or an endless belt, and an aqueous solution of a film forming material is cast onto the first heat roll (drum-type roll or endless belt).
- the film is dried on the first hot roll, and peeled in a state where the film moisture content is preferably 10 to 25%, more preferably 12 to 20%. If the moisture content is too low, the tension at the time of peeling tends to be high and the film tends to stretch, and if it is too high, the film tends to become uneven in the width direction at the time of peeling.
- the film peeled from the first heat roll is sent to at least five or more second heat roll groups so that the front and back surfaces of the film are alternately passed.
- the surface temperature of at least 5 or more second heat roll groups is preferably 30 to 95 ° C., more preferably 40 to 85 ° C., and particularly preferably 45 to 75 ° C. It is.
- the film that has passed through the second hot roll group is heat-treated in a relatively high temperature atmosphere as compared with the conventional case.
- the heat treatment conditions at this time are preferably 60 to 145 ° C., more preferably 90 to 140 ° C., and particularly 100 to 135 ° C.
- the film forming material is cast, dried and heat-treated, and the film is wound up.
- the draw ratio at this time is preferably 0.9 to 1.1, particularly preferably. Is from 0.95 to 1.07, more preferably from 0.98 to 1.05. If the draw ratio is too low, the film tends to be loosened during film conveyance, and wrinkles tend to occur. Tend to be higher.
- the draw ratio refers to a ratio determined by the film winding speed / the rotation speed of the first heat roll.
- the draw ratio is conventionally in the range of 0.9 to 1.1.
- the draw ratio is set lower than in the past from the viewpoint of suppressing swelling unevenness in the film width direction. It is preferable.
- the polyvinyl alcohol film of the present invention thus obtained has a thickness of usually 5 to 50 ⁇ m, particularly 10 to 45 ⁇ m, more preferably 15 to 40 ⁇ m, for example, when considering the use of a polarizing film. preferable.
- the thus obtained polyvinyl alcohol film of the present invention has a retardation value of 10 to 50 nm, particularly 10 to 30 nm, more preferably 10 to 25 nm in that it is uniformly stretched in the width direction. preferable.
- the degree of weight swelling (W) at 30 ° C. is preferably 190 to 240% from the viewpoint of dyeability of the dye, particularly 190 to 230%, more preferably 195. It is preferably 225%, in particular 195 to 220%. If the weight swelling degree (W) is too small, the stretchability at the time of producing the polarizing film tends to be lowered. If it is too large, the stretchability is improved, but the polarizing performance of the polarizing film tends to be lowered.
- the following method is used.
- the film forming material containing the polyvinyl alcohol resin (A) is cast on a drum-type roll or an endless belt, preferably a drum-type roll, and then the front and back surfaces are alternately dried by a plurality of rotary heating roll groups, so that the moisture content is
- the temperature of the floating dryer or rotary heating roll is adjusted by heat treatment in the range of 100 to 135 ° C. If the moisture content in the film is too high, the crystallization rate of the polyvinyl alcohol-based resin (A) is slowed, so that it is difficult to obtain a heat treatment effect. If the moisture content is too low, heat treatment at 150 ° C. or higher is required. Therefore, the quality of the film tends to be lowered, for example, the degree of weight swelling of the film becomes too low or the film tends to yellow.
- the present invention is not limited to these methods, and the same heat treatment conditions can be used depending on the type and amount of plasticizer.
- the amount of the plasticizer added is increased, the crystallinity of the polyvinyl alcohol-based resin (A) decreases, so that the degree of weight swelling (W) tends to decrease.
- the addition amount of a plasticizer is the same, it is possible to adjust the crystallinity degree of polyvinyl alcohol-type resin (A) with the kind of plasticizer, and it is compatible with polyvinyl alcohol-type resin (A).
- a good plasticizer has a high effect of lowering the crystallinity, and therefore the weight swelling degree (W) can be adjusted by reducing the amount added.
- plasticizers with poor compatibility have a low effect of reducing the crystallinity, so that the degree of weight swelling (W) can be adjusted by increasing the amount of plasticizer added.
- the degree of weight swelling (W) can be adjusted by the saponification degree and polymerization degree of the polyvinyl alcohol-based resin (A). Further, the degree of weight swelling (W) may also be adjusted by drying conditions during film formation, for example, conditions for drying moisture in the film such as high temperature drying, low temperature drying, and high humidity drying. Among them, in terms of productivity, it is preferable to adjust the degree of weight swelling (W) by heat treatment after the moisture content in film formation becomes 5 to 30% by weight, and glycerin is mainly used as a plasticizer. More preferably, the weight swelling degree (W) is adjusted in the heat treatment temperature range of 100 to 135 ° C.
