WO2018021274A1 - Film polarisant et son procédé de fabrication - Google Patents

Film polarisant et son procédé de fabrication Download PDF

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Publication number
WO2018021274A1
WO2018021274A1 PCT/JP2017/026789 JP2017026789W WO2018021274A1 WO 2018021274 A1 WO2018021274 A1 WO 2018021274A1 JP 2017026789 W JP2017026789 W JP 2017026789W WO 2018021274 A1 WO2018021274 A1 WO 2018021274A1
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Prior art keywords
polarizing film
film
mass
boron
pva
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PCT/JP2017/026789
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English (en)
Japanese (ja)
Inventor
亘 大橋
磯▲ざき▼　孝徳
純一 吉本
達也 大園
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株式会社クラレ
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Priority to KR1020197002918A priority Critical patent/KR102327242B1/ko
Priority to JP2018529894A priority patent/JP6788673B2/ja
Priority to CN201780046289.2A priority patent/CN109564313B/zh
Publication of WO2018021274A1 publication Critical patent/WO2018021274A1/fr

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    • 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
    • C08K5/55—Boron-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
    • 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
    • C08F216/00—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
    • C08F216/02—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
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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

Definitions

  • the present invention relates to a polarizing film excellent in moisture and heat resistance and a method for producing the same.
  • a polarizing plate having a light transmission and shielding function is a basic component of a liquid crystal display (LCD) together with a liquid crystal that changes a polarization state of light.
  • LCD liquid crystal display
  • Many polarizing plates have a structure in which a protective film such as cellulose triacetate (TAC) film is bonded to the surface of the polarizing film in order to prevent the polarizing film from fading or to prevent the polarizing film from shrinking.
  • TAC cellulose triacetate
  • a iodine film I 3 - or I 5 - etc.
  • PVA polyvinyl alcohol film
  • LCDs are used in a wide range of small devices such as calculators and watches, mobile phones, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, and measuring devices used indoors and outdoors. These devices are required to be thin and light. Therefore, each member of the LCD is also required to be thinned. However, if the protective film of the polarizing plate, which is one of the LCD members, is thinned, there is a concern that the function of preventing the fading of the iodine polarizing film is deteriorated. ing. Therefore, an iodine-based polarizing film excellent in so-called moist heat resistance with little fading at high temperature and high humidity is required.
  • Patent Document 1 a technique for crosslinking the polarizing film with a polyvalent aldehyde (Patent Document 1) or a method for crosslinking with a polyvalent carboxylic acid compound (Patent Document 2). ) Is known.
  • an object of the present invention is to provide a polarizing film that does not use an acid catalyst, does not require high-temperature treatment, and can be easily produced industrially, and has excellent wet heat resistance.
  • the present inventors have found that the above problems can be solved by a polarizing film containing polyvinyl alcohol and a specific boron-containing organic compound, and completed the present invention. It was.
  • the subject is a boron-containing compound (B) having at least one functional group selected from the group consisting of polyvinyl alcohol (A) and a boron-containing group that can be converted to a boronic acid group in the presence of a boronic acid group and water.
  • a content of boron element derived from the boron-containing compound (B) in the polarizing film is 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol (A). This is solved by providing a polarizing film.
  • boric acid is further contained, and the total boron element content in the polarizing film is 0.2 to 5% by mass. It is also preferred that the boron-containing compound (B) has a plurality of the functional groups.
  • the said subject is a manufacturing method of the polarizing film containing the dyeing
  • This film is made into the aqueous solution of a boron containing compound (B). It is solved also by providing the manufacturing method of the said polarizing film characterized by having the process to immerse.
  • a polarizing film having excellent moisture and heat resistance. Moreover, according to the manufacturing method of this invention, such a polarizing film can be manufactured industrially easily.
  • the polarizing film of the present invention is a boron-containing compound having at least one functional group selected from the group consisting of polyvinyl alcohol (A) and a boron-containing group that can be converted to a boronic acid group in the presence of a boronic acid group and water. It is a polarizing film containing (B). By cross-linking polyvinyl alcohol with a boron-containing compound (B), the wet heat resistance of the polarizing film is improved.
  • the boron-containing compound (B) used in the present invention is an organic compound having at least one functional group selected from the group consisting of a boron-containing group that can be converted to a boronic acid group in the presence of a boronic acid group and water.
  • the boronic acid group is a monovalent substituent represented by the following structural formula (1), and has a structure in which a boron atom is bonded to two hydroxyl groups and a carbon atom (not shown).
  • boric acid [B (OH) 3 ] a boron atom is bonded to three hydroxyl groups, whereas boronic acid is different in that it has a boron-carbon bond.
  • boron-carbon bond of the boronic acid group is not hydrolyzed, it is stable even in an environment where water is present.
  • boron-containing groups that can be converted to boronic acid groups in the presence of water include, but are not limited to, boronic acid ester groups described below.
  • the hydroxyl group of a boronic acid group can form an ester with an alcohol, like the hydroxyl group of boric acid.
  • the following structural formula (2) is a boronic acid monoester group obtained by reacting one molecule of alcohol (R—OH) with a boronic acid group.
  • R in the structural formula (2) is a PVA chain, and the carbon-containing group is bonded to the PVA chain via a boron atom, The moisture and heat resistance of the film is improved.
  • the following structural formula (3) is a boronic acid diester group obtained by reacting two molecules of alcohol (R—OH) with a boronic acid group.
