WO2013146458A1 - Polyvinyl alcohol-type polymer film and polarizing film - Google Patents
Polyvinyl alcohol-type polymer film and polarizing film Download PDFInfo
- Publication number
- WO2013146458A1 WO2013146458A1 PCT/JP2013/057791 JP2013057791W WO2013146458A1 WO 2013146458 A1 WO2013146458 A1 WO 2013146458A1 JP 2013057791 W JP2013057791 W JP 2013057791W WO 2013146458 A1 WO2013146458 A1 WO 2013146458A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- pva
- mass
- polyvinyl alcohol
- content
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Definitions
- the present invention relates to a polyvinyl alcohol polymer film having few defects and good transparency (hereinafter, “polyvinyl alcohol polymer” may be abbreviated as “PVA”), and a polarizing film produced therefrom. .
- PVA polyvinyl alcohol polymer film having few defects and good transparency
- PVA films are used in various applications by utilizing unique properties such as transparency, optical characteristics, mechanical strength, and water solubility, and recently, liquid crystal displays (
- the use as a raw material (raw film) of a polarizing film constituting a polarizing plate which is a basic component of LCD) is expanding.
- the polarizing plate for LCD is required to have high optical performance, and high optical performance is also required for the polarizing film which is a constituent element thereof.
- a polarizing plate is produced by dyeing, uniaxially stretching a PVA film and, if necessary, further applying a fixing treatment with a boron compound or the like to produce a polarizing film, and thereafter, on the surface of the polarizing film, a cellulose triacetate (TAC) film or the like. It is manufactured by laminating a protective film.
- the PVA film is produced by drying a film-forming stock solution containing PVA using a cast film-forming method or the like.
- the content of calcium or silicon in the PVA film is defined as a specific range for the purpose of obtaining a PVA film in which the occurrence of optical streaks and optical color unevenness is suppressed.
- the Patent Document 1 specifically describes a PVA film containing about 0.01 parts by mass of a surfactant with respect to 100 parts by mass of PVA.
- the content of calcium is about 280 ppm
- the content of silicon It is shown that if the amount is about 70 ppm, the optical streak and optical color unevenness which are problems in Patent Document 1 can be sufficiently reduced.
- the inventor of the present invention has deteriorated the transparency of the PVA film obtained when the PVA film is formed by using a relatively large amount of a specific surfactant for the purpose of eliminating the streaky defects in the PVA film. It was recognized that the optical performance of the polarizing film produced using it could be improved by improving the transparency in the PVA film. Particularly in recent years, there has been a strong demand for reducing power consumption in LCDs, and in order to maintain high screen brightness even when the backlight intensity is low, the light transmittance of the polarizing plate and thus the polarizing film must be increased. Although it is desired to improve, if the transparency in a PVA film is improved, it was thought that the polarizing film which improved the light transmittance can be obtained easily.
- an object of the present invention is to provide a PVA film having few defects and good transparency, and a high-quality polarizing film having an improved light transmittance produced therefrom.
- the present inventor when a specific surfactant is used in a relatively large amount, forms a film-forming stock solution used in a PVA film or for film formation thereof. It has been found that the transparency of the obtained PVA film deteriorates due to the influence of a specific metal in the inside. And, if the content of the metal in the obtained PVA film is adjusted, for example, by adjusting the content of the metal in the stock solution to a specific range, the PVA film has few defects and good transparency. I found out that The inventor has further studied based on these findings and completed the present invention.
- a PVA film comprising a PVA composition containing PVA (A) and a nonionic surfactant (B), wherein in the PVA composition, the content of the nonionic surfactant (B) is PVA ( A)
- the content of at least one metal (C) selected from the group consisting of alkali metals and alkaline earth metals in PVA (A) is 0.02 to 1 parts by mass with respect to 100 parts by mass.
- a PVA film with few defects and good transparency and a high-quality polarizing film with improved light transmittance produced therefrom.
- the PVA film of the present invention comprises a PVA composition containing PVA (A) and a nonionic surfactant (B).
- the content of the nonionic surfactant (B) is 0.02 to 1 part by mass with respect to 100 parts by mass of PVA (A), and alkali metal and alkaline earth metal.
- the content of at least one metal (C) selected from the group consisting of is 100 ppm or less on a mass basis with respect to PVA (A).
- PVA (A) one produced by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester monomer can be used.
- vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like.
- vinyl acetate is preferable from the viewpoints of availability, cost, and productivity of PVA (A).
- the vinyl ester polymer is preferably obtained by using only one or two or more vinyl ester monomers as a monomer, and using only one vinyl ester monomer as a monomer. Although what was obtained is more preferable, the copolymer of 1 type, or 2 or more types of vinyl-ester type monomers and the other monomer copolymerizable with this may be sufficient.
- vinyl ester monomers include, for example, ethylene; olefins having 3 to 30 carbon atoms such as propylene, 1-butene and isobutene; acrylic acid or salts thereof; methyl acrylate, acrylic Such as ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc.
- Acrylic acid ester methacrylic acid or salt thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, methacrylic acid 2-ethylhexyl, dodecyl methacrylate
- Methacrylic acid esters such as octadecyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamide propanesulfonic acid or salt thereof, acrylamidopropyldimethylamine or salt thereof, N Acrylamide derivatives such as methylolacrylamide or derivatives thereof; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid or
- Vinyl amides such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; acrylonitrile, methacrylonitrile, etc.
- Vinyl cyanide vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid or its salt, ester or acid anhydride; itaconic acid or its salt , Esters or acid anhydrides; vinylsilyl compounds such as vinyltrimethoxysilane; isopropenyl acetate and the like.
- the vinyl ester polymer can have a structural unit derived from one or more of these other monomers.
- the proportion of the structural unit derived from the other monomer in the vinyl ester polymer is not particularly limited, but based on the number of moles of all structural units constituting the vinyl ester polymer, it is 15 mol% or less. It is preferable that it is 5 mol% or less.
- the degree of polymerization of PVA (A) is not necessarily limited, but is preferably 200 or more, more preferably 300 or more, more preferably 400 or more, because the film strength tends to decrease as the degree of polymerization decreases. Particularly preferred is 500 or more. Further, if the degree of polymerization is too high, the viscosity of the aqueous solution or molten PVA (A) tends to be high, and film formation tends to be difficult, and therefore it is preferably 10,000 or less, more preferably 9,000. Hereinafter, it is more preferably 8,000 or less, and particularly preferably 7,000 or less.
- the degree of polymerization of PVA (A) means the average degree of polymerization measured according to the description of JIS K6726-1994.
- the saponification degree of PVA (A) is preferably 95 mol% or more, more preferably 98 mol% or more, and even more preferably 99 mol% or more.
- the degree of saponification of PVA (A) is the total number of moles of structural units (typically vinyl ester monomer units) that can be converted into vinyl alcohol units by saponification, and vinyl alcohol units, which PVA (A) has. Is the ratio (mol%) occupied by the number of moles of the vinyl alcohol unit.
- the degree of saponification of PVA (A) can be measured according to the description of JIS K6726-1994.
- the PVA composition may contain one type of PVA alone as PVA (A), and one or more of the degree of polymerization, the degree of saponification, the degree of modification, etc. are different from each other.
- the PVA may be contained.
- the PVA composition has an acidic functional group such as a carboxyl group or a sulfonic acid group.
- the PVA composition does not contain any of PVA having an acidic functional group, PVA having an acid anhydride group, PVA having a basic functional group, and neutralized products thereof.
- PVA (A) a vinyl ester PVA produced by saponifying a vinyl ester polymer obtained using only monomers as monomers, Preliminary / or, more preferably containing only PVA produced by saponifying a vinyl ester based polymer obtained by using only the vinyl ester monomer and ethylene monomer.
- the content of PVA (A) in the PVA composition is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 85% by mass or more.
- the PVA composition further contains a nonionic surfactant (B) in addition to the above PVA (A).
- the nonionic surfactant (B) include alkyl ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl ester types such as polyoxyethylene laurate; polyoxy Alkylamine types such as ethylene lauryl amino ether; Alkylamides type such as polyoxyethylene lauric acid amide; Polypropylene glycol ether types such as polyoxyethylene polyoxypropylene ether; Alkanolamide types such as lauric acid diethanolamide and oleic acid diethanolamide An allyl phenyl ether type such as polyoxyalkylene allyl phenyl ether.
- the PVA composition may contain only one kind of nonionic surfactant, or may contain two or more kinds of nonionic surfactant.
- the nonionic surfactant (B) is preferably a nonionic surfactant having an alkyl chain (alkyl group) having 9 or more carbon atoms.