- the weight swelling degree (W) is measured as follows. That is, the film is cut into 10 cm ⁇ 10 cm and immersed in an ion exchange water bath adjusted to 30 ° C. for 15 minutes. Next, the film is taken out and spread out on the filter paper (5A), and the filter paper (5A) is overlaid on the film, and 15 cm ⁇ 15 cm ⁇ 0.4 cm (4.4 g / cm 2 ) thereon. The SUS plate is placed for 5 seconds to remove water adhering to the film surface. This film is immediately put into a weighing bottle, the weight is measured, and this is defined as the film weight A at the time of swelling. The above operation is performed in an environment of 23 ° C. and 50% RH.
- the area swelling degree (Y) at 30 ° C. is preferably 130 to 170% from the viewpoint of dyeing property of the dye, particularly 135 to 165%, and more preferably 140%. It is preferably ⁇ 160%. If the area swelling degree (Y) is too small, the stress during stretching increases rapidly and tends to break, and if it is too large, the stress during stretching does not rise and orientation tends to decrease.
- the following method is used.
- the film forming material containing the polyvinyl alcohol resin (A) is cast on a drum-type roll or an endless belt, preferably a drum-type roll, and then the front and back surfaces are alternately dried by a plurality of rotary heating roll groups, so that the moisture content is
- the temperature of the floating dryer or rotary heating roll is adjusted by heat treatment in the range of 100 to 135 ° C. If the moisture content in the film is too high, the crystallization rate of the polyvinyl alcohol-based resin (A) is slowed, so that it is difficult to obtain a heat treatment effect. If the moisture content is too low, heat treatment at 150 ° C. or higher is required. Therefore, the area swelling degree (Y) of the film tends to be too low, or the film tends to yellow, and the quality tends to decrease.
- the present invention is not limited to these methods, and the same heat treatment conditions can be used depending on the type and amount of plasticizer.
- the crystallinity of polyvinyl alcohol-type resin (A) will fall if the addition amount of a plasticizer is increased, there exists a tendency for an area swelling degree (Y) to become low.
- the addition amount of a plasticizer is the same, it is possible to adjust the crystallinity degree of polyvinyl alcohol-type resin (A) with the kind of plasticizer, and it is compatible with polyvinyl alcohol-type resin (A).
- a good plasticizer has a high effect of lowering the crystallinity. Therefore, the area swelling degree (Y) can be adjusted by reducing the amount of addition.
- plasticizers with poor compatibility have a low effect of reducing the degree of crystallinity, and therefore the area swelling degree (Y) can be adjusted by increasing the amount of plasticizer added.
- the area swelling degree (Y) can be adjusted by the saponification degree and the polymerization degree of the polyvinyl alcohol resin (A).
- the area swelling degree (Y) may be adjusted by drying conditions during film formation, for example, conditions for drying moisture in the film such as high temperature drying, low temperature drying, and high humidity drying.
- the area swelling degree (Y) is measured as follows. That is, the film is cut into a 10 cm ⁇ 10 cm square so as to be parallel to the machine (MD) direction and the width (TD) direction, placed on a flat glass plate, and the dimensions in the MD direction and the TD direction are measured. Next, after immersing in an ion exchange water bath adjusted to 30 ° C. for 5 minutes, the film is taken out and immediately placed on a flat glass plate, and the dimensions in the MD direction and the TD direction are measured with calipers, Obtained by the following formula. The above operation is performed in an environment of 23 ° C. and 50% RH.
- the syndiotacticity of the polyvinyl alcohol film is preferably 40 to 60%, particularly 45 to 55%, more preferably 50 to 54%. If the syndiotacticity is too small, However, if it is too large, the stretchability tends to be lowered and the film tends to break.
- a method of blending a polyvinyl alcohol resin having a high syndiotacticity with a polyvinyl alcohol resin having a low syndiotacticity, or a polymerization temperature of vinyl acetate is set.
- a method of saponifying a changed one a method of saponifying a polymer of vinyl ester such as vinyl pivalate, vinyl trifluoroacetate, vinyl trichloroacetate and the like.
- syndiotacticity is measured as follows. That is, it is a value by dyad display measured by a 13 C-NMR method for a polyvinyl alcohol film in a solvent (D 2 O).
- the obtained polyvinyl alcohol film has a light transmittance of 90% or more in the entire visible light range, and is very useful as an optical polyvinyl alcohol film. Therefore, the polyvinyl alcohol film of the present invention is preferably used as a raw film for an optical film, particularly as a raw film for a polarizing film.
- the polarizing film of the present invention is produced through processes such as normal dyeing, stretching, boric acid crosslinking and heat treatment.
- a method for producing a polarizing film a polyvinyl alcohol film is stretched and dyed by dipping in an iodine or dichroic dye solution, and then treated with a boron compound. After stretching and dyeing at the same time, a boron compound treatment is performed.
- the polyvinyl alcohol film may be stretched and dyed, and further subjected to boron compound treatment separately or simultaneously, but during at least one of the dyeing step and the boron compound treatment step. It is desirable in terms of productivity to perform uniaxial stretching.