  • R—OH alcohol
  • two Rs in the structural formula (3) are both PVA chains, and a plurality of PVA chains are cross-linked to each other, and thus obtained.
  • the wet heat resistance of the polarizing film is effectively improved.
  • Examples of the boron-containing compound (B) used in the present invention include methyl boronic acid, ethyl boronic acid, propyl boronic acid, butyl boronic acid, pentyl boronic acid, hexyl boronic acid, and isomers thereof, and phenyl boronic acid. . These have at least one functional group selected from the group consisting of a boronic acid group and a boron-containing group that can be converted to a boronic acid group in the presence of water in the molecule.
  • the heat and humidity resistance of the polarizing film may be improved.
  • the reason for this is not clear, but it is presumed that ⁇ - ⁇ stacking of the aromatic ring makes it difficult for moisture to permeate and the effect of improving the heat and humidity resistance of the polarizing film is enhanced.
  • Examples of such boron-containing compound (B) include phenylboronic acid, 1,4-benzenediboronic acid, 1,3-benzenediboronic acid, 1,3,5-benzenetriboronic acid, and the like.
  • the boron-containing compound (B) has a plurality of at least one functional group selected from the group consisting of boron-containing groups that can be converted into boronic acid groups in the presence of boronic acid groups and water in the molecule.
  • the wet heat resistance of the polarizing film is effectively improved.
  • the following structural formula (4) shows the boron-containing compound (B) in the case where the molecule has two boronic acid groups.
  • X is a divalent organic group, such as an alkylene group or an arylene group. In this case, there are four points that react with the hydroxyl group of PVA to form an ester, and the PVA chain is more effectively cross-linked.
  • Examples of the boron-containing compound (B) having a plurality of functional groups include methanediboronic acid, ethanediboronic acid, propanediboronic acid, butanediboronic acid, pentanediboronic acid, hexanediboronic acid, and isomers thereof, and 1,4 -Benzenediboronic acid, 1,3-benzenediboronic acid, 1,3,5-benzenetriboronic acid and the like.
  • the boron element content derived from the boron-containing compound (B) in the polarizing film of the present invention needs to be 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyvinyl alcohol (A).
  • the boron element content derived from the boron-containing compound (B) is less than 0.1 parts by mass, the crosslinking amount of the polyvinyl alcohol (A) is small, and the effect of improving the heat and moisture resistance is insufficient.
  • the boron element content derived from the boron-containing compound (B) is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more.
  • the boron element content derived from the boron-containing compound (B) is preferably 2 parts by mass or less, particularly preferably 1 part by mass or less.
  • the boron element content derived from the boron-containing compound (B) can be obtained by 1 H-NMR measurement.
  • the polarizing film of the present invention further contains boric acid.
  • the total boron element content in the polarizing film is preferably 0.2 to 5% by mass.
  • the total boron element content is an amount obtained by totaling the contents of all boron elements including the boron element content derived from the boron-containing compound (B) and the boron element content derived from boric acid.
  • the total boron element content in the polarizing film is more preferably 1% by mass or more.
  • the total boron element content in the polarizing film is more than 5% by mass, the dimensional change of the polarizing film at high temperatures may increase.
  • the total boron element content in the polarizing film is more preferably 4.5% by mass or less.
  • the total boron element content in the polarizing film can be determined by ICP emission analysis or the like.
  • the degree of polymerization of PVA contained in the polarizing film of the present invention is preferably in the range of 1,500 to 6,000, more preferably in the range of 1,800 to 5,000, and 2,000. More preferably within the range of ⁇ 4,000.
  • the degree of polymerization of PVA means the average degree of polymerization measured according to the description of JIS K6726-1994.
  • the saponification degree of PVA contained in the polarizing film of the present invention is preferably 95 mol% or more, more preferably 96 mol% or more from the viewpoint of water resistance of the polarizing film obtained by uniaxially stretching the film. Preferably, it is 98 mol% or more.
  • the degree of saponification of PVA refers to the structural units (typically vinyl ester units) that can be converted into vinyl alcohol units (—CH 2 —CH (OH) —) by saponification, which PVA has, and vinyl.
  • the saponification degree can be measured according to the description of JIS K6726-1994.
  • the method for producing PVA used in the present invention is not particularly limited.
  • the method of converting the vinyl ester unit of polyvinyl ester obtained by polymerizing a vinyl ester monomer into a vinyl alcohol unit is mentioned.
  • the vinyl ester monomer used for the production of PVA is not particularly limited.
  • vinyl, vinyl caprate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and vinyl benzoate From the economical viewpoint, vinyl acetate is preferred.
  • the PVA used in the present invention is obtained by converting a vinyl ester unit of a polyvinyl ester copolymer obtained by copolymerizing a vinyl ester monomer and another monomer copolymerizable therewith into a vinyl alcohol unit. It may be a thing.
  • Examples of other monomers copolymerizable with the vinyl ester monomer include ⁇ -olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene; (meth) acrylic acid or a salt thereof; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (Meth) acrylic acid esters such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate; (meth) acrylamide; N-methyl (Meth) acrylamide, N-ethyl (meth) acrylamide, N,
  • Vinyl ether vinyl cyanide such as (meth) acrylonitrile; halogenated vinyl such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride; vinegar Allyl compounds such as allyl acid and allyl chloride; maleic acid or its salt, ester or acid anhydride; itaconic acid or its salt, ester or acid anhydride; vinylsilyl compound such as vinyltrimethoxysilane; unsaturated sulfonic acid be able to.