- a nonionic surfactant is likely to deteriorate in transparency in a PVA film due to low polarity or the like depending on the prior art. Therefore, when the nonionic surfactant is used, the nonionic surfactant is related to transparency. The effect of the present invention is more remarkable.
- the nonionic surfactant (B) is a nonionic surfactant having an alkyl chain having 9 or more carbon atoms, the occurrence of streak-like defects can be further reduced when a PVA film is formed.
- the number of carbon atoms (alkyl chain length) of the alkyl chain is more preferably 10 or more, preferably 30 or less, more preferably 22 or less, and 16 or less. More preferably, it is 12 or less.
- the alkyl chain may be linear or branched, and is preferably linear. Moreover, it is preferable that said alkyl chain is contained in the principal chain part (longest chain) of nonionic surfactant (B).
- the nonionic surfactant (B) is preferably an alkanolamide type nonionic surfactant, and more preferably a fatty acid dialkanolamide.
- such nonionic surfactants are likely to interact with the metal (C), which will be described later, and the transparency in the PVA film is likely to deteriorate.
- the nonionic surfactant is used, the effect of the present invention relating to transparency is more remarkably exhibited.
- the nonionic surfactant (B) is an alkanolamide type nonionic surfactant, the occurrence of streak-like defects can be further reduced when a PVA film is formed.
- the content of the nonionic surfactant (B) in the PVA composition needs to be in the range of 0.02 to 1 part by mass with respect to 100 parts by mass of PVA (A).
- the content is less than 0.02 parts by mass with respect to 100 parts by mass of PVA (A)
- streaky defects are likely to occur when a PVA film is formed.
- the content exceeds 1 part by mass with respect to 100 parts by mass of PVA (A)
- the PVA film moves to the surface and blocking is likely to occur, resulting in poor handling.
- the content is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and 0.2 parts by mass with respect to 100 parts by mass of PVA (A). More preferably, it is 0.7 mass parts or less, and more preferably 0.5 mass parts or less.
- the PVA composition may further contain a surfactant other than the nonionic surfactant (B).
- a surfactant other than the nonionic surfactant (B) examples include anionic surfactants.
- anionic surfactant examples include carboxylic acid types such as potassium laurate; sulfate ester types such as octyl sulfate; sulfonic acid types such as dodecylbenzene sulfonate and the like.
- nonionic surfactant (B) and other surfactants other than that it is preferable to use them in the form of a mixture containing these surfactants because they are easily available and inexpensive.
- the surfactant content in the mixture is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
- 99.99 mass% is mentioned, for example.
- the components other than the surfactant contained in the mixture For example, raw materials, catalysts, and solvents used in the production of the surfactant; decomposition products generated by the decomposition of the surfactant; And a stabilizer added to improve the stability of the surfactant. More specifically, when the surfactant is an alkanolamide-type nonionic surfactant, a corresponding alkanolamine is exemplified.
- the content of at least one metal (C) selected from the group consisting of alkali metals and alkaline earth metals is based on mass relative to PVA (A) (that is, metal relative to the mass of PVA (A))
- the ratio of the mass of (C) is required to be 100 ppm or less.
- the content of the metal (C) is preferably 60 ppm or less, more preferably 50 ppm or less, and further preferably 30 ppm or less, based on mass with respect to PVA (A). It is particularly preferably 10 ppm or less.
- the content of the metal (C) is too small, wrinkles tend to occur when the formed PVA film is wound on a film roll, so the content is relative to PVA (A). It is preferably 0.2 ppm or more on a mass basis, more preferably 0.4 ppm or more, further preferably 0.5 ppm or more, and particularly preferably 0.7 ppm or more.
- the sum total of content of each metal should just be in the said range.
- the content of metal (C) can be determined by ICP-MS analysis.
- the metal (C) examples include lithium, sodium, potassium, rubidium and the like as the alkali metal, and magnesium and calcium as the alkaline earth metal.
- the PVA film contains a nonionic surfactant (B) in a relatively large amount as described above, it has a strong influence on the transparency of the PVA film, so that the metal (C) is an alkaline earth.
- a metal is preferable, and calcium is more preferable.
- limiting in particular in the form of a metal (C) Since the effect of this invention is show
- the PVA composition preferably contains a plasticizer because it can impart flexibility to the PVA film.
- Preferred plasticizers include polyhydric alcohols, and specific examples include ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane.
- the PVA composition may contain only one kind of plasticizer or may contain two or more kinds of plasticizers. Among these plasticizers, ethylene glycol or glycerin is preferable from the viewpoint of compatibility with PVA (A) and availability.
- the content of the plasticizer in the PVA composition is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of PVA (A).
- the PVA composition further contains other components other than the above-mentioned surfactants such as PVA (A) and nonionic surfactant (B), metal (C), and plasticizer as necessary. Also good.
- examples of such other components include water, antioxidants, ultraviolet absorbers, lubricants, colorants, fillers (inorganic particles, starch, etc.), preservatives, antifungal agents, and other components other than those described above. Examples thereof include polymer compounds.
- the thickness of the PVA film of the present invention is not particularly limited, and can be set as appropriate according to the use of the PVA film.
- the thickness can be 300 ⁇ m or less.
- the PVA film of the present invention is an optical film such as a polarizing film. When used as a raw film for production, the thickness is preferably in the range of 5 to 150 ⁇ m.
- the thickness of a PVA film can be calculated
- the shape of the PVA film of the present invention is not particularly limited, but a more uniform PVA film can be produced continuously and smoothly, and it can be continuously produced even when an optical film such as a polarizing film is produced using the PVA film. It is preferable that the film is a long film.
- the length of the long film (the length in the flow direction) is not particularly limited, and can be set as appropriate according to the application, for example, within a range of 5 to 30,000 m.
- the long film is preferably wound around a core to form a film roll.
- the width of the PVA film of this invention is preferably 1 m or more, and 3 m More preferably, it is 4.5 m or more, more preferably 5.0 m or more, and most preferably 5.5 m or more.
- the width of the PVA film is preferably 7.5 m or less, more preferably 7.0 m or less, and 6.5 m or less. Further preferred.
- a PVA film having good transparency can be obtained.
- the degree of transparency of the PVA film is not particularly limited.
- the haze value of the PVA film is preferably 3.0% or less, more preferably 2.5% or less, and 2.0% More preferably, it is more preferably 1.5% or less.
- an optical film such as a polarizing film having improved light transmittance can be easily obtained.
- the haze value of the PVA film was determined at 10 measurement points arbitrarily per 50 cm in the width direction over the entire width direction of the PVA film, and individual haze values were measured at the measurement points, as described later in Examples. In this case, the average value of the measured individual haze values can be obtained.
- each haze value is represented by the following formula showing the ratio of the diffuse transmittance (Td) to the total light transmittance (Tt) when the film is irradiated with visible light.
- Individual haze value (%) 100 ⁇ Td / Tt
- a PVA film with little variation in transparency in the width direction in addition to obtaining a PVA film with good transparency, a PVA film with little variation in transparency in the width direction can be obtained.
- an optical film such as a polarizing film with little unevenness in light transmittance over the entire film surface.
- the PVA film of the present invention was measured when 10 measurement points were arbitrarily determined per 50 cm in the width direction over the entire width direction of the PVA film as described above, and individual haze values were measured at the measurement points.
- the maximum value among the individual haze values is preferably 3.5% or less, more preferably 3.0% or less, further preferably 2.5% or less, and 2.0% or less. It is particularly preferred that
- the difference between the maximum value and the minimum value among the individual haze values is preferably 0.8% or less, more preferably 0.6% or less, and It is more preferably 3% or less, and particularly preferably 0.2% or less.
- the manufacturing method of the PVA film of this invention For example, surfactant, liquid media, such as PVA (A) and nonionic surfactant (B), and the above-mentioned plasticizer and others as needed It can manufacture by employ
- the adjustment method is not particularly limited.
- the content of the metal (C) is obtained by using a raw material with a reduced content of the metal (C), or conversely, by adding a salt of the metal (C). And a method of increasing the value.
- the film-forming stock solution may be one obtained by dissolving PVA (A) in a liquid medium, or one obtained by melting PVA (A).
- liquid medium in the film-forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, Examples thereof include ethylenediamine and diethylenetriamine, and one or more of these can be used.
- water is preferable from the viewpoint of a small environmental load and recoverability.
- a liquid medium having a reduced metal (C) content such as a distilled liquid medium, is used as at least a part of the liquid medium in order to bring the metal (C) content in the film-forming stock solution into a desired range. It is preferable.
- the volatile fraction of the film-forming stock solution (the content ratio of volatile components such as a liquid medium removed by volatilization or evaporation during film-forming in the film-forming stock solution) varies depending on the film-forming method, film-forming conditions, etc. It is preferably in the range of 90% by mass, and more preferably in the range of 55-80% by mass.