- Stretching is desirably 2.5 to 10 times, preferably 2.8 to 7 times, in the uniaxial direction.
- a polarizing film having excellent optical characteristics even with stretching up to 6 times is particularly preferable. can do.
- a slight stretching may be performed in a direction perpendicular to the stretching direction.
- the temperature during stretching is preferably selected from 20 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 film is dyed 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.
- concentration of iodine is 0.1 to 2 g / L
- concentration of potassium iodide is 10 to 50 g / L
- the weight ratio of potassium iodide / iodine is 20 to 100. Is appropriate.
- 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.
- any means such as dipping, coating, spraying and the like can be applied.
- the dyed film is then treated with a boron compound.
- a boron compound As the boron compound, boric acid and borax are practical.
- the boron compound is used in the form of an aqueous solution or a water-organic solvent mixed solution at a concentration of about 0.3 to 2 mol / L, and it is practically desirable that potassium iodide coexist in the solution at 10 to 100 g / L.
- the treatment method is preferably an immersion method, but of course, an application method and a spray method can also be carried out.
- the temperature during the treatment is preferably about 20 to 60 ° C., and the treatment time is preferably about 3 to 20 minutes. If necessary, the stretching operation may be performed during the treatment.
- the polarizing film of the present invention thus obtained can also be used as a polarizing plate by laminating and bonding an optically isotropic polymer film or sheet as a protective film on one or both sides thereof.
- the protective film used in the polarizing plate of the present invention include cellulose triacetate, cellulose diacetate, polycarbonate, polymethyl methacrylate, polystyrene, polyethersulfone, polyarylene ester, poly-4-methylpentene, polyphenylene oxide, and cyclo-type. Or a film or sheet of norbornene-based polyolefin.
- a curable resin such as urethane resin, acrylic resin, urea resin or the like can be applied and laminated on one side or both sides.
- a polarizing film (including at least one surface laminated with a protective film or a curable resin) has a transparent pressure-sensitive adhesive layer formed on a surface of the polarizing film as required by a generally known method. In some cases, it may be put to practical use.
- Pressure sensitive adhesive layers include acrylic esters such as butyl acrylate, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, and ⁇ - such as acrylic acid, maleic acid, itaconic acid, methacrylic acid, and crotonic acid.
- the main component is a copolymer with a monoolefin carboxylic acid (including those added with vinyl monomers such as acrylonitrile, vinyl acetate, and styrene), the polarizing properties of the polarizing film are not impaired.
- a monoolefin carboxylic acid including those added with vinyl monomers such as acrylonitrile, vinyl acetate, and styrene
- the present invention is not limited to this, and any pressure-sensitive adhesive having transparency can be used.
- polyvinyl ether or rubber may be used.
- the polarizing film of the present invention is an electronic desk calculator, electronic clock, word processor, personal computer, television, portable information terminal, liquid crystal display device such as automobiles and machinery instruments, sunglasses, eyeglasses, stereoscopic glasses, display element ( CRT, LCD, etc.) for reflection reduction layer, medical equipment, building materials, toys and the like.
- stretching in a 5% boric acid aqueous solution is performed by fixing the cut out film to a predetermined jig so that both ends on the short side are 96 mm, and in a 5% boric acid aqueous solution at 56 ° C. Immersion for 0.5 minutes (this is referred to as “initial state”).
- the grip interval was widened to the extent that no force was applied to remove the slack in the film.
- tensile_strength with respect to a draw ratio was measured continuously, uniaxially stretching in a machine (MD) direction at a drawing speed of 70 mm / sec. And the tension
- MD machine
- a testing machine equipped with a structure in which a gate-type chuck was attached to a water tank having a glass window on the bottom so that the film could be stretched in water or the like.
- one end of the film is fixed in a 5% boric acid aqueous solution, and the opposite side can be operated.
- a video camera for measuring the film sample width was installed in the water tank.
- the center of the film in the MD direction moves with stretching, so a video camera for measuring the film sample width is also installed so that it moves in synchronization with the stretching speed, and the width at the center of the film can always be measured. It is like that.
- the tension measured by such a testing machine is divided by the cross-sectional area after stretching taken by the camera at the same time as stretching, and the value calculated by the following formula is defined as true stress (MPa). And the same measurement was performed 3 times and the average value was employ
- Cross-sectional area after stretching (S) sample cross-sectional area before stretching (S0) ⁇ rate of change in width (W / W0)
- W is the sample (film) width after stretching
- W0 is the sample (film) width before stretching.
- Weight swelling degree (W) (%) The film was cut into 10 cm ⁇ 10 cm and immersed in an ion exchange water bath adjusted to 30 ° C. for 15 minutes. Next, the film is taken out, and the film is spread on the filter paper (5A). Further, the filter paper (5A) is overlaid on the film, and 15 cm ⁇ 15 cm ⁇ 0.4 cm (4.4 g / cm 2 ) thereon. The SUS plate was placed for 5 seconds to remove water adhering to the film surface. This film was immediately put into a weighing bottle, the weight was measured, and this was defined as the film weight A at the time of swelling. The above operation was performed in an environment of 23 ° C. and 50% RH.