  • the vinyl ester copolymer can have a structural unit derived from one or more of the other monomers described above.
  • the other monomer may be pre-existed in the reaction vessel when the vinyl ester monomer is subjected to the polymerization reaction, or may be added to the reaction vessel during the polymerization reaction. Can be used. From the viewpoint of polarization performance, the content of units derived from other monomers is preferably 10 mol% or less, more preferably 5 mol% or less, and more preferably 2 mol% or less. Further preferred.
  • the stretchability is improved and the film can be stretched at a higher temperature.
  • Ethylene is preferred because the productivity of the film is further improved.
  • the content of the ethylene unit is 1 to 4 mol% with respect to the number of moles of all the structural units constituting the PVA from the viewpoints of stretchability and stretchable temperature as described above.
  • 2 to 3 mol% is more preferable.
  • the polymerization method for polymerizing the vinyl ester monomer may be any of batch polymerization, semi-batch polymerization, continuous polymerization, semi-continuous polymerization, etc., and polymerization methods include bulk polymerization, solution polymerization, suspension Known methods such as a polymerization method and an emulsion polymerization method can be applied.
  • a bulk polymerization method or a solution polymerization method in which polymerization is allowed to proceed in a solvent-free or solvent such as alcohol is usually employed.
  • an emulsion polymerization method is also preferable.
  • the solvent of the solution polymerization method is not particularly limited, for example, alcohol.
  • the alcohol used as the solvent for the solution polymerization method is, for example, a lower alcohol such as methanol, ethanol, or propanol.
  • the amount of solvent used in the polymerization solution may be selected in consideration of the chain transfer of the solvent in accordance with the degree of polymerization of the target PVA.
  • the mass ratio of the solvent to all monomers is preferably selected within the range of 0.01 to 10, more preferably within the range of 0.05 to 3.
  • the polymerization initiator used for the polymerization of the vinyl ester monomer may be selected from known polymerization initiators such as azo initiators, peroxide initiators, and redox initiators according to the polymerization method.
  • azo initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile).
  • peroxide initiator examples include percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate; t-butyl peroxyneodecanate, ⁇ - Perester compounds such as cumylperoxyneodecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate; acetyl peroxide. Potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like may be combined with the above initiator to form a polymerization initiator.
  • percarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate
  • the redox initiator is, for example, a polymerization initiator in which the peroxide initiator is combined with a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
  • a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, or longalite.
  • the amount of the polymerization initiator used varies depending on the type of the polymerization initiator and cannot be determined unconditionally, but may be selected according to the polymerization rate. For example, when 2,2′-azobisisobutyronitrile or acetyl peroxide is used as the polymerization initiator, 0.01 to 0.2 mol% is preferable with respect to the vinyl ester monomer, and 0.02 to 0.8%. 15 mol% is more preferable.
  • the polymerization temperature is not particularly limited, but is suitably about room temperature to 150 ° C., preferably 40
  • the polymerization of the vinyl ester monomer may be performed in the presence of a chain transfer agent.
  • chain transfer agent examples include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; and phosphinic acid salts such as sodium phosphinate monohydrate. Of these, aldehydes and ketones are preferably used.
  • the amount of the chain transfer agent used can be determined according to the chain transfer coefficient of the chain transfer agent to be used and the polymerization degree of the target PVA, but is generally 0.1% with respect to 100 parts by mass of the vinyl ester monomer. ⁇ 10 parts by mass are preferred.
  • Polyvinyl ester can be saponified, for example, in a state where the polyvinyl ester is dissolved in alcohol or hydrous alcohol.
  • the alcohol used for saponification include lower alcohols such as methanol and ethanol, preferably methanol.
  • the alcohol used for saponification may contain other solvents such as acetone, methyl acetate, ethyl acetate, and benzene at a ratio of 40% by mass or less of the mass, for example.
  • the catalyst used for saponification is, for example, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an alkali catalyst such as sodium methylate, or an acid catalyst such as mineral acid.
  • the temperature at which saponification is performed is not limited, but is preferably within the range of 20 to 60 ° C.
  • the product is pulverized, washed and dried to obtain PVA.
  • the saponification method is not limited to the method described above, and a known method can be applied.
  • the PVA film used for producing the polarizing film of the present invention can contain a plasticizer in addition to the above PVA.
  • Preferred plasticizers include polyhydric alcohols, and specific examples include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like. Furthermore, 1 type, or 2 or more types of these plasticizers can be included. Among these, glycerin is preferable in terms of the effect of improving stretchability.
  • the content of the plasticizer in the PVA film used for producing the polarizing film of the present invention is preferably in the range of 1 to 20 parts by mass with respect to 100 parts by mass of PVA, and is in the range of 3 to 17 parts by mass. More preferably, the content is in the range of 5 to 15 parts by mass. When the content is 1 part by mass or more, the stretchability of the film is further improved. On the other hand, when the content is 20 parts by mass or less, it is possible to prevent the film from becoming too flexible and handling properties from being lowered.
  • the PVA film used for the production of the polarizing film of the present invention further includes a filler, a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, and an antistatic agent. , Flame retardants, other thermoplastic resins, lubricants, fragrances, antifoaming agents, deodorants, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, fungicides, preservatives, crystallization rate delay An additive such as an agent can be appropriately blended as necessary.