- the volatile fraction of the film-forming stock solution is 50% by mass or more, the viscosity of the film-forming stock solution does not become too high, and film formation becomes easy.
- the volatile fraction of the film-forming stock solution is 90% by mass or less, the thickness uniformity of the obtained PVA film is improved without the viscosity of the film-forming stock solution being too low.
- the film forming stock solution is a drum. It is cast or discharged in the form of a film on a support such as a belt or belt, dried on the support, and the resulting film is further dried by a drying roll or hot air drying device, if necessary, or heat-treated.
- the target PVA film can be manufactured by heat-processing with an apparatus, or adjusting humidity with a humidity control apparatus.
- the manufactured PVA film is preferably wound into a core to form a film roll. Moreover, you may cut off the both ends of the width direction of the manufactured PVA film.
- the PVA film of the present invention can be suitably used as a raw film for producing an optical film such as a high-quality polarizing film, a retardation film, and a special light collecting film with improved light transmittance.
- the PVA film of the present invention can also be used for other uses, for example, a packaging material, a water-soluble film such as a laundry bag, a release film for producing artificial marble, and the like.
- the PVA film of the present invention is particularly preferably used as a raw film for producing a polarizing film.
- the PVA film may be dyed, uniaxially stretched, fixed, dried, and further heat treated as necessary.
- the order of dyeing and uniaxial stretching is not particularly limited, and the dyeing process may be performed before the uniaxial stretching process, the dyeing process may be performed simultaneously with the uniaxial stretching process, or the dyeing process may be performed after the uniaxial stretching process. You may go.
- steps such as uniaxial stretching and dyeing may be repeated a plurality of times. In particular, it is preferable to divide the uniaxial stretching into two or more stages because uniform stretching is easily performed.
- Examples of the dye used for dyeing the PVA film include iodine or a dichroic organic dye (for example, DirectBlack 17, 19, 154; DirectBrown 44, 106, 195, 210, 223; DirectRed 2, 23, 28, 31, 37, 39. 79, 81, 240, 242, 247; DirectBlue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; DirectViolet 9, 12, 51, 98; DirectGreen 1, 85; Direct Yellow 8, 12, 44, 86, 87; dichroic dyes such as Direct Orange 26, 39, 106, 107) can be used. These dyes can be used alone or in combination of two or more. Dyeing can usually be performed by immersing the PVA film in a solution containing the dye, but the treatment conditions and treatment method are not particularly limited.
- Uniaxial stretching for stretching the PVA film in the flow direction (MD) or the like may be performed by either a wet stretching method or a dry heat stretching method, but from the viewpoint of the performance and quality stability of the obtained polarizing film, the wet stretching method. Is preferred.
- the wet stretching method include a method of stretching a PVA film in pure water, an aqueous solution containing various components such as an additive and an aqueous medium, or an aqueous dispersion in which various components are dispersed.
- Uniaxial stretching by a wet stretching method are preferred.
- the method include a method of uniaxially stretching in warm water containing boric acid, a method of uniaxially stretching in a solution containing the above-described dye or a fixing treatment bath described later, and the like. Moreover, you may uniaxially stretch in the air using the PVA film after water absorption, and you may uniaxially stretch by another method.
- the stretching temperature for uniaxial stretching is not particularly limited, but in the case of wet stretching, a temperature in the range of preferably 20 to 90 ° C, more preferably 25 to 70 ° C, and even more preferably 30 to 65 ° C is adopted. In the case of hot stretching, a temperature within the range of 50 to 180 ° C. is preferably employed.
- the stretching ratio of the uniaxial stretching treatment (the total stretching ratio when performing uniaxial stretching in multiple stages) is preferably stretched as much as possible from the point of polarization performance until just before the film is cut, and specifically 4 times or more. Is preferably 5 times or more, more preferably 5.5 times or more.
- the upper limit of the stretching ratio is not particularly limited as long as the film is not broken, but is preferably 8.0 times or less in order to perform uniform stretching.
- fixing treatment is often performed in order to strengthen the adsorption of the dye to the uniaxially stretched film.
- a method of immersing a film in a treatment bath to which boric acid and / or a boron compound is added is generally widely adopted. In that case, you may add an iodine compound in a processing bath as needed.
- the film subjected to the uniaxial stretching treatment or the uniaxial stretching treatment and the fixing treatment is then subjected to a drying treatment (heat treatment).
- the temperature of the drying treatment (heat treatment) is preferably 30 to 150 ° C., particularly 50 to 140 ° C. If the temperature of the drying treatment (heat treatment) is too low, the dimensional stability of the obtained polarizing film tends to be lowered, while if too high, the polarizing performance is likely to deteriorate due to the decomposition of the dye.
- Protective films that are optically transparent and have mechanical strength can be bonded to both sides or one side of the polarizing film obtained as described above to form a polarizing plate.
- a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like is used.
- a PVA adhesive or a urethane adhesive is generally used, and among them, a PVA adhesive is preferably used.
- the polarizing plate obtained as described above can be used as a component of a liquid crystal display device after being coated with an acrylic adhesive or the like and then bonded to a glass substrate.
- a retardation film, a viewing angle improving film, a brightness improving film, or the like may be bonded simultaneously.
- the content of calcium in the PVA film was determined by ICP-MS analysis (high frequency inductively coupled plasma mass spectrometry). Specifically, first, about 5 g of a sample piece is taken from the PVA film obtained in the following examples or comparative examples, weighed into a platinum crucible, subjected to dry decomposition using nitric acid and sulfuric acid, and ash After adding about 5 mL of hydrochloric acid to the converted sample, it was fixed in a 25 mL “Teflon” volumetric flask and filtered with a PTFE filter having a pore diameter of 0.45 ⁇ m to prepare a sample solution.
- ICP-MS analysis high frequency inductively coupled plasma mass spectrometry
- the calibration curve used to determine the calcium content is SPEX CertiPrep, Inc. It was prepared using a standard solution for preparing a calibration curve prepared by diluting a standard solution “XSTC-622” manufactured by the company. "Measurement condition" Equipment: ELAN DRCII manufactured by Perkin-Elmer Plasma output: 1100W Nebulizer gas flow rate: 1.01 L / min Auxiliary gas flow rate: 1.10 L / min Plasma gas flow rate: 18.00 L / min
- the streaky defects on the PVA film parallel to the flow direction (MD) during film formation were visually observed and evaluated. Specifically, the sample piece cut out from the PVA film obtained in the following examples or comparative examples is suspended so that the MD is horizontal, and a 30 W straight tube fluorescent lamp is horizontally placed behind and lighted. The streaky defects observed when the fluorescent lamp was viewed through the sample piece were evaluated according to the following criteria. A: No streak-like defects are observed B: Almost no streak-like defects are observed C: A few streak-like defects are observed D: Many streak-like defects are observed
- the number of haze value measurement points is 10 per 50 cm in the width direction.
- the haze value at the measurement point of a number proportional to the width that is, the number obtained by dividing the width of the sample piece by 5 cm and rounding up. It was measured. The average value of the obtained individual haze values was determined and used as the haze value of the PVA film. Moreover, the maximum value and the minimum value of the obtained individual haze values were obtained, and the difference between them was calculated.
- Example 1 As PVA (A), PVA (saponified product of homopolymer of vinyl acetate) having a polymerization degree of 2400 and a saponification degree of 99.9 mol% was used, and this PVA chip (calcium content is based on mass relative to PVA). After dipping 100 parts by mass (less than 0.005 ppm) in 2500 parts by mass of distilled water at 35 ° C. for 24 hours, centrifugal dehydration was performed to obtain a PVA water-containing chip. The volatile fraction in the obtained PVA water-containing chip was 70% by mass.
- a PVA film having a width of 165 cm was continuously produced by cutting off both ends of the film which became thick due to neck-in at the time of film formation.
- a length of 4000 m of the manufactured PVA film was wound around a cylindrical core to obtain a film roll.
- the obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll.
- the content of calcium is 1.8 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “A”, and the haze value is 0.4% (maximum value is 0.5%, minimum value) 0.4% and the difference between the two was 0.1%), and no blocking was observed.
- wrinkles particularly conspicuous on the surface of the film roll were not observed.
- Example 2 In Example 1, the PVA film (and film roll) was prepared in the same manner as in Example 1 except that the amount of calcium chloride dihydrate added was changed from 0.0002 parts by mass to 0.008 parts by mass in terms of calcium. Manufactured. The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 78 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “A”, the haze value is 2.8% (the maximum value is 3.3%, and the minimum value is 2). 0.6% and the difference between the two was 0.7%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
- Example 3 In Example 1, the nonionic surfactant (B) is changed from lauric acid diethanolamide (purity 95% by mass, mixture containing diethanolamine as an impurity) to polyoxyethylene laurylamine (purity 93% by mass, mixture containing impurities).