- Weight swelling degree (W) (%) A / B ⁇ 100
- Example 1 In a 200 L tank, 4% aqueous solution viscosity of 64 mPa ⁇ s as polyvinyl alcohol resin, 42 kg of polyvinyl alcohol resin (A) having an average saponification degree of 99.8 mol%, 100 kg of water, and glycerin as plasticizer (B) 2 kg, 21 g of sodium dodecyl sulfonate as surfactant (C) and 8 g of polyoxyethylene dodecylamine were added, and the mixture was heated to 150 ° C. with pressure and heating while stirring to dissolve uniformly. A 26% aqueous solution of film forming material was obtained.
- an aqueous solution of film-forming material (liquid temperature 147 ° C.) was supplied to a twin screw extruder and defoamed.
- the defoamed aqueous solution of the film forming material was cast from a T-type slit die (straight manifold die) to a drum-type roll (heat roll: R1) to form a film.
- Drum type roll heat roll: R1
- Diameter 3200 mm
- width 4.3 m
- rotation speed 15 m / min
- surface temperature 75 ° C.
- resin temperature at the exit of the T-type slit die 90 ° C.
- film moisture content at the time of peeling from a drum-type roll was measured, it was 17%.
- Drying was performed while the front and back surfaces of the obtained film were alternately passed through a drying roll under the following conditions. ⁇ First to 15th drying roll (heat roll: R2 to R16) Diameter: 320 mm, width: 4.3 m, rotation speed: 15 m / min, surface temperature: 60 ° C. In addition, when the film was sampled after drying and the film moisture content was measured, it was 7%.
- the membrane After drying, the membrane is continuously heat treated at 130 ° C. by a floating dryer (length 12 m) that blows warm air from both sides, and the polyvinyl alcohol system has a width of 4 m, a length of 4000 m, and a thickness of 30 ⁇ m at the center of the film. A film was obtained.
- the physical properties of the obtained polyvinyl alcohol film are shown in Table 1 below.
- the obtained polyvinyl alcohol film was stretched 1.5 times while being immersed in a water bath having a water temperature of 30 ° C. Next, it is stretched 1.3 times while being immersed for 240 seconds in a dyeing tank (30 ° C.) consisting of 0.2 g / L of iodine and 15 g / L of potassium iodide, and further 50 g / L of boric acid and 30 g of potassium iodide.
- / L was immersed in a boric acid treatment tank (50 ° C.) and boric acid treatment was performed for 5 minutes while uniaxially stretching 2.8 times. Thereafter, it was dried to obtain a polarizing film having a total draw ratio of 5.5 times.
- a polarizing film having a total draw ratio of 5.8 times was obtained by carrying out in the same manner except that it was uniaxially drawn by 2.97 times in the boric acid treatment tank.
- Example 2 Comparative Examples 1 to 3
- Example 1 it carried out similarly except having changed the film forming conditions as shown in following Table 1, and obtained the polyvinyl-alcohol-type film, Furthermore, it carried out similarly to Example 1, and obtained the polarizing film.
- Example 1 evaluation similar to Example 1 was performed. The evaluation results are shown in Table 1 below.
- the dichroic ratio in the polarizing film is a high polyvinyl alcohol film even at a low draw ratio.
- a polarizing film having excellent optical properties could not be obtained at a low stretch ratio of about 5.5 times or 5.8 times.
- the film was broken.
- the polyvinyl alcohol film of the present invention can provide a polarizing film having excellent polarization performance even when stretched at a low stretch ratio.
- Liquid crystal display devices such as instrumentation for machinery, sunglasses, eye protection glasses, stereoscopic glasses, reflection reduction layers for display elements (CRT, LCD, etc.), raw materials for polarizing films used in medical equipment, building materials, toys, etc. It is very useful as an original film used for a half-wave plate or a quarter-wave plate or a retardation film used for a liquid crystal display device.