  • a processing stabilizer such as a copper compound, a weather resistance stabilizer, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, and an antistatic agent.
  • Flame retardants other thermoplastic resins, lubricants, fragrances, antifoaming agents, deodorants, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, fungicides, preservative
  • the proportion of the total of PVA and plasticizer in the PVA film used for producing the polarizing film of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more based on the mass of the PVA film. Preferably, it is 95 mass% or more.
  • the swelling degree of the PVA film used for producing the polarizing film of the present invention is preferably in the range of 160 to 240%, more preferably in the range of 170 to 230%, and in the range of 180 to 220%. It is particularly preferred that When the degree of swelling is 160% or more, the crystallization can be prevented from proceeding extremely, and the film can be stably stretched to a high magnification. On the other hand, when the degree of swelling is 240% or less, dissolution during stretching is suppressed, and stretching is possible even under higher temperature conditions.
  • the thickness of the PVA film used for the production of the polarizing film of the present invention is not particularly limited, but is generally 1 to 100 ⁇ m, more preferably 5 to 60 ⁇ m, and particularly preferably about 10 to 45 ⁇ m.
  • the thickness is too thin, there is a tendency that stretching breakage is likely to occur during the uniaxial stretching process for producing the polarizing film.
  • the said thickness is too thick, it will become easy to generate
  • the width of the PVA film used for the production of the polarizing film of the present invention is not particularly limited, and can be determined according to the application of the produced polarizing film. In recent years, since the enlargement of screens of liquid crystal televisions and liquid crystal monitors has progressed, the width of the PVA film used for the production of the polarizing film is preferably 3 m or more, which is suitable for these applications. On the other hand, if the width of the PVA film used for the production of the polarizing film is too large, it is difficult to perform uniaxial stretching uniformly when the polarizing film is produced with a device that has been put to practical use. The width of the PVA film to be used is preferably 7 m or less.
  • the manufacturing method of the PVA film used for manufacture of the polarizing film of this invention is not specifically limited, The manufacturing method from which the thickness and width
  • the above-mentioned PVA constituting the PVA film used in the above, and if necessary, one or more of the above-described plasticizers, additives, and surfactants described later are dissolved in a liquid medium.
  • a membrane forming solution in which PVA is melted including one or more of a membrane stock solution, PVA, and, if necessary, a plasticizer, an additive, a surfactant, and a liquid medium.
  • the film-forming stock solution contains at least one of a plasticizer, an additive, and a surfactant, it is preferable that these components are uniformly mixed.
  • liquid medium used for the preparation of the membrane forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. , Trimethylolpropane, ethylenediamine, diethylenetriamine and the like, and one or more of them can be used. Among these, water is preferable from the viewpoint of environmental load and recoverability.
  • the volatile fraction of the film-forming stock solution (content ratio in the film-forming stock solution of volatile components such as liquid media removed by volatilization or evaporation during film formation) varies depending on the film-forming method, film-forming conditions, etc. Specifically, it is preferably in the range of 50 to 95% by mass, and more preferably in the range of 55 to 90% by mass.
  • the film-forming stock solution has a volatile content of 50% by mass or more, so that the viscosity of the film-forming stock solution does not become too high, and filtration and defoaming are smoothly performed during the preparation of the film-forming stock solution, and there are few foreign substances and defects. Is easy to manufacture.
  • the volatile fraction of the film-forming stock solution is 95% by mass or less, the concentration of the film-forming stock solution does not become too low, and industrial film production is facilitated.
  • the film forming stock solution preferably contains a surfactant.
  • a surfactant By including the surfactant, the film-forming property is improved and the occurrence of uneven thickness of the film is suppressed, and the film is easily peeled off from the metal roll or belt used for film formation.
  • the film may contain a surfactant.
  • the kind of said surfactant is not specifically limited, From a viewpoint of the peelability from a metal roll or a belt, an anionic surfactant or a nonionic surfactant is preferable.
  • anionic surfactant for example, a carboxylic acid type such as potassium laurate; a sulfuric acid ester type such as polyoxyethylene lauryl ether sulfate and octyl sulfate; and a sulfonic acid type such as dodecylbenzene sulfonate are suitable.
  • a carboxylic acid type such as potassium laurate
  • a sulfuric acid ester type such as polyoxyethylene lauryl ether sulfate and octyl sulfate
  • a sulfonic acid type such as dodecylbenzene sulfonate
  • Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl ester types such as polyoxyethylene laurate; polyoxyethylene laurylamino Alkylamine type such as ether; alkylamide type such as polyoxyethylene lauric acid amide; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; alkanolamide type such as lauric acid diethanolamide and oleic acid diethanolamide; polyoxy An allyl phenyl ether type such as alkylene allyl phenyl ether is preferred.
  • surfactants can be used alone or in combination of two or more.
  • the content thereof is preferably in the range of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of PVA contained in the film-forming stock solution, and 0.02 It is more preferably in the range of -0.3 parts by mass, and particularly preferably in the range of 0.05-0.2 parts by mass.
  • the content is 0.01 mass part or more, film forming property and peelability improve more.
  • the content is 0.5 parts by mass or less, it is possible to suppress that the surfactant bleeds out to the surface of the PVA film to cause blocking, and the handleability is deteriorated.