- a PVA film (and a film roll) was produced in the same manner as in Example 1 except that the change was made.
- the obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll.
- the content of calcium is 1.9 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “B”, and the haze value is 0.8% (maximum value is 1.0%, minimum value) 0.7% and the difference between the two was 0.3%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed.
- Table 1 The above results are summarized in Table 1.
- Example 4 In Example 1, the nonionic surfactant (B) was changed from lauric acid diethanolamide (purity 95 mass%, a mixture containing diethanolamine as an impurity) to stearic acid diethanolamide (purity 95 mass%, a mixture containing impurities).
- a PVA film (and a film roll) was produced in the same manner as in Example 1 except that. The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll.
- the content of calcium is 1.8 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “B”, and the haze value is 0.6% (maximum value is 0.8%, minimum value) 0.5% and the difference between the two was 0.3%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed.
- Table 1 The above results are summarized in Table 1.
- Example 5 In Example 1, a PVA film (and a film roll) was produced in the same manner as in Example 1 except that calcium chloride dihydrate was not added.
- the obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll.
- the content of calcium is 0.01 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “A”, and the haze value is 0.3% (maximum value is 0.3%, minimum value) 0.2%, the difference between the two was 0.1%), and no blocking was observed.
- wrinkles occurred on the surface of the film roll.
- Example 1 the addition amount of lauric acid diethanolamide (purity 95% by mass, a mixture containing diethanolamine as an impurity) was changed from 0.3 parts by mass to 0.01 parts by mass, and addition of calcium chloride dihydrate A PVA film (and a film roll) was produced in the same manner as in Example 1 except that the amount was changed from 0.0002 parts by mass to 0.015 parts by mass in terms of calcium.
- the obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll.
- C metal
- the content of calcium is 148 ppm on a mass basis with respect to PVA, the streak-like defect is evaluated as “D”, and the haze value is 0.4% (maximum value is 0.5%, minimum value is 0). 4% and the difference between the two was 0.1%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed.
- Table 1 The above results are summarized in Table 1.
- Example 2 In Example 1, except that the addition amount of lauric acid diethanolamide (purity 95% by mass, mixture containing diethanolamine as an impurity) was changed from 0.3 parts by mass to 0.01 parts by mass, the same as in Example 1 PVA films (and film rolls) were produced. The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll.
- C metal
- the content of calcium is 2.0 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “D”, and the haze value is 0.4% (the maximum value is 0.4%, the minimum value) 0.3% and the difference between the two was 0.1%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed.
- Table 1 The above results are summarized in Table 1.
- Example 3 the PVA film (and film roll) was prepared in the same manner as in Example 1 except that the amount of calcium chloride dihydrate added was changed from 0.0002 parts by mass to 0.015 parts by mass in terms of calcium. Manufactured. The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll.
- the content of calcium is 152 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “A”, and the haze value is 3.3% (maximum value is 5.0%, minimum value is 3). 0.0% and the difference between the two was 2.0%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed.
- Table 1 The above results are summarized in Table 1.
- Example 4 In Example 1, the addition amount of lauric acid diethanolamide (purity 95% by mass, a mixture containing diethanolamine as an impurity) is changed from 0.3 parts by mass to 2.0 parts by mass (1.9 parts by mass as lauric acid diethanolamide).
- a PVA film (and a film roll) was produced in the same manner as in Example 1 except that the change was made. The obtained PVA film was measured or evaluated for the content of metal (C) (calcium) and streak-like defects by the method described above, and blocking was evaluated by the method described above for the obtained film roll.
- C metal
- the content of is 1.8 ppm on a mass basis with respect to PVA, and the streak-like defect was evaluated as “A”, but blocking was seen, and an original film for producing an optical film such as a polarizing film was obtained. As a film, it was unbearable. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed.
- Table 1 The above results are summarized in Table 1.
- the present invention since a PVA film with few defects and good transparency is provided, if the PVA film is used as a raw film, for example, a high-quality polarizing film with improved light transmittance, etc. An optical film can be manufactured at a low cost with a high product yield.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polarising Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Description
[1]PVA(A)およびノニオン系界面活性剤(B)を含有するPVA組成物からなるPVAフィルムであって、当該PVA組成物において、ノニオン系界面活性剤(B)の含有量がPVA(A)100質量部に対して0.02~1質量部であり、かつ、アルカリ金属およびアルカリ土類金属からなる群より選ばれる少なくとも1種の金属(C)の含有量がPVA(A)に対して質量基準で100ppm以下である、PVAフィルム、
[2]ノニオン系界面活性剤(B)が炭素数9以上のアルキル鎖を有するノニオン系界面活性剤である、上記[1]のPVAフィルム、
[3]ノニオン系界面活性剤(B)がアルカノールアミド型のノニオン系界面活性剤である、上記[1]または[2]のPVAフィルム、
[4]金属(C)がアルカリ土類金属である、上記[1]~[3]のいずれか1つのPVAフィルム、
[5]金属(C)がカルシウムである、上記[1]~[3]のいずれか1つのPVAフィルム、
[6]金属(C)の含有量がPVA(A)に対して質量基準で0.2ppm以上である、上記[1]~[5]のいずれか1つのPVAフィルム、
[7]金属(C)の含有量がPVA(A)に対して質量基準で60ppm以下である、上記[1]~[6]のいずれか1つのPVAフィルム、
[8]上記[1]~[7]のいずれか1つのPVAフィルムから製造される偏光フィルム、
に関する。 That is, the present invention
[1] A PVA film comprising a PVA composition containing PVA (A) and a nonionic surfactant (B), wherein in the PVA composition, the content of the nonionic surfactant (B) is PVA ( A) The content of at least one metal (C) selected from the group consisting of alkali metals and alkaline earth metals in PVA (A) is 0.02 to 1 parts by mass with respect to 100 parts by mass. PVA film that is 100 ppm or less on a mass basis,
[2] The PVA film of the above [1], wherein the nonionic surfactant (B) is a nonionic surfactant having an alkyl chain having 9 or more carbon atoms,
[3] The PVA film of [1] or [2] above, wherein the nonionic surfactant (B) is an alkanolamide type nonionic surfactant,
[4] The PVA film according to any one of the above [1] to [3], wherein the metal (C) is an alkaline earth metal,
[5] The PVA film according to any one of the above [1] to [3], wherein the metal (C) is calcium,
[6] The PVA film according to any one of the above [1] to [5], wherein the content of the metal (C) is 0.2 ppm or more based on mass with respect to the PVA (A),
[7] The PVA film according to any one of the above [1] to [6], wherein the content of the metal (C) is 60 ppm or less based on mass relative to the PVA (A),
[8] A polarizing film produced from the PVA film of any one of [1] to [7] above,
About.
本発明のPVAフィルムはPVA(A)およびノニオン系界面活性剤(B)を含有するPVA組成物からなる。そして、当該PVA組成物において、ノニオン系界面活性剤(B)の含有量は、PVA(A)100質量部に対して0.02~1質量部であり、かつ、アルカリ金属およびアルカリ土類金属からなる群より選ばれる少なくとも1種の金属(C)の含有量は、PVA(A)に対して質量基準で100ppm以下である。 The present invention is described in further detail below.
The PVA film of the present invention comprises a PVA composition containing PVA (A) and a nonionic surfactant (B). In the PVA composition, the content of the nonionic surfactant (B) is 0.02 to 1 part by mass with respect to 100 parts by mass of PVA (A), and alkali metal and alkaline earth metal. The content of at least one metal (C) selected from the group consisting of is 100 ppm or less on a mass basis with respect to PVA (A).
重合度 = ([η]×103/8.29)(1/0.62) The degree of polymerization of PVA (A) is not necessarily limited, but is preferably 200 or more, more preferably 300 or more, more preferably 400 or more, because the film strength tends to decrease as the degree of polymerization decreases. Particularly preferred is 500 or more. Further, if the degree of polymerization is too high, the viscosity of the aqueous solution or molten PVA (A) tends to be high, and film formation tends to be difficult, and therefore it is preferably 10,000 or less, more preferably 9,000. Hereinafter, it is more preferably 8,000 or less, and particularly preferably 7,000 or less. Here, the degree of polymerization of PVA (A) means the average degree of polymerization measured according to the description of JIS K6726-1994. After re-saponifying and purifying PVA (A), it is measured in water at 30 ° C. The intrinsic viscosity [η] (unit: deciliter / g) is obtained by the following formula.