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Abstract
Description
上記偏光フィルムは、その原料であるポリビニルアルコール系フィルムをヨウ素などの二色性染料で染色し、延伸することにより、二色性染料が配向するため、配向性、すなわち、偏光性能を向上させるためには延伸倍率を高くする必要があった。
すなわち、本発明は、ポリビニルアルコール系樹脂(A)を含有するフィルム形成材料を製膜してなるポリビニルアルコール系フィルムであって、上記ポリビニルアルコール系フィルムを5重量%のホウ酸水溶液中、56℃で0.5分間浸漬した(初期状態)後、ホウ酸水溶液中で延伸速度70mm/secで初期状態の2.5倍延伸した時の真応力(Xa)と、引き続き延伸を継続しながら、ホウ酸水溶液中で初期状態の4.3倍延伸した時の真応力(Xc)において、下記式(1)を満たすポリビニルアルコール系フィルムを第1の要旨とする。
5.0≦Xc/Xa≦9.0・・・(1)
5.0≦Xc/Xa≦9.0・・・(1)
Xb/Xa≦Xc/Xa・・・(2)
本発明のポリビニルアルコール系フィルムは、ポリビニルアルコール系樹脂(A)を含有するフィルム形成材料を製膜してなるポリビニルアルコール系フィルムであり、下記の特性を備えるものである。
5.0≦Xc/Xa≦9.0・・・(1)
Xb/Xa≦Xc/Xa・・・(2)
1.9≦Xb/Xa≦3.0・・・(3)
2.0≦Xc/Xb≦3.5・・・(4)
上記真応力(MPa)は、つぎのようにして測定される。すなわち、ポリビニルアルコール系フィルムを準備し、上記フィルムを幅(TD)方向2cm×機械(MD)方向12.5cmになるように幅方向に対して中央部を切り出し、長辺両側を油性マーカーにて色づけした後、厚みをマイクロメーターにて5点計測する。
延伸中の断面積(S)=延伸前の試料断面積(S0)×幅の変化率(W/W0)
ここで、Wは延伸中の試料(フィルム)幅、W0は延伸前の試料(フィルム)幅である。
上記ポリビニルアルコール系樹脂(A)としては、通常、未変性のポリビニルアルコール系樹脂、すなわち、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(例えば、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(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(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。
ここで、本発明におけるケン化度は、残存酢酸ビニルの加水分解に要するアルカリ消費量で分析することにより得られる。
以下、本発明のポリビニルアルコール系フィルムの製造方法について具体的に説明する。
すなわち、フィルムを10cm×10cmに切り出し、30℃に調整されたイオン交換水槽に15分間浸漬する。次に、フィルムを取り出し、濾紙(5A)上にフィルムを広げて置き、さらに、濾紙(5A)をフィルムの上に重ね、その上に15cm×15cm×0.4cm(4.4g/cm2)のSUS板を5秒間載せ、フィルム表面の付着水を除去する。このフィルムを速やかに秤量瓶にいれ、重量を測定し、これを膨潤時のフィルム重量Aとする。上記操作は23℃、50%RHの環境にて行う。
次に、該フィルムを105℃の乾燥機に16時間フィルム放置し、フィルム中の水分の除去を行い、その後フィルムを取り出し、速やかに秤量瓶に入れ、重量を測定し、これを乾燥後のフィルム重量Bとする。そして、膨潤時のフィルム重量Aと乾燥後のフィルム重量Bを基に下式より求める。
重量膨潤度(W)(%)=A/B×100
すなわち、フィルムを10cm×10cm角に機械(MD)方向、幅(TD)方向と平行になるように切り出し、平坦なガラス板上に載せ、MD方向、およびTD方向の寸法を各々計測する。次に、30℃に調整されたイオン交換水槽に5分間浸漬させた後、フィルムを取り出し、直ちに、平坦なガラス板上に載せ、MD方向、およびTD方向の寸法を各々ノギスにて計測し、下式により求める。なお、上記操作は23℃、50%RHの環境下にて行なう。
MD方向の膨潤度(XMD)(%)
=(浸漬後のMD方向の寸法/浸漬前のMD方向の寸法)×100
TD方向の膨潤度(XTD)(%)
=(浸漬後のTD方向の寸法/浸漬前のTD方向の寸法)×100
面積膨潤度(Y)(%)
=(MD方向の膨潤度(XMD)/100)×(TD方向の膨潤度(XTD)/100)×100
したがって、本発明のポリビニルアルコール系フィルムは、光学フィルムの原反フィルムとして、特に偏光フィルムの原反フィルムとして好ましく用いられる。
以下、本発明のポリビニルアルコール系フィルムを用いた本発明の偏光フィルムの製造方法について説明する。
尚、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・算出を行った。
残酢酸ビニル単位の加水分解に要するアルカリ消費で分析を行った。
水温を20℃に調整しヘプラー粘度計により測定した。
ポリビニルアルコール系フィルムを準備し、上記フィルムを幅(TD)方向2cm×機械(MD)方向12.5cmになるように幅方向に対して中央部を切り出し、長辺両側を油性マーカーにて色づけした後、厚みをマイクロメーターにて5点計測した。
延伸後の断面積(S)=延伸前の試料断面積(S0)×幅の変化率(W/W0)
ここで、Wは延伸後の試料(フィルム)幅、W0は延伸前の試料(フィルム)幅である。
Xc/Xa