  • Examples of the film forming method for forming a PVA film used for the production of a polarizing film using the above-described film forming stock solution include a cast film forming method, an extrusion film forming method, a wet film forming method, a gel film forming method, and the like. Is mentioned. These film forming methods may be used alone or in combination of two or more. Among these film forming methods, the cast film forming method and the extrusion film forming method are preferable because a PVA film used for manufacturing a polarizing film having uniform thickness and width and good physical properties can be obtained. The formed PVA film can be dried or heat-treated as necessary.
  • Examples of a specific method for producing the PVA film used for producing the polarizing film of the present invention include, for example, using the T-type slit die, hopper plate, I-die, lip coater die, etc.
  • the volatile components are evaporated and dried from one side of the substrate, and then further dried on the peripheral surface of one or more rotating heated rolls arranged downstream thereof, or in a hot air dryer.
  • a method of winding with a winding device can be preferably employed industrially. Drying with a heated roll and drying with a hot air dryer may be performed in an appropriate combination.
  • the method for producing the polarizing film of the present invention is not particularly limited.
  • a preferred production method is a method for producing a polarizing film comprising a dyeing treatment for dyeing a polyvinyl alcohol film with a dichroic dye, and a stretching treatment for uniaxially stretching the film, wherein the film is made into an aqueous solution of a boron-containing compound (B). It is a manufacturing method of the polarizing film which has the process to immerse.
  • the PVA film used for the production of the polarizing film of the present invention is subjected to a dyeing process, a uniaxial stretching process, and, if necessary, a swelling process, a boric acid crosslinking process, a fixing process, a washing process, a drying process, a heat treatment and the like.
  • a method is mentioned.
  • the order of each treatment such as swelling treatment, dyeing treatment, boric acid crosslinking treatment, uniaxial stretching treatment, and fixing treatment is not particularly limited, and one or two or more treatments can be performed simultaneously. Also, one or more of each process can be performed twice or more.
  • the swelling treatment can be performed by immersing the PVA film in water.
  • the temperature of the water when immersed in water is preferably in the range of 20 to 40 ° C., more preferably in the range of 22 to 38 ° C., and preferably in the range of 25 to 35 ° C. Further preferred.
  • the time for dipping in water is, for example, preferably within a range of 0.1 to 5 minutes, and more preferably within a range of 0.2 to 3 minutes.
  • the water at the time of immersing in water is not limited to pure water, The aqueous solution in which various components melt
  • the dyeing treatment can be performed by bringing a dichroic dye into contact with the PVA film.
  • a dichroic dye an iodine dye is generally used.
  • the timing of the dyeing process may be any stage before the uniaxial stretching process, at the time of the uniaxial stretching process, or after the uniaxial stretching process.
  • the dyeing treatment is generally performed by immersing the PVA film in a solution (particularly an aqueous solution) containing iodine-potassium iodide as a dyeing bath.
  • the iodine concentration in the dyeing bath is preferably in the range of 0.01 to 0.5% by mass, and the potassium iodide concentration is preferably in the range of 0.01 to 10% by mass.
  • the temperature of the dyeing bath is preferably 20 to 50 ° C., particularly 25 to 40 ° C.
  • the preferred staining time is 0.2 to 5 minutes.
  • the boric acid crosslinking treatment is preferably performed before the uniaxial stretching treatment.
  • the boric acid crosslinking treatment can be performed by immersing the PVA film in an aqueous solution containing a boric acid crosslinking agent.
  • the boric acid crosslinking agent one or more of boron-containing inorganic compounds such as borates such as boric acid and borax can be used.
  • the concentration of the boric acid crosslinking agent in the aqueous solution containing the boric acid crosslinking agent is preferably in the range of 1 to 15% by mass, and more preferably in the range of 2 to 7% by mass. Sufficient stretchability can be maintained when the concentration of the boric acid crosslinking agent is in the range of 1 to 15% by mass.
  • the aqueous solution containing the boric acid crosslinking agent may contain an auxiliary agent such as potassium iodide.
  • the temperature of the aqueous solution containing the boric acid crosslinking agent is preferably in the range of 20 to 50 ° C., particularly in the range of 25 to 40 ° C. By setting the temperature within the range of 20 to 50 ° C., boric acid crosslinking can be performed efficiently.
  • the uniaxial stretching treatment may be performed by either a wet stretching method or a dry stretching method.
  • the wet stretching method it can be carried out in an aqueous solution containing boric acid, or can be carried out in the dyeing bath described above or in a fixing treatment bath described later.
  • the dry stretching method the uniaxial stretching treatment may be performed at room temperature, the uniaxial stretching treatment may be performed while heating, or the uniaxial stretching treatment is performed in the air using the PVA film after water absorption. You can also Among these, the wet stretching method is preferable, and it is more preferable to perform the uniaxial stretching process in an aqueous solution containing boric acid.
  • the concentration of boric acid in the boric acid aqueous solution is preferably in the range of 0.5 to 6% by mass, and more preferably in the range of 1 to 5% by mass. Further, the aqueous boric acid solution may contain potassium iodide, and its concentration is preferably in the range of 0.01 to 10% by mass.
  • the stretching temperature in the uniaxial stretching treatment is preferably in the range of 30 to 90 ° C, more preferably in the range of 40 to 80 ° C, and particularly preferably in the range of 50 to 70 ° C.