Degree of polymerization = ([η] × 10 3 /8.29) (1 / 0.62)
個々のヘイズ値(%)=100×Td/Tt According to the present invention, a PVA film having good transparency can be obtained. The degree of transparency of the PVA film is not particularly limited. For example, the haze value of the PVA film is preferably 3.0% or less, more preferably 2.5% or less, and 2.0% More preferably, it is more preferably 1.5% or less. Thus, according to the PVA film having good transparency, an optical film such as a polarizing film having improved light transmittance can be easily obtained. In addition, the haze value of the PVA film was determined at 10 measurement points arbitrarily per 50 cm in the width direction over the entire width direction of the PVA film, and individual haze values were measured at the measurement points, as described later in Examples. In this case, the average value of the measured individual haze values can be obtained. Here, each haze value is represented by the following formula showing the ratio of the diffuse transmittance (Td) to the total light transmittance (Tt) when the film is irradiated with visible light.
Individual haze value (%) = 100 × Td / Tt
ICP-MS分析(高周波誘導結合プラズマ質量分析)によりPVAフィルム(PVA組成物)中におけるカルシウムの含有量を求めた。具体的には、まず、以下の実施例または比較例で得られたPVAフィルムから約5gのサンプル片を採取し、それを白金るつぼに量り取り、硝酸と硫酸を用いて乾式分解を行い、灰化した試料に塩酸約5mLを加えた後、25mL容「テフロン」製メスフラスコに定容し、孔径0.45μmのPTFEフィルターでろ過して試料溶液を調製した。次いで、得られた試料溶液を用いて、以下の条件でICP-MS分析を行い、PVAフィルム(PVA組成物)中におけるカルシウムの含有量を、PVA(A)の質量に対する金属(C)の質量の割合として求めた。なお、カルシウムの含有量を求める際に使用した検量線は、SPEX CertiPrep,Inc.社製の標準液「XSTC-622」を希釈することにより調製した検量線作成用標準液を用いて作成した。
《測定条件》
装置:Perkin-Elmer社製ELAN DRCII
プラズマ出力:1100W
ネブライザーガス流量:1.01L/分
補助ガス流量:1.10L/分
プラズマガス流量:18.00L/分 [Measuring method of content of metal (C)]
The content of calcium in the PVA film (PVA composition) was determined by ICP-MS analysis (high frequency inductively coupled plasma mass spectrometry). Specifically, first, about 5 g of a sample piece is taken from the PVA film obtained in the following examples or comparative examples, weighed into a platinum crucible, subjected to dry decomposition using nitric acid and sulfuric acid, and ash After adding about 5 mL of hydrochloric acid to the converted sample, it was fixed in a 25 mL “Teflon” volumetric flask and filtered with a PTFE filter having a pore diameter of 0.45 μm to prepare a sample solution. Next, using the obtained sample solution, ICP-MS analysis was performed under the following conditions, and the calcium content in the PVA film (PVA composition) was determined based on the mass of the metal (C) relative to the mass of PVA (A). As a percentage of The calibration curve used to determine the calcium content is SPEX CertiPrep, Inc. It was prepared using a standard solution for preparing a calibration curve prepared by diluting a standard solution “XSTC-622” manufactured by the company.
"Measurement condition"
Equipment: ELAN DRCII manufactured by Perkin-Elmer
Plasma output: 1100W
Nebulizer gas flow rate: 1.01 L / min Auxiliary gas flow rate: 1.10 L / min Plasma gas flow rate: 18.00 L / min
PVAフィルム上の、製膜時の流れ方向(MD)に平行に存在するスジ状の欠点を目視で観察して評価した。具体的には、以下の実施例または比較例で得られたPVAフィルムから切り出したサンプル片をMDが水平になるように吊り下げ、その背後に30Wの直管状蛍光灯を水平に置いて点灯し、サンプル片を通して蛍光灯を見たときに観察されるスジ状の欠点について、以下の基準で評価した。
A:スジ状の欠点が認められない
B:スジ状の欠点がほとんどない
C:スジ状の欠点がわずかに認められる
D:スジ状の欠点が多数認められる [Evaluation method for streaks]
The streaky defects on the PVA film parallel to the flow direction (MD) during film formation were visually observed and evaluated. Specifically, the sample piece cut out from the PVA film obtained in the following examples or comparative examples is suspended so that the MD is horizontal, and a 30 W straight tube fluorescent lamp is horizontally placed behind and lighted. The streaky defects observed when the fluorescent lamp was viewed through the sample piece were evaluated according to the following criteria.
A: No streak-like defects are observed B: Almost no streak-like defects are observed C: A few streak-like defects are observed D: Many streak-like defects are observed
以下の実施例または比較例で得られたPVAフィルムから、MDに15cm、幅方向(TD)に全幅の、横に長い短冊状のサンプルを採取した。このサンプルをさらに一方の端からTDに50cmずつの幅に裁断した。なお幅が50cmに満たないサンプル片が残った場合には(以下の実施例および比較例では幅165cmのPVAフィルムを製造しているので幅が15cmのサンプル片が残る)、そのサンプル片についてはその幅のままとした。
得られた50cm幅のサンプル片の上から任意に10ヶ所の測定地点を選定し、その測定地点でのヘイズ値をスガ試験機株式会社製のヘーズメーター「HZ-1」を用い、ASTM D1003-61に従って測定した。すなわち、ヘイズ値の測定地点の数は、幅方向50cmあたり10ヶ所になる。なお、幅が50cmに満たないサンプル片については、その幅に比例した数(すなわち、そのサンプル片の幅を5cmで除し、端数は切り上げて得られた数)の測定地点でのヘイズ値を測定した。得られた個々のヘイズ値の平均値を求めてそのPVAフィルムのヘイズ値とした。また、得られた個々のヘイズ値のうちの最大値と最小値を求め、両者の差を算出した。 [Measurement method of haze value]
From the PVA film obtained in the following examples or comparative examples, a strip-like sample having a length of 15 cm in the MD and a full width in the width direction (TD) was taken. This sample was further cut from one end to a width of 50 cm in TD. When a sample piece with a width of less than 50 cm remains (in the following examples and comparative examples, a sample piece with a width of 15 cm remains because a PVA film with a width of 165 cm remains). The width was left as it was.
Ten arbitrary measurement points were selected from the top of the obtained 50 cm wide sample piece, and the haze value at the measurement point was measured using ASTM H100-1 manufactured by Suga Test Instruments Co., Ltd. according to ASTM D1003- Measured according to 61. That is, the number of haze value measurement points is 10 per 50 cm in the width direction. For sample pieces whose width is less than 50 cm, the haze value at the measurement point of a number proportional to the width (that is, the number obtained by dividing the width of the sample piece by 5 cm and rounding up) is obtained. It was measured. The average value of the obtained individual haze values was determined and used as the haze value of the PVA film. Moreover, the maximum value and the minimum value of the obtained individual haze values were obtained, and the difference between them was calculated.
以下の実施例または比較例で得られたフィルムロールからPVAフィルムを巻き出した際のブロッキングの有無を確認した。 [Method for evaluating blocking in film roll]
The presence or absence of blocking when the PVA film was unwound from the film roll obtained in the following Examples or Comparative Examples was confirmed.
PVA(A)として、重合度2400、けん化度99.9モル%のPVA(酢酸ビニルの単独重合体のけん化物)を用い、このPVAのチップ(カルシウムの含有量はPVAに対して質量基準で0.005ppm未満)100質量部を35℃の蒸留水2500質量部に24時間浸漬した後、遠心脱水を行い、PVA含水チップを得た。得られたPVA含水チップ中の揮発分率は70質量%であった。そのPVA含水チップ333質量部(乾燥状態のPVAは100質量部)に対して、グリセリンを12質量部、ノニオン系界面活性剤(B)としてラウリン酸ジエタノールアミド(純度95質量%、ジエタノールアミンを不純物として含む混合物)を0.3質量部、塩化カルシウム二水和物をカルシウム換算で0.0002質量部添加した後、よく混合して混合物とし、これを最高温度130℃のベント付き二軸押出機で加熱溶融して製膜原液とした。
この製膜原液を熱交換機で100℃に冷却した後、180cm幅のコートハンガーダイから表面温度を90℃にしたドラム上に押出製膜して、さらに熱風乾燥装置内を通して乾燥し、次いで、製膜時のネックインにより厚くなったフィルムの両端部を切り取ることにより、幅165cmのPVAフィルムを連続的に製造した。なお、製造されたPVAフィルムのうちの長さ4000m分を円筒状のコアに巻き取ってフィルムロールとした。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、スジ状の欠点およびヘイズ値を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で1.8ppmであり、スジ状の欠点は評価が「A」であり、ヘイズ値は0.4%(最大値は0.5%、最小値は0.4%、両者の差は0.1%)であり、ブロッキングは見られなかった。また、フィルムロールの表面に特に目立ったシワは観察されなかった。以上の結果を表1にまとめた。 [Example 1]
As PVA (A), PVA (saponified product of homopolymer of vinyl acetate) having a polymerization degree of 2400 and a saponification degree of 99.9 mol% was used, and this PVA chip (calcium content is based on mass relative to PVA). After dipping 100 parts by mass (less than 0.005 ppm) in 2500 parts by mass of distilled water at 35 ° C. for 24 hours, centrifugal dehydration was performed to obtain a PVA water-containing chip. The volatile fraction in the obtained PVA water-containing chip was 70% by mass. 12 parts by mass of glycerin and lauric acid diethanolamide (purity 95% by mass, diethanolamine as an impurity) with respect to 333 parts by mass of the PVA hydrous chip (100 parts by mass of dry PVA) 0.3 parts by weight of the mixture) and 0.0002 parts by weight of calcium chloride dihydrate in terms of calcium, and then mixed well to obtain a mixture. A film forming stock solution was obtained by heating and melting.