=4.3倍まで延伸した時の真応力(Xc)/2.5倍まで延伸した時の真応力(Xa)
Xb/Xa
=3.4倍まで延伸した時の真応力(Xb)/2.5倍まで延伸した時の真応力(Xa)
Xc/Xb
=4.3倍まで延伸した時の真応力(Xc)/3.4倍まで延伸した時の真応力(Xc)
フィルムを10cm×10cm角に機械(MD)方向、幅(TD)方向と平行になるように切り出し、平坦なガラス板上に載せ、MD方向、およびTD方向の寸法を各々ノギスにて計測した。次に、30℃に調整されたイオン交換水槽に5分間浸漬させた後、フィルムを取り出し、直ちに、平坦なガラス板上に載せ、MD方向、およびTD方向の寸法を各々ノギスにて計測し、下式により算出した。なお、上記操作は23℃、50%RHの環境下で行った。
MD方向の膨潤度(XMD)(%)
=(浸漬後のMD方向の寸法/浸漬前のMD方向の寸法)×100
TD方向の膨潤度(XTD)(%)
=(浸漬後のTD方向の寸法/浸漬前のTD方向の寸法)×100
面積膨潤度(Y)(%)
=(MD方向の膨潤度(XMD)/100)×(TD方向の膨潤度(XTD)/100)×100
フィルムを10cm×10cmに切り出し、30℃に調整されたイオン交換水槽に15分間浸漬した。次に、フィルムを取り出し、濾紙(5A)上にフィルムを広げて置き、さらに、濾紙(5A)をフィルムの上に重ね、その上に15cm×15cm×0.4cm(4.4g/cm2)のSUS板を5秒間載せ、フィルム表面の付着水を除去した。このフィルムを速やかに秤量瓶にいれ、重量を測定し、これを膨潤時のフィルム重量Aとした。上記操作は23℃、50%RHの環境にて行った。
次に、該フィルムを105℃の乾燥機に16時間フィルム放置し、フィルム中の水分の除去を行い、その後フィルムを取り出し、速やかに秤量瓶に入れ、重量を測定し、これを乾燥後のフィルム重量Bとした。そして、膨潤時のフィルム重量Aと乾燥後のフィルム重量Bを基に下式より求めた。
重量膨潤度(W)(%)=A/B×100
リターデーション測定装置(「KOBRA-WFD」王子計測機器社製 測定波長:590nm)を用いて、ポリビニルアルコール系フィルムの幅方向の中央の部分のリターデーション値を測定した。
200Lのタンクに、ポリビニルアルコール系樹脂として、4%水溶液粘度64mPa・s、平均ケン化度99.8モル%のポリビニルアルコール系樹脂(A)42kg、水100kg、可塑剤(B)としてグリセリン4.2kg、界面活性剤(C)としてドデシルスルホン酸ナトリウム21g、ポリオキシエチレンドデシルアミン8gを入れ、撹拌しながら加圧加熱にて150℃まで昇温して、均一に溶解した後、濃度調整により濃度26%のフィルム形成材料の水溶液を得た。
ドラム型ロール(熱ロール:R1)
直径:3200mm、幅:4.3m、回転速度:15m/分、表面温度:75℃、T型スリットダイ出口の樹脂温度:90℃
なお、ドラム型ロールから剥離する際のフィルム水分率を測定したところ17%であった。
・乾燥ロールの1本目~15本目(熱ロール:R2~R16)
直径:320mm、幅:4.3m、回転速度:15m/分、表面温度:60℃
なお、乾燥後フィルムをサンプリングし、フィルム水分率を測定したところ7%であった。
得られたポリビニルアルコール系フィルムの各物性を後記の表1に示す。
また、上記ホウ酸処理槽において2.97倍一軸延伸する以外は同様に行うことで、総延伸倍率5.8倍の偏光フィルムを得た。
上記で得られた各偏光フィルム(総延伸倍率5.5倍の偏光フィルム、総延伸倍率5.8倍の偏光フィルム)の幅方向の中央部から、偏光フィルムの配向方向に平行に4cm×4cmの正方形のサンプルを採取した。
これらのサンプルについて、日本分光社製の分光光度計V-7070を用いて、得られた偏光フィルムの透過率(%)、偏光度(%)および二色比を測定した。
実施例1において、フィルム製膜の条件を下記の表1に示す通りに変更した以外は同様に行い、ポリビニルアルコール系フィルムを得、更に、実施例1と同様にして偏光フィルムを得た。
得られたポリビニルアルコール系フィルム、及び、偏光フィルムについて、実施例1と同様の評価を行った。評価結果を下記の表1に示す。
Claims (15)
- ポリビニルアルコール系樹脂(A)を含有するフィルム形成材料を製膜してなるポリビニルアルコール系フィルムであって、上記ポリビニルアルコール系フィルムを5重量%のホウ酸水溶液中、56℃で0.5分間浸漬した(初期状態)後、ホウ酸水溶液中で延伸速度70mm/secで初期状態の2.5倍延伸した時の真応力(Xa)と、引き続き延伸を継続しながら、ホウ酸水溶液中で初期状態の4.3倍延伸した時の真応力(Xc)において、下記式(1)を満たすことを特徴とするポリビニルアルコール系フィルム。
5.0≦Xc/Xa≦9.0・・・(1) - ポリビニルアルコール系樹脂(A)を含有するフィルム形成材料を製膜してなるポリビニルアルコール系フィルムであって、上記ポリビニルアルコール系フィルムを5重量%のホウ酸水溶液中、56℃で0.5分間浸漬した(初期状態)後、ホウ酸水溶液中で延伸速度70mm/secで初期状態の2.5倍延伸した時の真応力(Xa)と、引き続き延伸を継続しながら、ホウ酸水溶液中で初期状態の3.4倍延伸した時の真応力(Xb)と、更に延伸を継続しながら、ホウ酸水溶液中で初期状態の4.3倍延伸した時の真応力(Xc)において、下記式(1)及び(2)を満たすことを特徴とするポリビニルアルコール系フィルム。
5.0≦Xc/Xa≦9.0・・・(1)
Xb/Xa≦Xc/Xa・・・(2) - 真応力(Xa)が4.0~7.0MPaであることを特徴とする請求項1または2記載のポリビニルアルコール系フィルム。