  • the stretching ratio in the uniaxial stretching treatment is preferably 5 times or more from the viewpoint of the polarizing performance of the obtained polarizing film, and more preferably 5.5 times or more. preferable.
  • the upper limit of the draw ratio is not particularly limited, but the draw ratio is preferably 8 times or less.
  • the direction of the uniaxial stretching treatment when performing a uniaxial stretching treatment on a long PVA film, and a uniaxial stretching treatment or a lateral uniaxial stretching treatment in the long direction or a so-called oblique stretching treatment can be employed.
  • a uniaxial stretching treatment in the longitudinal direction is preferable because a polarizing film having excellent polarization performance can be obtained.
  • the uniaxial stretching process in the longitudinal direction can be performed by changing the peripheral speed between the rolls using a stretching apparatus including a plurality of rolls parallel to each other.
  • the lateral uniaxial stretching treatment can be performed using a tenter type stretching machine.
  • the fixing treatment bath used for the fixing treatment an aqueous solution containing a boron-containing compound (B) can be preferably used.
  • a boric acid, an iodine compound, a metal compound, etc. in a fixed treatment bath as needed.
  • the temperature of the fixing treatment bath is preferably 15 to 60 ° C., particularly 25 to 40 ° C.
  • the boron-containing compound (B) may be adsorbed to the polarizing film in any of the dyeing process, boric acid crosslinking process, uniaxial stretching process, and fixing process. It is particularly preferable because it does not affect Further, the boron-containing compound (B) is not limited to one type, and two or more types may be mixed and used.
  • the aqueous solution concentration of the boron-containing compound (B) is preferably 0.05 to 15% by mass, particularly preferably 0.1 to 10% by mass.
  • the aqueous solution concentration of the boron-containing compound (B) is lower than 0.05% by mass, the adsorption may be slow, and when the aqueous solution concentration is higher than 15% by mass, the boron-containing compound (B) Precipitation may occur.
  • the aqueous solution containing a boron containing compound (B) contains adjuvants, such as potassium iodide, from the point of a polarizing performance improvement.
  • the temperature of the treatment bath is preferably 10 to 70 ° C., more preferably 20 to 60 ° C., and particularly preferably 20 to 50 ° C. If the temperature is too low, the boron-containing compound (B) may precipitate in the treatment bath. On the other hand, if the temperature is too high, it is difficult to easily produce industrially under relatively mild conditions.
  • a suitable production method is to perform a swelling treatment, a boric acid crosslinking treatment, a uniaxial stretching treatment, and a fixing treatment in this order. Thereafter, if necessary, one or more processes selected from a cleaning process, a drying process, and a heat treatment may be performed in this order.
  • the washing treatment is generally performed by immersing the film in water, distilled water, pure water or the like.
  • the aqueous solution used for the washing treatment preferably contains an iodide such as potassium iodide as an auxiliary agent, and the concentration of the iodide is preferably 0.5 to 10% by mass.
  • the temperature of the aqueous solution in the washing treatment is generally 5 to 50 ° C., preferably 10 to 45 ° C., more preferably 15 to 40 ° C. From an economical viewpoint, it is not preferable that the temperature of the aqueous solution is too low. If the temperature of the aqueous solution is too high, the polarization performance may be deteriorated.
  • Drying conditions are not particularly limited, but it is preferable to perform drying at a temperature within the range of 30 to 150 ° C, particularly within the range of 50 to 130 ° C.
  • a polarizing film excellent in dimensional stability can be easily obtained by drying at a temperature in the range of 30 to 150 ° C.
  • a polarizing film having further excellent dimensional stability can be obtained by performing a heat treatment after the drying treatment.
  • the heat treatment is a treatment for further heating the polarizing film after the drying treatment having a moisture content of 5% or less to improve the dimensional stability of the polarizing film.
  • the conditions for the heat treatment are not particularly limited, but it is preferable to perform the heat treatment within a range of 60 ° C. to 150 ° C., particularly within a range of 70 ° C. to 150 ° C.
  • the heat treatment is performed at a temperature lower than 60 ° C., the dimensional stabilization effect by the heat treatment is insufficient, and when the heat treatment is performed at a temperature higher than 150 ° C., the polarizing film may be severely reddened.
  • the wet heat resistance performance of the polarizing film obtained as described above can be evaluated by using the fading of the color derived from the PVA-iodine complex at high temperature and high humidity as an index. Specifically, the evaluation is based on the percentage of absorbance D (610 nm) after fading with respect to absorbance C (610 nm) before fading when two polarizing films are superposed on crossed Nicols. be able to.
  • the absorbance remaining rate after fading for 8 hours at 60 ° C./90% RH is preferably 22% or more, and more preferably 25% or more.
  • the polarizing film is usually used as a polarizing plate by attaching an optically transparent protective film having mechanical strength to both sides or one side.
  • an optically transparent protective film having mechanical strength to both sides or one side.
  • the adhesive for bonding include PVA adhesives and urethane adhesives, among which PVA adhesives are suitable.
  • the polarizing plate obtained as described above can be used as an LCD component after being coated with an acrylic adhesive or the like and bonded to a glass substrate. At the same time, it may be bonded to a retardation film, a viewing angle improving film, a brightness improving film, or the like.