After this film-forming stock solution is cooled to 100 ° C. with a heat exchanger, it is formed into a film by extrusion from a coat hanger die having a width of 180 cm onto a drum having a surface temperature of 90 ° C., and further dried through a hot air dryer, and then manufactured. A PVA film having a width of 165 cm was continuously produced by cutting off both ends of the film which became thick due to neck-in at the time of film formation. In addition, a length of 4000 m of the manufactured PVA film was wound around a cylindrical core to obtain a film roll.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 1.8 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “A”, and the haze value is 0.4% (maximum value is 0.5%, minimum value) 0.4% and the difference between the two was 0.1%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
実施例1において、塩化カルシウム二水和物の添加量をカルシウム換算で0.0002質量部から0.008質量部に変更したこと以外は実施例1と同様にしてPVAフィルム(およびフィルムロール)を製造した。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、スジ状の欠点およびヘイズ値を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で78ppmであり、スジ状の欠点は評価が「A」であり、ヘイズ値は2.8%(最大値は3.3%、最小値は2.6%、両者の差は0.7%)であり、ブロッキングは見られなかった。また、フィルムロールの表面に特に目立ったシワは観察されなかった。以上の結果を表1にまとめた。 [Example 2]
In Example 1, the PVA film (and film roll) was prepared in the same manner as in Example 1 except that the amount of calcium chloride dihydrate added was changed from 0.0002 parts by mass to 0.008 parts by mass in terms of calcium. Manufactured.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 78 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “A”, the haze value is 2.8% (the maximum value is 3.3%, and the minimum value is 2). 0.6% and the difference between the two was 0.7%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
実施例1においてノニオン系界面活性剤(B)を、ラウリン酸ジエタノールアミド(純度95質量%、ジエタノールアミンを不純物として含む混合物)から、ポリオキシエチレンラウリルアミン(純度93質量%、不純物を含む混合物)に変更したこと以外は実施例1と同様にしてPVAフィルム(およびフィルムロール)を製造した。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、スジ状の欠点およびヘイズ値を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で1.9ppmであり、スジ状の欠点は評価が「B」であり、ヘイズ値は0.8%(最大値は1.0%、最小値は0.7%、両者の差は0.3%)であり、ブロッキングは見られなかった。また、フィルムロールの表面に特に目立ったシワは観察されなかった。以上の結果を表1にまとめた。 [Example 3]
In Example 1, the nonionic surfactant (B) is changed from lauric acid diethanolamide (purity 95% by mass, mixture containing diethanolamine as an impurity) to polyoxyethylene laurylamine (purity 93% by mass, mixture containing impurities). A PVA film (and a film roll) was produced in the same manner as in Example 1 except that the change was made.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 1.9 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “B”, and the haze value is 0.8% (maximum value is 1.0%, minimum value) 0.7% and the difference between the two was 0.3%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
実施例1においてノニオン系界面活性剤(B)を、ラウリン酸ジエタノールアミド(純度95質量%、ジエタノールアミンを不純物として含む混合物)から、ステアリン酸ジエタノールアミド(純度95質量%、不純物を含む混合物)に変更したこと以外は実施例1と同様にしてPVAフィルム(およびフィルムロール)を製造した。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、スジ状の欠点およびヘイズ値を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で1.8ppmであり、スジ状の欠点は評価が「B」であり、ヘイズ値は0.6%(最大値は0.8%、最小値は0.5%、両者の差は0.3%)であり、ブロッキングは見られなかった。また、フィルムロールの表面に特に目立ったシワは観察されなかった。以上の結果を表1にまとめた。 [Example 4]
In Example 1, the nonionic surfactant (B) was changed from lauric acid diethanolamide (purity 95 mass%, a mixture containing diethanolamine as an impurity) to stearic acid diethanolamide (purity 95 mass%, a mixture containing impurities). A PVA film (and a film roll) was produced in the same manner as in Example 1 except that.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 1.8 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “B”, and the haze value is 0.6% (maximum value is 0.8%, minimum value) 0.5% and the difference between the two was 0.3%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
実施例1において、塩化カルシウム二水和物を添加しなかったこと以外は実施例1と同様にしてPVAフィルム(およびフィルムロール)を製造した。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、スジ状の欠点およびヘイズ値を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で0.01ppmであり、スジ状の欠点は評価が「A」であり、ヘイズ値は0.3%(最大値は0.3%、最小値は0.2%、両者の差は0.1%)であり、ブロッキングは見られなかった。但し、フィルムロールの表面にシワが生じた。以上の結果を表1にまとめた。 [Example 5]
In Example 1, a PVA film (and a film roll) was produced in the same manner as in Example 1 except that calcium chloride dihydrate was not added.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 0.01 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “A”, and the haze value is 0.3% (maximum value is 0.3%, minimum value) 0.2%, the difference between the two was 0.1%), and no blocking was observed. However, wrinkles occurred on the surface of the film roll. The above results are summarized in Table 1.
実施例1において、ラウリン酸ジエタノールアミド(純度95質量%、ジエタノールアミンを不純物として含む混合物)の添加量を0.3質量部から0.01質量部に変更するとともに、塩化カルシウム二水和物の添加量をカルシウム換算で0.0002質量部から0.015質量部に変更したこと以外は実施例1と同様にしてPVAフィルム(およびフィルムロール)を製造した。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、スジ状の欠点およびヘイズ値を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で148ppmであり、スジ状の欠点は評価が「D」であり、ヘイズ値は0.4%(最大値は0.5%、最小値は0.4%、両者の差は0.1%)であり、ブロッキングは見られなかった。また、フィルムロールの表面に特に目立ったシワは観察されなかった。以上の結果を表1にまとめた。 [Comparative Example 1]
In Example 1, the addition amount of lauric acid diethanolamide (purity 95% by mass, a mixture containing diethanolamine as an impurity) was changed from 0.3 parts by mass to 0.01 parts by mass, and addition of calcium chloride dihydrate A PVA film (and a film roll) was produced in the same manner as in Example 1 except that the amount was changed from 0.0002 parts by mass to 0.015 parts by mass in terms of calcium.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 148 ppm on a mass basis with respect to PVA, the streak-like defect is evaluated as “D”, and the haze value is 0.4% (maximum value is 0.5%, minimum value is 0). 4% and the difference between the two was 0.1%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
実施例1において、ラウリン酸ジエタノールアミド(純度95質量%、ジエタノールアミンを不純物として含む混合物)の添加量を0.3質量部から0.01質量部に変更したこと以外は実施例1と同様にしてPVAフィルム(およびフィルムロール)を製造した。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、スジ状の欠点およびヘイズ値を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で2.0ppmであり、スジ状の欠点は評価が「D」であり、ヘイズ値は0.4%(最大値は0.4%、最小値は0.3%、両者の差は0.1%)であり、ブロッキングは見られなかった。また、フィルムロールの表面に特に目立ったシワは観察されなかった。以上の結果を表1にまとめた。 [Comparative Example 2]
In Example 1, except that the addition amount of lauric acid diethanolamide (purity 95% by mass, mixture containing diethanolamine as an impurity) was changed from 0.3 parts by mass to 0.01 parts by mass, the same as in Example 1 PVA films (and film rolls) were produced.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 2.0 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “D”, and the haze value is 0.4% (the maximum value is 0.4%, the minimum value) 0.3% and the difference between the two was 0.1%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
実施例1において、塩化カルシウム二水和物の添加量をカルシウム換算で0.0002質量部から0.015質量部に変更したこと以外は実施例1と同様にしてPVAフィルム(およびフィルムロール)を製造した。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、スジ状の欠点およびヘイズ値を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で152ppmであり、スジ状の欠点は評価が「A」であり、ヘイズ値は3.3%(最大値は5.0%、最小値は3.0%、両者の差は2.0%)であり、ブロッキングは見られなかった。また、フィルムロールの表面に特に目立ったシワは観察されなかった。以上の結果を表1にまとめた。 [Comparative Example 3]
In Example 1, the PVA film (and film roll) was prepared in the same manner as in Example 1 except that the amount of calcium chloride dihydrate added was changed from 0.0002 parts by mass to 0.015 parts by mass in terms of calcium. Manufactured.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium), streak-like defects and haze value by the method described above, and the blocking was evaluated by the method described above for the obtained film roll. The content of calcium is 152 ppm on a mass basis with respect to PVA, the streaky defect is evaluated as “A”, and the haze value is 3.3% (maximum value is 5.0%, minimum value is 3). 0.0% and the difference between the two was 2.0%), and no blocking was observed. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
実施例1において、ラウリン酸ジエタノールアミド(純度95質量%、ジエタノールアミンを不純物として含む混合物)の添加量を0.3質量部から2.0質量部(ラウリン酸ジエタノールアミドとして1.9質量部)に変更したこと以外は実施例1と同様にしてPVAフィルム(およびフィルムロール)を製造した。
得られたPVAフィルムについて上記した方法により金属(C)(カルシウム)の含有量、およびスジ状の欠点を測定または評価するとともに、得られたフィルムロールについて上記した方法によりブロッキングを評価したところ、カルシウムの含有量はPVAに対して質量基準で1.8ppmであり、スジ状の欠点は評価が「A」であったが、ブロッキングが見られ、偏光フィルム等の光学フィルムを製造するための原反フィルムとしては使用に耐えないものであった。なお、フィルムロールの表面に特に目立ったシワは観察されなかった。以上の結果を表1にまとめた。 [Comparative Example 4]
In Example 1, the addition amount of lauric acid diethanolamide (purity 95% by mass, a mixture containing diethanolamine as an impurity) is changed from 0.3 parts by mass to 2.0 parts by mass (1.9 parts by mass as lauric acid diethanolamide). A PVA film (and a film roll) was produced in the same manner as in Example 1 except that the change was made.