- 真応力(Xc)が35.0~45.0MPaであることを特徴とする請求項1~3のいずれか一項に記載のポリビニルアルコール系フィルム。
- 真応力(Xb)が11.0~15.0MPaであることを特徴とする請求項2~4のいずれか一項に記載の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を5重量%のホウ酸水溶液中、56℃で0.5分間浸漬した(初期状態)後、ホウ酸水溶液中で延伸速度70mm/secで初期状態の2.5倍延伸した時の真応力(Xa)と、引き続き延伸を継続しながら、ホウ酸水溶液中で初期状態の3.4倍延伸した時の真応力(Xb)において、下記式(3)を満たすことを特徴とする請求項2~5のいずれか一項に記載のポリビニルアルコール系フィルム。
1.9≦Xb/Xa≦3.0・・・(3) - ポリビニルアルコール系フィルムを5重量%のホウ酸水溶液中、56℃で0.5分間浸漬した(初期状態)後、延伸を継続しながら、ホウ酸水溶液中で初期状態の3.4倍延伸した時の真応力(Xb)と、更に延伸を継続しながら、ホウ酸水溶液中で初期状態の4.3倍延伸した時の真応力(Xc)において、下記式(4)を満たすことを特徴とする請求項2~6のいずれか一項に記載のポリビニルアルコール系フィルム。
2.0≦Xc/Xb≦3.5・・・(4) - 厚みが5~50μmであることを特徴とする請求項1~7のいずれか一項に記載の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を30℃の水に5分間浸漬し膨潤させた時の面積膨潤度(Y)が130~170%であることを特徴とする請求項1~8のいずれか一項に記載のポリビニルアルコール系フィルム。
- 30℃での重量膨潤度(W)が190~240%であることを特徴とする請求項1~9のいずれか一項に記載のポリビニルアルコール系フィルム。
- リターデーション値が10~50nmであることを特徴とする請求項1~10のいずれか一項に記載のポリビニルアルコール系フィルム。
- 偏光フィルムの原反フィルムとして用いられることを特徴とする請求項1~11のいずれか一項に記載のポリビニルアルコール系フィルム。
- 請求項1~12のいずれか一項に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、上記ポリビニルアルコール系樹脂(A)を含有するフィルム形成材料の水溶液を第1熱ロールに流延してフィルム状に製膜する工程[I]と、上記第1熱ロールからフィルムを剥離する工程[II]と、ロール表面温度が30~95℃の第2熱ロール群に、フィルムの表裏を交互に通過させる工程[III]と、上記第2熱ロール群を通過させたフィルムを60~145℃の雰囲気下にて熱処理を行なう工程[IV]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。
- 請求項1~12のいずれか一項に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フィルム。
- 請求項14記載の偏光フィルムの少なくとも片面に保護フィルムを設けてなることを特徴とする偏光板。
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WO2018003671A1 (ja) * | 2016-06-27 | 2018-01-04 | 日本合成化学工業株式会社 | 偏光膜用ポリビニルアルコール系フィルム、およびその製造方法、ならびにその偏光膜用ポリビニルアルコール系フィルムを用いた偏光膜 |
WO2018199140A1 (ja) * | 2017-04-26 | 2018-11-01 | 日本合成化学工業株式会社 | ポリビニルアルコール系フィルム、偏光膜および偏光板、ならびにポリビニルアルコール系フィルムの製造方法 |
WO2019208618A1 (ja) * | 2018-04-27 | 2019-10-31 | 株式会社クラレ | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 |
WO2020116414A1 (ja) * | 2018-12-04 | 2020-06-11 | 株式会社クラレ | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 |
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WO2022138720A1 (ja) * | 2020-12-23 | 2022-06-30 | 三菱ケミカル株式会社 | 偏光膜製造用ポリビニルアルコール系フィルム、偏光膜製造用ポリビニルアルコール系フィルムの製造方法、偏光膜 |
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JP7192198B2 (ja) | 2016-06-13 | 2022-12-20 | 三菱ケミカル株式会社 | 偏光膜用ポリビニルアルコール系フィルム、およびその製造方法、ならびに偏光膜、およびその製造方法 |
JP2017223941A (ja) * | 2016-06-13 | 2017-12-21 | 日本合成化学工業株式会社 | 偏光膜用ポリビニルアルコール系フィルム、およびその製造方法、ならびに偏光膜 |
KR102295492B1 (ko) * | 2016-06-27 | 2021-08-30 | 미쯔비시 케미컬 주식회사 | 편광막용 폴리비닐알코올계 필름, 및 이의 제조 방법, 및 상기 편광막용 폴리비닐알코올계 필름을 사용한 편광막 |
WO2018003671A1 (ja) * | 2016-06-27 | 2018-01-04 | 日本合成化学工業株式会社 | 偏光膜用ポリビニルアルコール系フィルム、およびその製造方法、ならびにその偏光膜用ポリビニルアルコール系フィルムを用いた偏光膜 |
KR20190022550A (ko) * | 2016-06-27 | 2019-03-06 | 닛폰고세이가가쿠고교 가부시키가이샤 | 편광막용 폴리비닐알코올계 필름, 및 이의 제조 방법, 및 상기 편광막용 폴리비닐알코올계 필름을 사용한 편광막 |
JPWO2018003671A1 (ja) * | 2016-06-27 | 2019-04-18 | 日本合成化学工業株式会社 | 偏光膜用ポリビニルアルコール系フィルム、およびその製造方法、ならびにその偏光膜用ポリビニルアルコール系フィルムを用いた偏光膜 |
WO2018199140A1 (ja) * | 2017-04-26 | 2018-11-01 | 日本合成化学工業株式会社 | ポリビニルアルコール系フィルム、偏光膜および偏光板、ならびにポリビニルアルコール系フィルムの製造方法 |
KR20190139852A (ko) * | 2017-04-26 | 2019-12-18 | 미쯔비시 케미컬 주식회사 | 폴리비닐알코올계 필름, 편광막 및 편광판, 및 폴리비닐알코올계 필름의 제조 방법 |
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KR102463852B1 (ko) * | 2017-04-26 | 2022-11-04 | 미쯔비시 케미컬 주식회사 | 폴리비닐알코올계 필름, 편광막 및 편광판, 및 폴리비닐알코올계 필름의 제조 방법 |
CN111819226A (zh) * | 2018-03-29 | 2020-10-23 | 三菱化学株式会社 | 水溶性薄膜及其制造方法、以及药剂包装体 |
CN112004881A (zh) * | 2018-04-27 | 2020-11-27 | 株式会社可乐丽 | 聚乙烯醇膜和使用其而得的偏振膜的制备方法 |
JPWO2019208618A1 (ja) * | 2018-04-27 | 2021-06-10 | 株式会社クラレ | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 |
JP7165724B2 (ja) | 2018-04-27 | 2022-11-04 | 株式会社クラレ | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 |
WO2019208618A1 (ja) * | 2018-04-27 | 2019-10-31 | 株式会社クラレ | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 |
CN112004881B (zh) * | 2018-04-27 | 2023-03-10 | 株式会社可乐丽 | 聚乙烯醇膜和使用其而得的偏振膜的制备方法 |
JPWO2020116414A1 (ja) * | 2018-12-04 | 2021-10-21 | 株式会社クラレ | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 |
WO2020116414A1 (ja) * | 2018-12-04 | 2020-06-11 | 株式会社クラレ | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 |
JP7282100B2 (ja) | 2018-12-04 | 2023-05-26 | 株式会社クラレ | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 |
WO2022138720A1 (ja) * | 2020-12-23 | 2022-06-30 | 三菱ケミカル株式会社 | 偏光膜製造用ポリビニルアルコール系フィルム、偏光膜製造用ポリビニルアルコール系フィルムの製造方法、偏光膜 |
WO2022202861A1 (ja) * | 2021-03-24 | 2022-09-29 | 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、およびその製造方法、ならびにそれを用いた偏光膜、偏光板 |
WO2024143239A1 (ja) * | 2022-12-26 | 2024-07-04 | 三菱ケミカル株式会社 | 偏光膜製造用ポリビニルアルコール系フィルムおよびその製造方法、並びにそれを用いてなる偏光膜 |
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CN107073764A (zh) | 2017-08-18 |
KR20170068443A (ko) | 2017-06-19 |
TWI692486B (zh) | 2020-05-01 |
JP6805493B2 (ja) | 2020-12-23 |
TW201619211A (zh) | 2016-06-01 |
KR102331874B1 (ko) | 2021-11-26 |
JPWO2016060097A1 (ja) | 2017-08-03 |
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