  • Optical properties of polarizing film (1) Measurement of transmittance Ts From the central part of the polarizing film obtained in the following examples or comparative examples, two samples of 4 cm in the stretching direction of the polarizing film and 2 cm in the width direction were collected, and spectroscopy with an integrating sphere Using a photometer (“V7100” manufactured by JASCO Corporation), in accordance with JIS Z 8722 (object color measurement method), the visibility correction of the visible light region of the C light source and the 2 ° field of view is performed. With respect to the samples, the light transmittance when tilted by + 45 ° with respect to the length direction and the light transmittance when tilted by ⁇ 45 ° were measured, and an average value Ts1 (%) thereof was obtained.
  • V7100 manufactured by JASCO Corporation
  • Ts1 and Ts2 were averaged by the following calculation formula (6) to obtain the transmittance Ts (%) of the polarizing film.
  • Ts (Ts1 + Ts2) / 2 (6)
  • the phase was adjusted so that the baseline was smooth, and then the average point was set to 20 and the baseline was automatically corrected. Next, it was automatically set as a reference so that the peak of heavy water as a measurement solvent was at a position of 4.65 ppm. Thereafter, as shown in FIG. 1, the hydrogen peak of the hydrocarbon group contained in the boron-containing compound (B) was integrated to determine the peak area.
  • the sum of the hydrogen peak areas of the hydrocarbon groups contained in the boron-containing compound (B) that does not overlap with the hydrogen peak derived from PVA (area G) is used as a reference for the peak area, and the boron-containing compound (B) The number of hydrogen of the corresponding hydrocarbon group and the value of the area G were set to be the same.
  • the peak area (area H) was determined by regarding the total of the hydrogen peaks.
  • Calculation formula (8) is a formula used when unmodified PVA is used. When modified PVA is used as a raw material, calculation formula (8) needs to be appropriately modified.
  • Content of boron element derived from boron-containing compound (B) with respect to 100 parts by mass of polyvinyl alcohol (A) (parts by mass) ⁇ (area G / X) / (area I / 2) ⁇ ⁇ ⁇ (10.811 ⁇ Y) /44.0526 ⁇ 100 (8) 10.0.811 is the atomic weight of boron, and 44.0526 is the molecular weight per mole of unmodified PVA repeating units.
  • the 1 H-NMR chart of FIG. 1 is obtained by measuring the polarizing film of Example 1.
  • the boron element content derived from the boron-containing compound (B) with respect to 100 parts by mass of the polyvinyl alcohol (A) is the second decimal place. To 0.5 parts by mass.
  • Example 1 100 parts by mass of PVA (saponification degree 99.9 mol%, polymerization degree 2400), 10 parts by mass of glycerin as a plasticizer, and 0.1 parts by mass of sodium polyoxyethylene lauryl ether sulfate as a surfactant, the content of PVA Using an aqueous solution of 10% by mass as a film-forming stock solution, this was dried on a metal roll at 80 ° C., and the resulting film was swollen by heat treatment at 120 ° C. for 10 minutes in a hot air dryer. The degree was adjusted to 200%, and a PVA film having a thickness of 30 ⁇ m was produced.
  • a sample having a width of 5 cm and a length of 9 cm was cut from the central portion in the width direction of the PVA film thus obtained so that the range of width 5 cm ⁇ length 5 cm could be uniaxially stretched.
  • the sample While immersing this sample in pure water at 30 ° C. for 30 seconds, the sample was uniaxially stretched 1.1 times in the length direction and swelled.
  • an aqueous solution containing 0.04% by mass of iodine and 4.0% by mass of potassium iodide (temperature 30 ° C.) for 60 seconds, it is 2.2 times (2.4 times as a whole).
  • the iodine was adsorbed by uniaxial stretching in the length direction.
  • Example 2 to 4 and Comparative Examples 1 to 3 the sample was immersed in an aqueous solution (dyeing bath) containing 100 parts by mass of potassium iodide with respect to 1 part by mass of iodine (temperature 30 ° C.) for 60 seconds. However, it was uniaxially stretched in the length direction 2.2 times (total 2.4 times) to adsorb iodine. At this time, the iodine or potassium iodide concentration in the dyeing bath is such that the absorbance (610 nm) when the two polarizing films after drying are fixed to a metal frame and superimposed on crossed Nicols is 3.6 to 4 .2 adjusted.
  • Example 2 Example 1 was used except that an aqueous solution (temperature 30 ° C.) containing 0.5% by mass of 1,3-propanediboronic acid and 3% by mass of potassium iodide was used for the fixing treatment bath. A polarizing film was prepared, and each measurement or evaluation was performed. The results are shown in Table 1.
  • Example 3 A polarizing film in the same manner as in Example 1 except that an aqueous solution (temperature 30 ° C.) containing 1.0% by mass of phenylboronic acid and 2.0% by mass of potassium iodide was used for the fixing treatment bath. And each measurement or evaluation was performed. The results are shown in Table 1.
  • Example 4 Except that an aqueous solution (temperature 30 ° C.) containing 4.0% by mass of n-propylboronic acid and 3.0% by mass of potassium iodide was used for the fixing treatment bath, the same procedure as in Example 1 was performed. A polarizing film was produced and each measurement or evaluation was performed. The results are shown in Table 1.
  • Example 1 A polarizing film was prepared in the same manner as in Example 1 except that an aqueous solution (temperature 30 ° C.) containing 2% by mass of boric acid and 3% by mass of potassium iodide was used in the fixing treatment bath. Each measurement or evaluation was performed. The results are shown in Table 1.