The obtained PVA film was measured or evaluated for the content of metal (C) (calcium) and streak-like defects by the method described above, and blocking was evaluated by the method described above for the obtained film roll. The content of is 1.8 ppm on a mass basis with respect to PVA, and the streak-like defect was evaluated as “A”, but blocking was seen, and an original film for producing an optical film such as a polarizing film was obtained. As a film, it was unbearable. In addition, wrinkles particularly conspicuous on the surface of the film roll were not observed. The above results are summarized in Table 1.
Claims (8)
- ポリビニルアルコール系重合体(A)およびノニオン系界面活性剤(B)を含有するポリビニルアルコール系重合体組成物からなるポリビニルアルコール系重合体フィルムであって、当該ポリビニルアルコール系重合体組成物において、ノニオン系界面活性剤(B)の含有量がポリビニルアルコール系重合体(A)100質量部に対して0.02~1質量部であり、かつ、アルカリ金属およびアルカリ土類金属からなる群より選ばれる少なくとも1種の金属(C)の含有量がポリビニルアルコール系重合体(A)に対して質量基準で100ppm以下である、ポリビニルアルコール系重合体フィルム。 A polyvinyl alcohol polymer film comprising a polyvinyl alcohol polymer composition containing a polyvinyl alcohol polymer (A) and a nonionic surfactant (B), wherein the polyvinyl alcohol polymer composition comprises: The content of the system surfactant (B) is 0.02 to 1 part by mass with respect to 100 parts by mass of the polyvinyl alcohol polymer (A), and is selected from the group consisting of alkali metals and alkaline earth metals The polyvinyl alcohol-type polymer film whose content of at least 1 sort (s) of metal (C) is 100 ppm or less on a mass basis with respect to a polyvinyl alcohol-type polymer (A).
- ノニオン系界面活性剤(B)が炭素数9以上のアルキル鎖を有するノニオン系界面活性剤である、請求項1に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to claim 1, wherein the nonionic surfactant (B) is a nonionic surfactant having an alkyl chain having 9 or more carbon atoms.
- ノニオン系界面活性剤(B)がアルカノールアミド型のノニオン系界面活性剤である、請求項1または2に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to claim 1 or 2, wherein the nonionic surfactant (B) is an alkanolamide type nonionic surfactant.
- 金属(C)がアルカリ土類金属である、請求項1~3のいずれか1項に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to any one of claims 1 to 3, wherein the metal (C) is an alkaline earth metal.
- 金属(C)がカルシウムである、請求項1~3のいずれか1項に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to any one of claims 1 to 3, wherein the metal (C) is calcium.
- 金属(C)の含有量がポリビニルアルコール系重合体(A)に対して質量基準で0.2ppm以上である、請求項1~5のいずれか1項に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to any one of claims 1 to 5, wherein the content of the metal (C) is 0.2 ppm or more based on mass with respect to the polyvinyl alcohol polymer (A).
- 金属(C)の含有量がポリビニルアルコール系重合体(A)に対して質量基準で60ppm以下である、請求項1~6のいずれか1項に記載のポリビニルアルコール系重合体フィルム。 The polyvinyl alcohol polymer film according to any one of claims 1 to 6, wherein the content of the metal (C) is 60 ppm or less on a mass basis with respect to the polyvinyl alcohol polymer (A).
- 請求項1~7のいずれか1項に記載のポリビニルアルコール系重合体フィルムから製造される偏光フィルム。 A polarizing film produced from the polyvinyl alcohol polymer film according to any one of claims 1 to 7.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380018359.5A CN104185653B (en) | 2012-03-30 | 2013-03-19 | Polyvinyl alcohol film and light polarizing film |
JP2013538387A JP6100167B2 (en) | 2012-03-30 | 2013-03-19 | POLYVINYL ALCOHOL POLYMER FILM AND POLARIZING FILM |
KR1020147030019A KR102135487B1 (en) | 2012-03-30 | 2013-03-19 | Polyvinyl alcohol-type polymer film and polarizing film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-079497 | 2012-03-30 | ||
JP2012079497 | 2012-03-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013146458A1 true WO2013146458A1 (en) | 2013-10-03 |
Family
ID=49259715
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/057791 WO2013146458A1 (en) | 2012-03-30 | 2013-03-19 | Polyvinyl alcohol-type polymer film and polarizing film |
Country Status (5)
Country | Link |
---|---|
JP (2) | JP6100167B2 (en) |
KR (1) | KR102135487B1 (en) |
CN (1) | CN104185653B (en) |
TW (2) | TWI626261B (en) |
WO (1) | WO2013146458A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015093499A1 (en) * | 2013-12-19 | 2015-06-25 | 株式会社クラレ | Film |
JP2016221954A (en) * | 2015-05-26 | 2016-12-28 | 日本合成化学工業株式会社 | Manufacturing method of polyvinyl alcohol-based film, polyvinyl alcohol-based film, polarization film, and cast mold |
JP2017053924A (en) * | 2015-09-08 | 2017-03-16 | 日本合成化学工業株式会社 | Film for polarizing film, and polarizing film using the same |
WO2018003671A1 (en) * | 2016-06-27 | 2018-01-04 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing films, method for producing same, and polarizing film using said polyvinyl alcohol film for polarizing films |
JP2018090691A (en) * | 2016-12-01 | 2018-06-14 | 株式会社クラレ | Polyvinyl alcohol film and method for producing polarizing film using the same |
WO2018168903A1 (en) * | 2017-03-15 | 2018-09-20 | 株式会社クラレ | Resin composition, production method for resin composition, and molded body using resin composition |
WO2019124310A1 (en) * | 2017-12-22 | 2019-06-27 | 株式会社クラレ | Polyvinyl alcohol film, film roll, and method for producing film roll |
CN112004881A (en) * | 2018-04-27 | 2020-11-27 | 株式会社可乐丽 | Polyvinyl alcohol film and method for producing polarizing film using same |
CN113227858A (en) * | 2018-12-28 | 2021-08-06 | 株式会社可乐丽 | Polyvinyl alcohol film and method for producing polarizing film using same |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113167959B (en) * | 2018-12-04 | 2023-05-30 | 株式会社可乐丽 | Polyvinyl alcohol film and method for producing polarizing film using same |
KR20210108957A (en) * | 2018-12-28 | 2021-09-03 | 주식회사 쿠라레 | Polyvinyl alcohol film and manufacturing method of polarizing film using same |
WO2020256052A1 (en) * | 2019-06-20 | 2020-12-24 | 株式会社クラレ | Polyvinyl alcohol film, and method for producing polarizing film using same |
CN112778673A (en) * | 2020-12-31 | 2021-05-11 | 中国科学技术大学先进技术研究院 | Polyvinyl alcohol membrane casting solution, preparation method and application of polyvinyl alcohol membrane |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001253993A (en) * | 2000-03-10 | 2001-09-18 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol film and method of producing the same |
JP2001311828A (en) * | 2000-05-02 | 2001-11-09 | Kuraray Co Ltd | Polyvinyl alcohol film for polarizing film, its manufacturing method and polarizing film |
JP2003248123A (en) * | 2001-12-17 | 2003-09-05 | Kuraray Co Ltd | Polyvinyl alcohol film and polarizing film |
JP2005206810A (en) * | 2003-12-24 | 2005-08-04 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based film and use of the same |
JP2006249407A (en) * | 2005-02-14 | 2006-09-21 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol film and manufacturing method thereof |
JP2007009056A (en) * | 2005-06-30 | 2007-01-18 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol film for optical film, its manufacturing method and polarizing film and polarizing plate obtained using the same |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1690891B1 (en) * | 2000-05-01 | 2017-01-11 | Kuraray Co., Ltd., Kurashiki Plant | Polyvinyl alcohol polymer film and polarization film |