  • Example 2 A polarizing film was produced in the same manner as in Example 1 except that an aqueous solution (temperature 30 ° C.) containing 1.0% by mass of boric acid and 3% by mass of potassium iodide was used for the fixing treatment bath. Each measurement or evaluation was performed. The results are shown in Table 1.
  • Example 3 A polarizing film was prepared in the same manner as in Example 1 except that an aqueous solution (temperature 30 ° C.) containing 0.5% by mass of boric acid and 3% by mass of potassium iodide was used for the fixing treatment bath. Each measurement or evaluation was performed. The results are shown in Table 1.
  • Hydrogen peak derived from heavy water as measurement solvent Hydrogen peak derived from methine group of PVA 3 Hydrogen peak derived from methylene group of PVA 4 Derived from hydrocarbon group contained in boron-containing compound (B) overlapping with hydrogen peak derived from PVA 5 Hydrogen peak derived from hydrocarbon group contained in boron-containing compound (B) that does not overlap with hydrogen peak derived from PVA

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Abstract

L'invention concerne un film polarisant qui comprend de l'alcool polyvinylique (A) et un composé contenant du bore (B) ayant au moins un groupe fonctionnel choisi dans le groupe constitué par un groupe acide boronique et des groupes contenant du bore capables d'être convertis en un groupe acide boronique en présence d'eau, et qui est caractérisé en ce que la quantité contenue de bore élémentaire dérivée du composé contenant du bore (B) dans le film polarisant est de 0,1 à 3 parties en masse par rapport à 100 parties en masse de l'alcool polyvinylique (A). Il est préférable que de l'acide boronique soit en outre inclus, et que la quantité totale de bore élémentaire contenue dans le film polarisant soit de 0,2 à 5 % en masse. Cette configuration fournit un film polarisant qui présente d'excellentes performances de résistance à la chaleur humide.
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WO2019146677A1 (fr) * 2018-01-25 2019-08-01 株式会社クラレ Film polarisant et son procédé de fabrication
WO2019146678A1 (fr) * 2018-01-25 2019-08-01 株式会社クラレ Film polarisant et son procédé de fabrication
WO2021020349A1 (fr) * 2019-07-29 2021-02-04 株式会社クラレ Film polarisant et son procédé de production
JP2021138824A (ja) * 2020-03-04 2021-09-16 株式会社クラレ エチレン−ビニルアルコール共重合体含有樹脂組成物及び成形体
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KR20220149535A (ko) 2020-03-13 2022-11-08 주식회사 쿠라레 편광 필름 및 그 제조 방법
JP2023073942A (ja) * 2021-11-16 2023-05-26 長春石油化學股▲分▼有限公司 ポリビニルアルコールフィルム、それを含む偏光フィルム及びそれらの製造方法

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JP2018180022A (ja) * 2017-04-03 2018-11-15 日東電工株式会社 偏光子の製造方法
WO2019146677A1 (fr) * 2018-01-25 2019-08-01 株式会社クラレ Film polarisant et son procédé de fabrication
WO2019146678A1 (fr) * 2018-01-25 2019-08-01 株式会社クラレ Film polarisant et son procédé de fabrication
JPWO2019146677A1 (ja) * 2018-01-25 2021-01-28 株式会社クラレ 偏光フィルム及びその製造方法
JP7284716B2 (ja) 2018-01-25 2023-05-31 株式会社クラレ 偏光フィルム及びその製造方法
JPWO2019146678A1 (ja) * 2018-01-25 2021-02-04 株式会社クラレ 偏光フィルム及びその製造方法
JP7282042B2 (ja) 2018-01-25 2023-05-26 株式会社クラレ 偏光フィルム及びその製造方法
KR20220007091A (ko) 2019-05-09 2022-01-18 주식회사 쿠라레 편광 필름 및 그 제조 방법
KR20220027959A (ko) 2019-06-27 2022-03-08 주식회사 쿠라레 편광 필름 및 그 제조 방법
WO2021020349A1 (fr) * 2019-07-29 2021-02-04 株式会社クラレ Film polarisant et son procédé de production
KR20220041093A (ko) 2019-07-29 2022-03-31 주식회사 쿠라레 편광 필름 및 그 제조 방법
JPWO2021020349A1 (fr) * 2019-07-29 2021-02-04
JP2021138824A (ja) * 2020-03-04 2021-09-16 株式会社クラレ エチレン−ビニルアルコール共重合体含有樹脂組成物及び成形体
JP7504628B2 (ja) 2020-03-04 2024-06-24 株式会社クラレ エチレン－ビニルアルコール共重合体含有樹脂組成物及び成形体
KR20220149535A (ko) 2020-03-13 2022-11-08 주식회사 쿠라레 편광 필름 및 그 제조 방법
JP2023073942A (ja) * 2021-11-16 2023-05-26 長春石油化學股▲分▼有限公司 ポリビニルアルコールフィルム、それを含む偏光フィルム及びそれらの製造方法
JP7288526B2 (ja) 2021-11-16 2023-06-07 長春石油化學股▲分▼有限公司 ポリビニルアルコールフィルム、それを含む偏光フィルム及びそれらの製造方法

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CN109564313A (zh) 2019-04-02
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CN109564313B (zh) 2022-04-01
TW201821507A (zh) 2018-06-16

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