JP4573404B2 (en) * | 2000-07-18 | 2010-11-04 | 株式会社クラレ | Manufacturing method of polarizing film |
JP4544425B2 (en) * | 2005-06-29 | 2010-09-15 | 信越化学工業株式会社 | Rare earth metal member manufacturing method |
-
2013
- 2013-03-19 JP JP2013538387A patent/JP6100167B2/en active Active
- 2013-03-19 WO PCT/JP2013/057791 patent/WO2013146458A1/en active Application Filing
- 2013-03-19 CN CN201380018359.5A patent/CN104185653B/en active Active
- 2013-03-19 KR KR1020147030019A patent/KR102135487B1/en active IP Right Grant
- 2013-03-28 TW TW106107882A patent/TWI626261B/en active
- 2013-03-28 TW TW102111070A patent/TWI602831B/en active
-
2017
- 2017-01-17 JP JP2017005968A patent/JP6334748B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001253993A (en) * | 2000-03-10 | 2001-09-18 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol film and method of producing the same |
JP2001311828A (en) * | 2000-05-02 | 2001-11-09 | Kuraray Co Ltd | Polyvinyl alcohol film for polarizing film, its manufacturing method and polarizing film |
JP2003248123A (en) * | 2001-12-17 | 2003-09-05 | Kuraray Co Ltd | Polyvinyl alcohol film and polarizing film |
JP2005206810A (en) * | 2003-12-24 | 2005-08-04 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based film and use of the same |
JP2006249407A (en) * | 2005-02-14 | 2006-09-21 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol film and manufacturing method thereof |
JP2007009056A (en) * | 2005-06-30 | 2007-01-18 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol film for optical film, its manufacturing method and polarizing film and polarizing plate obtained using the same |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015093499A1 (en) * | 2013-12-19 | 2015-06-25 | 株式会社クラレ | Film |
CN105814123A (en) * | 2013-12-19 | 2016-07-27 | 株式会社可乐丽 | Film |
KR20160101912A (en) * | 2013-12-19 | 2016-08-26 | 주식회사 쿠라레 | Film |
JPWO2015093499A1 (en) * | 2013-12-19 | 2017-03-16 | 株式会社クラレ | the film |
KR102341903B1 (en) * | 2013-12-19 | 2021-12-21 | 주식회사 쿠라레 | Film |
CN105814123B (en) * | 2013-12-19 | 2019-10-25 | 株式会社可乐丽 | Film |
JP2016221954A (en) * | 2015-05-26 | 2016-12-28 | 日本合成化学工業株式会社 | Manufacturing method of polyvinyl alcohol-based film, polyvinyl alcohol-based film, polarization film, and cast mold |
JP2017053924A (en) * | 2015-09-08 | 2017-03-16 | 日本合成化学工業株式会社 | Film for polarizing film, and polarizing film using the same |
JPWO2018003671A1 (en) * | 2016-06-27 | 2019-04-18 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing film, method for producing the same, and polarizing film using polyvinyl alcohol film for polarizing film |
WO2018003671A1 (en) * | 2016-06-27 | 2018-01-04 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing films, method for producing same, and polarizing film using said polyvinyl alcohol film for polarizing films |
JP2018090691A (en) * | 2016-12-01 | 2018-06-14 | 株式会社クラレ | Polyvinyl alcohol film and method for producing polarizing film using the same |
CN110603292B (en) * | 2017-03-15 | 2022-04-19 | 株式会社可乐丽 | Resin composition, method for producing same, and molded article using same |
CN110603292A (en) * | 2017-03-15 | 2019-12-20 | 株式会社可乐丽 | Resin composition, method for producing same, and molded article using same |
WO2018168903A1 (en) * | 2017-03-15 | 2018-09-20 | 株式会社クラレ | Resin composition, production method for resin composition, and molded body using resin composition |
JP6411705B1 (en) * | 2017-03-15 | 2018-10-24 | 株式会社クラレ | Resin composition, method for producing the same, and molded article using the same |
US11560464B2 (en) | 2017-03-15 | 2023-01-24 | Kuraray Co., Ltd. | Resin composition, production method for resin composition, and molded body using resin composition |
WO2019124310A1 (en) * | 2017-12-22 | 2019-06-27 | 株式会社クラレ | Polyvinyl alcohol film, film roll, and method for producing film roll |
JPWO2019124310A1 (en) * | 2017-12-22 | 2020-12-24 | 株式会社クラレ | Polyvinyl alcohol film, film roll and film roll manufacturing method |
JP7223709B2 (en) | 2017-12-22 | 2023-02-16 | 株式会社クラレ | POLYVINYL ALCOHOL FILM, FILM ROLL AND METHOD FOR PRODUCING FILM ROLL |
CN112004881A (en) * | 2018-04-27 | 2020-11-27 | 株式会社可乐丽 | Polyvinyl alcohol film and method for producing polarizing film using same |
CN113227858A (en) * | 2018-12-28 | 2021-08-06 | 株式会社可乐丽 | Polyvinyl alcohol film and method for producing polarizing film using same |
CN113227858B (en) * | 2018-12-28 | 2023-03-14 | 株式会社可乐丽 | Polyvinyl alcohol film and method for producing polarizing film using same |
Also Published As
Publication number | Publication date |
---|---|
JPWO2013146458A1 (en) | 2015-12-10 |
JP6100167B2 (en) | 2017-03-22 |
CN104185653B (en) | 2018-07-06 |
TWI626261B (en) | 2018-06-11 |
TWI602831B (en) | 2017-10-21 |
TW201734104A (en) | 2017-10-01 |
TW201345930A (en) | 2013-11-16 |
KR102135487B1 (en) | 2020-07-17 |
JP6334748B2 (en) | 2018-05-30 |
JP2017095729A (en) | 2017-06-01 |
KR20140143205A (en) | 2014-12-15 |
CN104185653A (en) | 2014-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6334748B2 (en) | POLYVINYL ALCOHOL POLYMER FILM AND POLARIZING FILM | |
JP6030528B2 (en) | Manufacturing method of polarizing film | |
JPWO2019054487A1 (en) | Polyvinyl alcohol film and its manufacturing method | |
WO2013137056A1 (en) | Ethylene-modified polyvinyl alcohol polymer film | |
JP2018135426A (en) | Polyvinyl alcohol film and method for producing the same, and polarization film prepared therewith | |
JP2018090691A (en) | Polyvinyl alcohol film and method for producing polarizing film using the same | |
JP7223709B2 (en) | POLYVINYL ALCOHOL FILM, FILM ROLL AND METHOD FOR PRODUCING FILM ROLL | |
JP7282100B2 (en) | Polyvinyl alcohol film and method for producing polarizing film using the same | |
JP7490675B2 (en) | Polyvinyl alcohol film | |
CN113950506B (en) | Polyvinyl alcohol film and method for producing polarizing film using same | |
CN113227858B (en) | Polyvinyl alcohol film and method for producing polarizing film using same | |
JP7512205B2 (en) | Polyvinyl alcohol film and method for producing polarizing film using the same | |
JP7512309B2 (en) | Polyvinyl alcohol film and method for producing polarizing film using the same | |
CN113227857B (en) | Polyvinyl alcohol film and method for producing polarizing film using same | |
CN114829489A (en) | Polyvinyl alcohol film and method for producing polarizing film using same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013538387 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13767314 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147030019 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13767314 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |