WO2020184587A1 - ポリビニルアルコールフィルム、偏光フィルム、及び偏光板 - Google Patents
ポリビニルアルコールフィルム、偏光フィルム、及び偏光板 Download PDFInfo
- Publication number
- WO2020184587A1 WO2020184587A1 PCT/JP2020/010392 JP2020010392W WO2020184587A1 WO 2020184587 A1 WO2020184587 A1 WO 2020184587A1 JP 2020010392 W JP2020010392 W JP 2020010392W WO 2020184587 A1 WO2020184587 A1 WO 2020184587A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- pva
- polyvinyl alcohol
- polarizing
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
-
- 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
- B32B2329/04—Polyvinylalcohol
Definitions
- the present invention relates to a polyvinyl alcohol film, a polarizing film, and a polarizing plate.
- a polarizing plate having a function of transmitting and shielding light is a basic component of a liquid crystal display (LCD) together with a liquid crystal that changes the polarization state of light.
- LCD liquid crystal display
- Many polarizing plates have a structure in which a protective film such as a triacetyl cellulose (TAC) film is bonded to the surface of the polarizing film.
- TAC triacetyl cellulose
- the polarizing film constituting the polarizing plate a polyvinyl alcohol film (hereinafter, "polyvinyl alcohol” and "PVA” and is sometimes abbreviated) uniaxially stretched iodine to stretched film was oriented dye (I 3 - Ya I 5 - etc.) And dichroic organic dyes that adsorb dichroic dyes are the mainstream.
- Such a polarizing film can be obtained by uniaxially stretching a PVA film containing a dichroic dye in advance, adsorbing a bicolor dye at the same time as uniaxially stretching the PVA film, or uniaxially stretching the PVA film and then dichroic. Manufactured by adsorbing dyes.
- LCDs have come to be widely used in small devices such as calculators and wristwatches, notebook computers, LCD TVs, mobile phones, tablet terminals, and the like. In recent years, LCDs have also been used as in-vehicle image display devices such as car navigation devices and back monitors. Along with this, LCDs are required to have high durability in harsher environments than before.
- An image display device configured by laminating a polarizing plate between an image display cell and a transparent plate such as a front plate or a touch panel via an adhesive layer is provided at a high temperature for a long time required for an in-vehicle display. It is known that the light transmittance of a polarizing plate decreases when it is subjected to a durability test. One of the causes is the polyene formation of PVA constituting the polarizing film, and the higher the temperature condition, the more remarkable the decrease in the light transmittance of the polarizing plate.
- Patent Document 1 describes that polyene formation can be suppressed by adopting a polarizing plate having a protective film having a high moisture permeability on the surface of the polarizing film.
- Patent Document 2 describes that polyene formation can be suppressed by adjusting the thickness of the pressure-sensitive adhesive used for bonding the polarizing plate to the image display cell or the transparent plate and the absorbance of the polarizing film.
- Patent Documents 1 and 2 tend to suppress the decrease in the light transmittance of the polarizing plate, the temperature is 105 ° C. or higher, which has been required in recent years. In the durability test in a high temperature environment, a sufficient effect of suppressing polyene formation could not be confirmed.
- the present invention has been made based on the above circumstances, and is a PVA film capable of producing a polarizing film capable of sufficiently suppressing a decrease in the light transmittance of a polarizing plate in a high temperature durability test, such a PVA. It is an object of the present invention to provide a polarizing film obtained by using a film and a polarizing plate obtained by using the polarizing film.
- the present inventors have found that the polyene formation of PVA in the polarizing film provided on the polarizing plate is promoted by the acid generated from the protective film, and that the polarizing film or the polarizing film is promoted. It was found that polyene formation was suppressed by imparting a function of capturing acid to the PVA film, which is the original film of the above, and further studies were carried out based on these findings to complete the present invention.
- the present invention [1] A polyvinyl alcohol film containing polyvinyl alcohol and having an absorbance A1 at a wavelength of 210 nm and an average thickness D1 (mm) satisfying the following formula (1); A1 / D1 ⁇ 9 ⁇ ⁇ ⁇ (1) [2] The polyvinyl alcohol film of [1], wherein the absorbance A1 and the average thickness D1 (mm) satisfy the following formula (2); 9 ⁇ A1 / D1 ⁇ 80 ...
- a PVA film capable of producing a polarizing film capable of sufficiently suppressing a decrease in the light transmittance of a polarizing plate in a high temperature durability test, a polarizing film obtained by using such a PVA film, and a polarizing film thereof.
- a polarizing plate obtained by using a film can be provided.
- FIG. 1 is an absorption spectrum of PVA films of Examples 1 to 3 and Comparative Example 1.
- the PVA film according to the embodiment of the present invention is a PVA film containing PVA and having an absorbance A1 at a wavelength of 210 nm and an average thickness D1 (mm) satisfying the following formula (1).
- the average thickness D1 of the PVA film means an average value of values measured at arbitrary 10 points.
- the unit of A1 / D1 is mm -1 .
- Absorption at a wavelength of 210 nm is derived from a group capable of capturing an acid. As shown in Comparative Example 1 described later, even in a PVA film to which a component having a group capable of capturing an acid is not added, there is some absorption in the vicinity of a wavelength of 210 nm, and the value of A1 / D1 is 8 mm -1. (See Table 1 and Fig. 1). On the other hand, by adding a component having a group capable of capturing an acid, absorption near a wavelength of 210 nm is increased (see Examples 1 to 3 in FIG. 1).
- the PVA film sufficiently captures the acid. can do.
- a polarizing plate including a polarizing film which is a stretched PVA film and a protective film containing a cellulose ester is exposed to a high temperature for a long period of time, the cellulose ester constituting the protective film is hydrolyzed to generate acid. Generate. It is speculated that this acid catalyzes the dehydration reaction of PVA and PVA becomes polyene.
- the acid generated from the protective film is captured by the group capable of capturing the acid existing in the polarizing film. It is possible to suppress polyene formation of PVA in the polarizing film in the polarizing plate. That is, according to the PVA film, it is possible to produce a polarizing film capable of sufficiently suppressing a decrease in the light transmittance of the polarizing plate in the high temperature durability test.
- the PVA film according to one embodiment of the present invention may contain a compound having a carbodiimide group (acid scavenger), or PVA having a carbodiimide group may be used, but it may contain an acid scavenger. Is preferable.
- a compound having a carbodiimide group (acid scavenger) usually has a maximum absorption near a wavelength of 210 nm.
- the PVA film according to one embodiment of the present invention may exhibit absorption at a wavelength of 210 nm derived from an acid scavenger.
- the PVA film according to one embodiment of the present invention may have an acid scavenger having an absorption maximum in the vicinity of a wavelength of 210 nm. Further, the PVA film according to the embodiment of the present invention may be a substantially transparent film. The specific form of the acid scavenger will be described later.
- the substantially transparent film preferably has an absorbance of 0.2 or less, and more preferably 0.1 or less in the entire wavelength range of 360 nm to 780 nm.
- the lower limit of the A1 / D1 is preferably 10 mm -1, more preferably 12 mm -1, further preferably 14 mm -1, further preferably more that 20 mm -1, 25 mm -1 Is particularly preferable.
- the upper limit of A1 / D1 may be, for example, 100 mm -1 , but 80 mm -1 is preferable, and 50 mm -1 is more preferable.
- the absorbance A1 and the average thickness D1 (mm) satisfy the following formula (2). 9 ⁇ A1 / D1 ⁇ 80 ... (2)
- A1 / D1 depends on the abundance of groups having absorption at a wavelength of 210 nm.
- the value of A1 / D1 can be adjusted by the amount of the compound having a carbodiimide group, which is a group having absorption at a wavelength of 210 nm.
- PVA is a polymer having a vinyl alcohol unit (-CH 2- CH (OH)-) as a main structural unit.
- the PVA may have a vinyl ester unit or another unit in addition to the vinyl alcohol unit.
- the PVA one obtained by saponifying a polyvinyl ester obtained by polymerizing one or more kinds of vinyl esters can be used.
- the vinyl ester include vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatic acid, vinyl laurate, vinyl stearate, vinyl benzoate, isopropenyl acetate and the like.
- the polyvinyl ester is preferably obtained by using only one kind or two or more kinds of vinyl esters as a monomer, and more preferably the polyvinyl ester obtained by using only one kind of vinyl ester as a monomer.
- a copolymer resin of one kind or two or more kinds of vinyl esters and another monomer copolymerizable therewith may be used as long as the effect of the present invention is not significantly impaired.
- the upper limit of the proportion of structural units derived from other copolymerizable monomers is preferably 15 mol%, more preferably 10 mol%, based on the number of moles of all structural units constituting PVA. Is even more preferable, and 1 mol% is even more preferable.
- ⁇ -olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene, and isobutene; (meth) acrylic acid or a salt thereof; (meth) acrylic.
- Vinyl halide Acrylic compounds such as allyl acetate and allyl chloride; Maleic acid or salts thereof, esters or acid anhydrides; Itaconic acid or salts thereof, esters or acid anhydrides; Vinylsilyl compounds such as vinyltrimethoxysilane; Saturated sulfonic acid or a salt thereof and the like can be mentioned.
- the polyvinyl ester can have a structural unit derived from one or more of the above-mentioned monomers.
- PVA one that has not been graft-copolymerized can be preferably used.
- PVA may be modified with one or more graft copolymerizable monomers. Graft copolymerization can be carried out on at least one of the polyvinyl ester and the PVA obtained by saponifying it.
- the graft copolymerizable monomer include unsaturated carboxylic acids or derivatives thereof; unsaturated sulfonic acids or derivatives thereof; ⁇ -olefins having 2 to 30 carbon atoms, and the like.
- the proportion of structural units derived from the graft copolymerizable monomer in the polyvinyl ester or PVA is preferably 5 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester or PVA.
- Part of the hydroxy group of PVA may or may not be crosslinked.
- a part of the hydroxy group of PVA may react with an aldehyde compound such as acetaldehyde or butyraldehyde to form an acetal structure.
- the degree of polymerization of PVA As the lower limit of the degree of polymerization of PVA, 1,000 is preferable, 1,500 is more preferable, and 1,700 is further preferable. When the degree of polymerization of PVA is at least the above lower limit, the flexibility of the PVA film can be improved.
- the upper limit of the degree of polymerization is preferably 10,000, more preferably 8,000, and even more preferably 5,000. When the degree of polymerization of PVA is not more than the above upper limit, it is possible to suppress an increase in the production cost of PVA and the occurrence of defects during film formation.
- 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 is preferably 90 mol% or more, more preferably 95 mol% or more, and more preferably 99 mol% or more, because the obtained polarizing film has good moisture and heat resistance. It is more preferably 99.5 mol% or more, and particularly preferably 99.5 mol% or more.
- the upper limit of the saponification degree is not particularly limited, and may be 100 mol% or 99.99 mol%.
- the degree of saponification of PVA is the ratio (mol%) of the number of moles of vinyl alcohol units to the total number of moles of structural units (typically vinyl ester units) that can be converted to vinyl alcohol units by saponification. Say. The degree of saponification can be measured according to the description of JIS K6726-1994.
- the lower limit of the PVA content in the PVA film according to the embodiment of the present invention is preferably 50% by mass, more preferably 80% by mass, and even more preferably 85% by mass.
- the upper limit of the PVA content is preferably 99% by mass, more preferably 95% by mass.
- the acid scavenger which is a suitable component of the PVA film according to the embodiment of the present invention, is a compound that reacts with the acid to inactivate the acid.
- the acid trapping agent include compounds having a carbodiimide group, compounds having an epoxy group, compounds having an oxazoline group, alkyl phosphate metal salts, strongly basic amino compounds, terpene compounds, organic compounds such as oxazine compounds, and Examples thereof include inorganic compounds such as hydrotalcite stones.
- the organic compound means a compound containing carbon
- the inorganic compound means a compound other than the organic compound.
- the acid scavenger may be referred to as an acid scavenger, an acid scavenger, an acid catcher, etc., but in the present invention, it can be used without any difference depending on these names.
- the acid scavenger may be used alone or in combination of two or more.
- the acid scavenger is preferably an organic compound.
- an organic compound as the acid scavenger, the acid scavenger is likely to be deformed together with PVA in the stretching direction when the PVA film is stretched in the polarizing film manufacturing process. Therefore, defects such as voids are less likely to occur in the obtained polarizing film, and the polarization performance of the obtained polarizing film is improved.
- a carbodiimide compound having at least one carbodiimide group is more preferable.
- the carbodiimide compound has a large effect of suppressing polyene formation, and is also preferable from the viewpoint of handleability and safety.
- the mass (molecular formula amount) per 1 mol of the group capable of capturing the acid in the acid scavenger is preferably, for example, 200 g / mol or more and 1,000 g / mol or less.
- the acid scavenger is a carbodiimide compound
- the mass (molecular formula amount) per 1 mol of the group capable of capturing the acid is also referred to as the carbodiimide group equivalent and is the mass per 1 mol of the carbodiimide group.
- the acid scavenger is preferably water-soluble.
- a water-soluble acid trapping agent that is easily compatible with PVA, it is possible to obtain a PVA film having high light transmittance, low haze, and a good film surface, and a polarizing film having good polarization performance.
- water-soluble means that the solubility in water is 1 g / 100 g or more of water. Solubility in water refers to the limit amount (mass) of dissolution in 100 g of water at 20 ° C. As the lower limit of the solubility of the acid scavenger in water, 2 g / 100 g of water is preferable, and 3 g / 100 g of water is more preferable.
- the solubility in water By setting the solubility in water to the above lower limit or more, the acid trapping agent and PVA are more easily compatible with each other, the film surfaces of the obtained PVA film and polarizing film can be improved, and the polarizing performance of the polarizing film can be improved. ..
- the upper limit of the solubility may be, for example, 200 g / 100 g of water, but 100 g / 100 g of water is preferable, and 50 g / water 100 g, 20 g / water 100 g, and further 8 g / water 100 g may be more preferable.
- the molecular weight of the acid scavenger is not particularly limited, and for example, an acid scavenger having a molecular weight of 100 or more or 200 or more can be used, but the acid scavenger is preferably a polymer.
- an acid scavenger having a molecular weight of 100 or more or 200 or more can be used, but the acid scavenger is preferably a polymer.
- the acid scavenger in the PVA film is difficult to elute into the treatment liquid.
- the acid scavenger is a polymer
- the elution of the acid scavenger in the treatment liquid is suppressed due to the entanglement of the PVA molecular chain and the acid scavenger molecular chain, and the light transmission of the polarizing plate in the high temperature durability test. It is possible to obtain a polarizing film capable of more sufficiently suppressing a decrease in the rate.
- the water-soluble acid scavenger tends to elute into the treatment liquid which is an aqueous solution, especially when the molecular weight is low.
- an acid scavenger that is water-soluble and is a polymer a polarizing film that has good polarization performance and can more sufficiently suppress a decrease in the light transmittance of the polarizing plate in a high-temperature durability test can be obtained. Can be manufactured.
- the "polymer” refers to a molecule having a weight average molecular weight of 300 or more, and the weight average molecular weight is preferably 1,000 or more, more preferably 3,000 or more.
- the upper limit of the weight average molecular weight of the high molecular weight acid scavenger may be, for example, 100,000 or 10,000.
- Examples of commercially available products of high molecular weight acid scavengers include the Epocross series manufactured by Nippon Shokubai Co., Ltd. and the carbodilite series manufactured by Nisshinbo Chemical Co., Ltd., which is a water-soluble polycarbodiimide resin.
- the lower limit of the content of the acid scavenger in the PVA film is preferably 0.1 part by mass, more preferably 0.5 part by mass, further preferably 2 parts by mass, and more preferably 5 parts by mass with respect to 100 parts by mass of PVA. More preferred.
- the upper limit of this content is preferably 40 parts by mass, more preferably 20 parts by mass, and even more preferably 15 parts by mass.
- the PVA film may contain a plasticizer.
- a plasticizer When the PVA film contains a plasticizer, the handleability and stretchability of the PVA film can be improved.
- Polyhydric alcohol is preferably used as the plasticizer, and specific examples thereof include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like, and PVA films. Can contain one or more of these plasticizers. Of these, glycerin is preferable because the stretchability of the PVA film becomes better.
- the lower limit of the content of the plasticizer in the PVA film is preferably 2 parts by mass, more preferably 3 parts by mass, and even more preferably 4 parts by mass with respect to 100 parts by mass of PVA.
- the upper limit of this content is preferably 20 parts by mass, more preferably 17 parts by mass, and even more preferably 14 parts by mass with respect to 100 parts by mass of PVA.
- the content of the plasticizer in the PVA film is 20 parts by mass or less with respect to 100 parts by mass of PVA, it is possible to prevent the plasticizer from bleeding out to the surface of the PVA film and deteriorating the handleability of the PVA film. be able to.
- the PVA film may contain a surfactant.
- a surfactant When a PVA film is produced using a film-forming stock solution as described later, by adding a surfactant to the film-forming stock solution, the film-forming property is improved and the occurrence of thickness unevenness of the film is suppressed.
- the PVA film when a metal roll or belt is used for film formation, the PVA film can be easily peeled off from the metal roll or belt.
- the PVA film may contain the surfactant.
- the type of surfactant contained in the film-forming stock solution for producing PVA film and thus the type of surfactant contained in PVA film, is not particularly limited, but from the viewpoint of peelability from metal rolls and belts, anions are used.
- sexual surfactants and nonionic surfactants are preferable, and nonionic surfactants are particularly preferable.
- One type of surfactant may be used alone, or two or more types may be used in combination.
- anionic surfactant examples include a carboxylic acid type such as potassium laurate; a sulfate ester type such as octyl sulfate; and a sulfonic acid type such as dodecylbenzene sulfonate.
- nonionic surfactant examples include an alkyl ether type such as polyoxyethylene oleyl ether; an alkylphenyl ether type such as polyoxyethylene octylphenyl ether; an alkyl ester type such as polyoxyethylene laurate; and polyoxyethylene lauryl amino ether.
- Alkylamine type such as; 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; polyoxyalkylene Examples thereof include allylphenyl ether type such as allylphenyl ether.
- the lower limit of the surfactant content in the film-forming stock solution, and by extension, the surfactant content in the PVA film is the film-forming stock solution or 0.01 parts by mass is preferable, and 0.02 parts by mass is more preferable with respect to 100 parts by mass of PVA contained in the PVA film.
- the upper limit of the content of the surfactant in the film-forming stock solution and the content of the surfactant in the PVA film is 0.5 parts by mass with respect to 100 parts by mass of PVA contained in the film-forming stock solution or the PVA film.
- 0.1 part by mass is more preferable.
- the content of the surfactant is 0.01 part by mass or more with respect to 100 parts by mass of PVA, the film-forming property and the peelability can be improved.
- the content of the surfactant is 0.5 parts by mass or less with respect to 100 parts by mass of PVA, the surfactant bleeds out on the surface of the PVA film, causing blocking and lowering the handleability. It can be suppressed.
- the PVA film contains other components other than the above-mentioned PVA, acid scavenger, plasticizer and surfactant, such as antioxidant, antifreeze agent, pH adjuster, concealing agent, anticoloring agent and oil agent, if necessary. May be contained.
- the content of components other than PVA, acid scavenger, plasticizer and surfactant in the PVA film may be preferably 1% by mass or less, and more preferably 0.1% by mass or less.
- the content of the inorganic compound in the PVA film may be preferably 1% by mass or less, and more preferably 0.1% by mass or less.
- the other components and inorganic compounds may cause defects such as voids in the obtained polarizing film. Therefore, by reducing the content of the other components and inorganic compounds, the polarization performance of the obtained polarizing film tends to be improved.
- the PVA film does not substantially contain a component having a large absorption at a wavelength of 210 nm other than PVA and an acid scavenger.
- the content of components other than PVA, acid scavenger, plasticizer and surfactant in the PVA film may be preferably 1% by mass or less, more preferably 0.1% by mass or less. It may be preferable.
- the upper limit of the average thickness D1 of the PVA film is not particularly limited, but is, for example, 100 ⁇ m, preferably 80 ⁇ m, more preferably 60 ⁇ m, and even more preferably 40 ⁇ m.
- the lower limit of the average thickness D1 is preferably 5 ⁇ m, more preferably 10 ⁇ m, and even more preferably 15 ⁇ m.
- the shape of the PVA film is not particularly limited, but a long film is preferable because the polarizing film can be continuously produced with good productivity.
- the length of the long film is not particularly limited, and can be appropriately set according to the intended use of the polarizing film to be manufactured, and can be, for example, in the range of 5 to 20,000 m.
- the width of the long film is not particularly limited and may be, for example, 50 cm or more. However, since a wide polarizing film has been demanded in recent years, it is preferably 1 m or more, and more preferably 2 m or more. It is preferably 4 m or more, and more preferably 4 m or more.
- the width of the long film is preferably 7 m or less.
- the shape of the PVA film is not particularly limited and may be a single-layer film or a multilayer film (laminated body), but from the viewpoint of complexity and cost of laminating (coating, etc.) work, a single-layer film may be used. It is preferably a film.
- the PVA film may be a stretched film or a non-stretched film, but is preferably a non-stretched film.
- the non-stretched PVA film is suitably used as a raw film for a polarizing film described later.
- the polarizing film obtained by using the PVA film can sufficiently suppress a decrease in the light transmittance of the polarizing plate in the high temperature durability test, it is used for manufacturing a polarizing plate, more specifically, for a polarizing film provided on the polarizing plate. It can be preferably used.
- the PVA film may be used as an optical film such as another retardation film, an agricultural film, a packaging film, or the like.
- the PVA film according to another embodiment of the present invention is a PVA film containing PVA and an acid scavenger, and the content of the acid scavenger with respect to 100 parts by mass of the PVA is 0.1 part by mass or more.
- the PVA film contains 0.1 part by mass or more of an acid scavenger with respect to 100 parts by mass of PVA, and the absorbance A1 and the average thickness D1 (mm) at a wavelength of 210 nm satisfy the above formula (1).
- the description relating to the PVA film according to the above-described embodiment can be applied.
- the method for producing the PVA film of the present invention is not particularly limited, and a production method in which the thickness and width of the film after film formation become more uniform can be preferably adopted.
- a film-forming stock solution in which one or more of the above-mentioned PVA, acid trapping agent, and, if necessary, a plasticizer, a surfactant, and other components constituting the PVA film are dissolved in a liquid medium.
- the method of adding the acid scavenger to the film-forming stock solution is not particularly limited, and the acid scavenger may be added after the acid scavenger is charged together with PVA, or the acid scavenger may be added after the PVA is dissolved or melted. Good.
- the film-forming stock solution contains at least one of an acid scavenger, a plasticizer, a surfactant and other components, it is preferable that those components are uniformly mixed.
- liquid medium used for preparing the membrane-forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and the like.
- examples include trimethylolpropane, ethylenediamine and diethylenetriamine.
- water is preferable because it has a small impact on the environment and is recoverable.
- the volatile content of the membrane-forming stock solution (the content ratio of volatile components such as liquid media removed by volatilization or evaporation during membrane-forming in the membrane-forming stock solution) varies depending on the membrane-forming method, membrane-forming conditions, etc. 50% by mass is preferable, 55% by mass is more preferable, and 60% by mass is further preferable. On the other hand, as the upper limit, 95% by mass is preferable, 90% by mass is more preferable, and 85% by mass is further preferable.
- the volatile content of the membrane-forming stock solution is 50% by mass or more, the viscosity of the membrane-forming stock solution does not become too high, filtration and defoaming during preparation of the film-forming stock solution are smoothly performed, and PVA with few foreign substances and defects. Film production becomes easier.
- the volatile content 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 the production of an industrial PVA film becomes easy.
- Examples of the film-forming method for forming a PVA film using the above-mentioned film-forming stock solution include a cast film-forming method, an extrusion film-forming method, a wet film-forming method, and a gel film-forming method.
- the method and the extrusion film forming method are preferable. Above all, the extrusion film forming method is more preferable because a PVA film having a uniform thickness and width and good physical properties can be obtained.
- the PVA film can be dried or heat treated as needed.
- the heat treatment temperature is not particularly limited, and may be appropriately adjusted according to the degree of swelling of the PVA film in each range.
- the heat treatment temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, still more preferably 150 ° C. or lower, because discoloration or deterioration of the PVA film is observed if the heat treatment temperature is too high.
- the lower limit of the heat treatment temperature can be, for example, 80 ° C.
- the heat treatment time is not particularly limited and may be appropriately adjusted according to the degree of swelling of the PVA film, etc., but from the viewpoint of efficiently producing the PVA film of the present invention, 1 to 60 minutes is preferable, and 2 to 40 minutes is more preferable. It is preferable, and 3 to 30 minutes is more preferable.
- the polarizing film according to an embodiment of the present invention is a polarizing film formed from the above-mentioned PVA film of the present invention.
- a dichroic dye such as an iodine dye or a dichroic organic dye is usually adsorbed on a stretched film obtained by uniaxially stretching and orienting a non-stretched PVA film according to an embodiment of the present invention. It is a film that becomes.
- the polarizing film according to another embodiment of the present invention contains PVA, and has the absorbance A2 and the average thickness D2 (mm) at a wavelength of 210 nm after being allowed to stand in a 90% RH atmosphere at 60 ° C. for 100 hours according to the following formula ( It is a polarizing film that satisfies 3).
- a dichroic dye such as an iodine-based dye is volatilized to form a substantially transparent film. Therefore, by measuring the absorbance after allowing to stand in a 90% RH atmosphere at 60 ° C.
- A2 / D2 is mm -1 .
- the lower limit of A2 / D2 is preferably 10 mm -1, more preferably 12 mm -1, further preferably 14 mm -1, still more preferably from 20 mm -1, is 25 mm -1 Especially preferable.
- the polarizing film can further enhance the acid trapping ability, sufficiently suppress polyene formation in the high temperature durability test, and more sufficiently suppress the decrease in the light transmittance of the polarizing plate.
- the upper limit of A2 / D2 may be, for example, 100 mm -1 , but 80 mm -1 is preferable, and 50 mm -1 is more preferable.
- A2 / D2 By setting A2 / D2 to the above upper limit or less, the film surface becomes good and the polarization performance of the polarizing film can be improved.
- the polarizing film of another embodiment of the present invention also has a dichroism such as an iodine dye or a dichroic organic dye on a stretched film obtained by uniaxially stretching and orienting a non-stretched PVA film according to an embodiment of the present invention. It may be a film formed by adsorbing a dye.
- the upper limit of the average thickness D2 of the polarizing film of the present invention is, for example, 100 ⁇ m, preferably 50 ⁇ m, and more preferably 30 ⁇ m.
- the lower limit of this average thickness may be 1 ⁇ m, preferably 5 ⁇ m.
- the method for producing the polarizing film of the present invention is not particularly limited, and any conventionally adopted method may be adopted.
- a polarizing film can be produced by subjecting the PVA film of the present invention to a swelling treatment, a dyeing treatment, a uniaxial stretching treatment, and if necessary, a cross-linking treatment, a fixing treatment, a drying treatment, a heat treatment, and the like. ..
- the order of each treatment such as swelling treatment, dyeing treatment, uniaxial stretching, and fixing treatment is not particularly limited, and one or more treatments can be performed at the same time. It is also possible to perform one or more of each process twice or more.
- the swelling treatment can be performed by immersing the PVA film in water.
- the lower limit of the temperature of water when immersed in water is preferably 20 ° C, more preferably 22 ° C, and even more preferably 25 ° C.
- the upper limit is preferably 40 ° C, more preferably 38 ° C, and even more preferably 35 ° C.
- the time for immersion in water is preferably 0.1 to 5 minutes, for example.
- the water when immersed in water is not limited to pure water, and may be an aqueous solution in which various components are dissolved, or a mixture of water and an aqueous medium.
- the dyeing treatment is performed using a dichroic dye such as an iodine dye or a dye, and the dyeing time may be any stage before uniaxial stretching, during uniaxial stretching, and after uniaxial stretching.
- Dyeing is generally carried out by immersing the PVA film in a solution containing iodine-potassium iodide (particularly an aqueous solution) as a dyeing bath.
- concentration of iodine in the dyeing bath is preferably 0.01 to 0.5% by mass, and the concentration of potassium iodide is preferably 0.01 to 10% by mass.
- the temperature of the dyeing bath is preferably 20 to 60 ° C.
- the cross-linking treatment can be performed by immersing the PVA film in an aqueous solution containing a cross-linking agent.
- a cross-linking agent used, one or more kinds of boron compounds such as borate such as boric acid and borax can be used.
- the concentration of the cross-linking agent in the aqueous solution containing the cross-linking agent is preferably 1 to 15% by mass, more preferably 2 to 7% by mass.
- the temperature of the aqueous solution containing the cross-linking agent is preferably 20 to 60 ° C.
- Uniaxial stretching 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, in the above-mentioned dyeing bath or in the fixing treatment bath described later.
- the dry stretching method it can be carried out in air.
- the wet stretching method is preferable, and uniaxial stretching is more preferable in an aqueous solution containing boric acid.
- the concentration of boric acid in the boric acid aqueous solution is preferably 0.5 to 6.0% by mass, more preferably 1.0 to 5.0% by mass, still more preferably 1.5 to 4.0% by mass.
- the boric acid aqueous solution may contain potassium iodide, and the concentration thereof is preferably 0.01 to 10% by mass.
- the stretching temperature in uniaxial stretching is preferably 30 to 90 ° C, more preferably 40 to 80 ° C, and even more preferably 50 to 70 ° C.
- the draw ratio in uniaxial stretching is preferably 5 times or more, more preferably 5.5 times or more, from the viewpoint of the polarization performance of the obtained polarizing film.
- the upper limit of the draw ratio is not particularly limited, but the draw ratio is preferably 8 times or less.
- the fixing treatment bath used for the fixing treatment an aqueous solution containing one or more kinds of boron compounds such as boric acid and borax can be used. Further, if necessary, an iodine compound or a metal compound may be added to the fixing treatment bath.
- concentration of the boron compound in the fixing treatment bath is generally preferably about 2 to 15% by mass, particularly preferably about 3 to 10% by mass.
- the temperature of the fixing treatment bath is preferably 15 to 60 ° C., particularly preferably 25 to 40 ° C.
- the drying treatment is preferably performed at 30 to 150 ° C., and more preferably 50 to 130 ° C. By drying at a temperature within the above range, a polarizing film having excellent dimensional stability can be easily obtained.
- the polarizing plate of the present invention has the polarizing film of the present invention and a protective film containing a cellulose ester resin.
- the polarizing plate according to the embodiment of the present invention has, for example, a protective film laminated on at least one surface of the polarizing film with an adhesive.
- the protective film is usually a cellulose ester film containing a cellulose ester resin as a main component.
- the content of the cellulose ester resin in the protective film is preferably 70% by mass or more, more preferably 90% by mass or more.
- the cellulose ester resin include cellulose triacetate (triacetyl cellulose: TAC), cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose acetate propionate benzoate, cellulose propionate, and cellulose buty. Rate, cellulose acetate biphenylate, cellulose acetate propionate biphenylate and the like can be mentioned, and among these, cellulose triacetate is preferable.
- Examples of the adhesive for adhering the polarizing film and the protective film include PVA-based adhesives and ultraviolet curable adhesives, but PVA-based adhesives are particularly preferable.
- An acid scavenger can also be contained in this PVA-based adhesive.
- As the PVA-based adhesive an aqueous solution of PVA or the like can be used.
- the light transmittance when tilted by 45 ° and the light transmittance when tilted by ⁇ 45 ° were measured, and their average value Ts2 (%) was obtained.
- the average value of Ts1 and Ts2 was defined as the light transmittance Ts (%) of the polarizing film.
- a sample was prepared so that the light transmittance Ts was 44.0% by adjusting the dyeing treatment conditions, and the degree of polarization was measured.
- the polarization performance was determined according to the following criteria. In addition, A, B, and C were judged to be good because they could be used without any problem in practical use, and D was judged to be defective.
- D When the transmittance Ts44.0%, the degree of polarization V is less than 90.0%
- Acid trapping agent A "Carbodilite V-04" (manufactured by Nisshinbo Chemical Co., Ltd., solubility 5 g / water 100 g, carbodiimide group equivalent 339 g / mol), which is a high molecular weight (molecular weight of about 1,000 to 5,000) carbodiimide compound.
- Acid trapping agent B "Carbodiimide V-02" (manufactured by Nisshinbo Chemical Co., Ltd., solubility 100 g / water 100 g, carbodiimide group equivalent 602 g / mol), which is a high molecular weight (molecular weight of about 1,000 to 5,000) carbodiimide compound.
- Acid trapping agent C "Carbodiimide SV-02" (manufactured by Nisshinbo Chemical Co., Ltd., solubility 100 g / water 100 g, carbodiimide group equivalent 429 g / mol), which is a high molecular weight (molecular weight of about 1,000 to 5,000) carbodiimide compound.
- Acid scavenger D N, N'-dicyclohexylcarbodiimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., solubility less than 1 g / 100 g of water)
- Acid scavenger E 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., solubility 10 g / water 100 g)
- Example 1 Production of PVA film PVA (a saponified product of a homopolymer of vinyl acetate, the degree of polymerization of PVA is 2,400, and the degree of saponification of PVA is 99.95 mol%) and glycerin (relative to 100 parts by mass of PVA). 10 parts by mass), a surfactant (0.03 parts by mass with respect to 100 parts by mass of PVA) and water were mixed and dissolved at 90 ° C. for 4 hours to obtain an aqueous PVA solution. Then, as an acid scavenger, 10 parts by mass of acid scavenger A was added to 100 parts by mass of PVA, and the mixture was stirred at 85 ° C. for 30 minutes.
- an acid scavenger 10 parts by mass of acid scavenger A was added to 100 parts by mass of PVA, and the mixture was stirred at 85 ° C. for 30 minutes.
- the amount of the acid scavenger added shown in Table 1 indicates the solid content (parts by mass) of the acid scavenger with respect to 100 parts by mass of PVA, and is equal to the content in the obtained PVA film. Then, the PVA aqueous solution was kept warm at 85 ° C. for 16 hours for defoaming of the PVA aqueous solution.
- the obtained PVA aqueous solution was dried on a metal roll at 80 ° C., and the obtained film was heat-treated in a dryer at 110 ° C. for 10 minutes to obtain a PVA film (average thickness 30 ⁇ m) having a swelling degree of 200%.
- the absorbance A1 and the average thickness D1 were measured based on the above method, and the ratio A1 / D1 of these was determined. The results are shown in Table 1.
- the absorption spectrum of the PVA film obtained in FIG. 1 in the wavelength range of 200 to 400 nm is shown.
- uniaxial stretching (second-stage stretching) was performed up to 3.3 times the original length at the stretching rate of.
- the test piece was then immersed in a boric acid / potassium iodide aqueous solution containing 3% by mass of boric acid and 3% by mass of potassium iodide at a temperature of 30 ° C. for about 20 seconds at 24 cm / min.
- uniaxial stretching (third step stretching) was performed up to 3.6 times the original length at the stretching rate of.
- the test piece was immersed in an aqueous solution of boric acid / potassium iodide at a temperature of 58 ° C. containing a concentration of 4% by mass of boric acid and about 5% by mass of potassium iodide at 24 cm / min.
- uniaxial stretching fourth step stretching
- the test piece is immersed in an aqueous potassium iodide solution containing 1.5% by mass of boric acid and 3% by mass of potassium iodide for 10 seconds for fixing treatment, and then dried at 60 ° C. It was dried in a machine for 4 minutes to obtain a polarizing film (average thickness 13 ⁇ m).
- the absorbance A2 and the average thickness D2 were measured based on the above method, and the ratio A2 / D2 of these was determined.
- the polarization performance was evaluated by the above method. The results are shown in Table 1.
- a polarizing plate is manufactured by laminating a triacetyl cellulose film on both sides of this test piece (polarizing film) using a PVA-based adhesive (3.5% by mass aqueous solution of PVA) and drying at 60 ° C. for 10 minutes. did.
- the PVA in the PVA-based adhesive used was a saponification of a homopolymer of vinyl acetate, the degree of polymerization of PVA was 2,400, and the degree of saponification of PVA was 99.95 mol%.
- Example 2 A PVA film, a polarizing film, and a polarizing plate were produced in the same manner as in Example 1 except that the acid scavenger B was used as the acid scavenger. Each evaluation was performed for these in the same manner as in Example 1. The results are shown in Table 1. In addition, the absorption spectrum of the PVA film obtained in FIG. 1 in the wavelength range of 200 to 400 nm is shown.
- Example 3 A PVA film, a polarizing film, and a polarizing plate were produced in the same manner as in Example 1 except that the acid scavenger C was used as the acid scavenger. Each evaluation was performed for these in the same manner as in Example 1. The results are shown in Table 1. In addition, the absorption spectrum of the PVA film obtained in FIG. 1 in the wavelength range of 200 to 400 nm is shown.
- Example 4 A PVA film, a polarizing film and a polarizing plate were produced in the same manner as in Example 1 except that the content (addition amount) of the acid scavenger A was 1 part by mass with respect to 100 parts by mass of PVA. Each evaluation was performed for these in the same manner as in Example 1. However, the high temperature durability test at 115 ° C. for 70 hours has not been performed. The results are shown in Table 1.
- Example 5 A PVA film, a polarizing film and a polarizing plate were produced in the same manner as in Example 1 except that the content (addition amount) of the acid scavenger A was 30 parts by mass with respect to 100 parts by mass of PVA. Each evaluation was performed for these in the same manner as in Example 1. However, the high temperature durability test at 115 ° C. for 70 hours has not been performed. The results are shown in Table 1. Since the amount of the acid scavenger added was too large, the film surfaces of the obtained PVA film and polarizing film were poor.
- Example 6 A PVA film, a polarizing film, and a polarizing plate were produced in the same manner as in Example 1 except that the acid scavenger D was used as the acid scavenger. Each evaluation was performed for these in the same manner as in Example 1. However, the high temperature durability test at 115 ° C. for 70 hours has not been performed. The results are shown in Table 1. Since the acid scavenger D does not have water solubility and has poor compatibility with PVA, the film surfaces of the obtained PVA film and polarizing film are poor.
- Example 7 A PVA film, a polarizing film, and a polarizing plate were produced in the same manner as in Example 1 except that the acid scavenger E was used as the acid scavenger. Each evaluation was performed for these in the same manner as in Example 1. However, the high temperature durability test at 115 ° C. for 70 hours has not been performed. The results are shown in Table 1. Since the molecular weight of the acid scavenger E was small and it was easy to elute during the polarizing film manufacturing process, the amount of the carbodiimide compound remaining in the polarizing film was small, and the A2 / D2 value was small.
- Example 1 A PVA film, a polarizing film and a polarizing plate were produced in the same manner as in Example 1 except that no acid scavenger was added. Each evaluation was performed for these in the same manner as in Example 1. The results are shown in Table 1. In addition, the absorption spectrum of the PVA film obtained in FIG. 1 in the wavelength range of 200 to 400 nm is shown.
- Example 2 A PVA film, a polarizing film and a polarizing plate were produced in the same manner as in Example 1 except that the content (addition amount) of the acid scavenger A was 0.01 part by mass with respect to 100 parts by mass of PVA. Each evaluation was performed for these in the same manner as in Example 1. The results are shown in Table 1.
- the polarizing plate including the polarizing film obtained from the PVA films of Examples 1 to 7 having A1 / D1 of 9 mm -1 or more transmits light in a high temperature durability test (105 ° C., 250 h). The decrease in the rate is sufficiently suppressed.
- Example 5 In Example 5 in which the amount of the acid scavenger added was large, and in Example 6 in which the water-insoluble acid scavenger was used, the polarization performance of the obtained polarizing film was slightly low due to the deterioration of the film surface. The result was. Further, in Example 4 in which the amount of the acid scavenger added is relatively small, and in Example 7 in which the low molecular weight acid scavenger is used, the residual amount of the acid scavenger in the obtained polarizing film is small, and the high temperature durability is achieved. The result was a little low sex. Comparing Examples 1 to 3 based on the results of the high temperature durability test (105 ° C., 250 ° C. + 115 ° C., 70 h), it can be seen that the higher the value of A2 / D2, the higher the high temperature durability.
- the PVA film according to the present invention is suitably used as a raw film or the like of a polarizing film used for a polarizing plate.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polarising Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
[1]ポリビニルアルコールを含み、波長210nmにおける吸光度A1と平均厚みD1(mm)とが下記式(1)を満たすポリビニルアルコールフィルム;
A1/D1≧9 ・・・(1)
[2]上記吸光度A1と上記平均厚みD1(mm)とが下記式(2)を満たす、[1]のポリビニルアルコールフィルム;
9≦A1/D1≦80 ・・・(2)
[3]酸捕捉剤を含む、[1]又は[2]のポリビニルアルコールフィルム;
[4]ポリビニルアルコールと酸捕捉剤とを含み、上記ポリビニルアルコール100質量部に対する上記酸捕捉剤の含有量が0.1質量部以上であるポリビニルアルコールフィルム;
[5]上記酸捕捉剤が有機化合物である、[3]又は[4]のポリビニルアルコールフィルム;
[6]上記酸捕捉剤が、少なくとも1個のカルボジイミド基を有するカルボジイミド化合物である、[5]のポリビニルアルコールフィルム。
[7]上記酸捕捉剤が水溶性である、[3]~[6]のいずれかのポリビニルアルコールフィルム;
[8]上記酸捕捉剤が高分子である、[7]のポリビニルアルコールフィルム;
[9]上記ポリビニルアルコールのけん化度が90モル%以上である、[1]~[8]のいずれかのポリビニルアルコールフィルム;
[10]偏光板製造用である、[1]~[9]のいずれかのポリビニルアルコールフィルム;
[11][1]~[10]のいずれかのポリビニルアルコールフィルムから形成された偏光フィルム;
[12]ポリビニルアルコールを含み、60℃、90%RH雰囲気下に100時間静置した後の波長210nmにおける吸光度A2と平均厚みD2(mm)とが下記式(3)を満たす偏光フィルム;
A2/D2≧9 ・・・(3)
[13][11]又は[12]の偏光フィルムと、セルロースエステル系樹脂を含む保護フィルムとを有する偏光板;
に関する。
<PVAフィルム>
本発明の一実施形態に係るPVAフィルムは、PVAを含み、波長210nmにおける吸光度A1と平均厚みD1(mm)とが下記式(1)を満たすPVAフィルムである。
A1/D1≧9 ・・・(1)
9≦A1/D1≦80 ・・・(2)
PVAは、ビニルアルコール単位(-CH2-CH(OH)-)を主の構造単位として有する重合体である。PVAは、ビニルアルコール単位の他、ビニルエステル単位やその他の単位を有していてもよい。
本発明の一実施形態に係るPVAフィルムの好適成分である酸捕捉剤は、酸と反応して酸を不活性化する化合物である。酸捕捉剤としては、例えばカルボジイミド基を有する化合物、エポキシ基を有する化合物、オキサゾリン基を有する化合物、アルキルリン酸金属塩、強塩基性アミノ化合物、テルペン系化合物、オキサジン化合物等の有機系化合物、及びハイドロタルサイト石群等の無機化合物などが挙げられる。有機化合物とは、炭素を含む化合物をいい、無機化合物とは、有機化合物以外の化合物をいう。なお、酸捕捉剤は、酸掃去剤、酸捕獲剤、酸キャッチャー等と称されることもあるが、本発明においては、これらの呼称による差異なく用いることができる。酸捕捉剤は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
PVAフィルムは、可塑剤を含んでいてもよい。PVAフィルムが可塑剤を含むことにより、PVAフィルムの取り扱い性や延伸性の向上等を図ることができる。可塑剤としては多価アルコールが好ましく用いられ、具体例としては、エチレングリコール、グリセリン、プロピレングリコール、ジエチレングリコール、ジグリセリン、トリエチレングリコール、テトラエチレングリコール、トリメチロールプロパンなどを挙げることができ、PVAフィルムはこれらの可塑剤の1種又は2種以上を含むことができる。これらのうちでもPVAフィルムの延伸性がより良好になることからグリセリンが好ましい。
PVAフィルムには、界面活性剤が含有されていてもよい。後述するような製膜原液を用いてPVAフィルムを製造する場合には、この製膜原液中に界面活性剤を配合することにより、製膜性が向上してフィルムの厚み斑の発生が抑制されると共に、製膜に金属ロールやベルトを使用した際、これらの金属ロールやベルトからのPVAフィルムの剥離が容易になる。界面活性剤が配合された製膜原液からPVAフィルムを製造した場合には、PVAフィルム中には界面活性剤が含有され得る。PVAフィルムを製造するための製膜原液に配合される界面活性剤、ひいてはPVAフィルム中に含有される界面活性剤の種類は特に限定されないが、金属ロールやベルトからの剥離性の観点から、アニオン性界面活性剤及びノニオン性界面活性剤が好ましく、ノニオン性界面活性剤が特に好ましい。界面活性剤は1種を単独で又は2種以上を組み合わせて使用することができる。
PVAフィルムは、必要に応じて、酸化防止剤、凍結防止剤、pH調整剤、隠蔽剤、着色防止剤、油剤など、上記したPVA、酸捕捉剤、可塑剤及び界面活性剤以外の他の成分を含有していてもよい。但し、PVAフィルムにおけるPVA、酸捕捉剤、可塑剤及び界面活性剤以外の他の成分の含有量は、1質量%以下が好ましいこともあり、0.1質量%以下がより好ましいことがある。また、PVAフィルムにおける無機化合物の含有量も、1質量%以下が好ましいこともあり、0.1質量%以下がより好ましいことがある。上記他の成分や無機化合物は、得られる偏光フィルムにおけるボイド等の欠陥の原因となる場合がある。このため、上記他の成分や無機化合物の含有量を少なくすることで、得られる偏光フィルムの偏光性能が向上する傾向にある。
当該PVAフィルムを用いて得られる偏光フィルムは、高温耐久試験において偏光板の光透過率の低下を十分に抑制できるため、偏光板製造用、より具体的には、偏光板に備わる偏光フィルム用に好適に用いることができる。当該PVAフィルムは、その他の位相差フィルム等の光学フィルム、農業用フィルム、包装用フィルム等として用いられてもよい。
本発明の他の実施形態に係るPVAフィルムは、PVAと酸捕捉剤とを含み、上記PVA100質量部に対する上記酸捕捉剤の含有量が0.1質量部以上であるPVAフィルムである。当該PVAフィルムは、PVA100質量部に対して酸捕捉剤が0.1質量部以上含有されていること、及び波長210nmにおける吸光度A1と平均厚みD1(mm)とが上記式(1)を満たすことを必須としないこと以外は、上述した一実施形態に係るPVAフィルムと同じである。他の実施形態に係るPVAフィルムの具体的態様及び好適態様は、上述した一実施形態に係るPVAフィルムに係る記載を適用することができる。
本発明のPVAフィルムの製造方法は特に限定されず、製膜後のフィルムの厚み及び幅がより均一になる製造方法を好ましく採用することができる。例えば、PVAフィルムを構成する上記したPVA、酸捕捉剤、ならびに必要に応じて更に可塑剤、界面活性剤及び他の成分のうちの1種又は2種以上が液体媒体中に溶解した製膜原液や、PVA、酸捕捉剤、ならびに必要に応じて更に可塑剤、界面活性剤、他の成分及び液体媒体のうちの1種又は2種以上を含み、PVAが溶融している製膜原液を用いて製造することができる。製膜原液への酸捕捉剤の添加方法は特に限定されず、PVAと共に酸捕捉剤を仕込んだ後に溶解又は溶融してもよいし、PVAを溶解又は溶融した後に酸捕捉剤を添加してもよい。当該製膜原液が酸捕捉剤、可塑剤、界面活性剤及び他の成分のうちの少なくとも1種を含有する場合には、それらの成分が均一に混合されていることが好ましい。
本発明の一実施形態に係る偏光フィルムは、上述した本発明のPVAフィルムから形成された偏光フィルムである。当該偏光フィルムは、通常、本発明の一実施形態である非延伸のPVAフィルムを一軸延伸して配向させた延伸フィルムにヨウ素系色素や二色性有機染料等の二色性色素が吸着してなるフィルムである。
A2/D2≧9 ・・・(3)
本発明の偏光フィルムを製造する際の方法は特に制限されず、従来から採用されているいずれの方法を採用してもよい。例えば、本発明のPVAフィルムに対して、膨潤処理、染色処理、一軸延伸、及び必要に応じてさらに、架橋処理、固定処理、乾燥処理、熱処理などを施すことにより偏光フィルムを製造することができる。この場合、膨潤処理、染色処理、一軸延伸、固定処理などの各処理の順序は特に制限されず、1つ又は2つ以上の処理を同時に行うこともできる。また、各処理の1つ又は2つ以上を2回又はそれ以上行うこともできる。
本発明の偏光板は、本発明の偏光フィルムとセルロースエステル系樹脂を含む保護フィルムとを有する。本発明の一実施形態に係る偏光板は、例えば偏光フィルムの少なくとも一方の面に接着剤を介して積層された保護フィルムを有する。
PVAフィルムを約1.5g採取し、これを約2mm×10cmに裁断した。その後、この裁断したPVAフィルムをメッシュ(株式会社NBCメッシュテック製「N-N0110S 115」)に包み、30℃の蒸留水中に15分間浸漬させた。続いて、メッシュで包んだPVAフィルムに対して3,000rpmで5分間遠心脱水を行い、メッシュを取り除いてからPVAフィルムの質量(W1)を求めた。続いて、そのPVAフィルムを105℃の乾燥機で16時間乾燥した後、質量(W2)を求めた。そして、下記式によりPVAフィルムの膨潤度を算出した。
膨潤度(%)={(W1)/(W2)}×100
PVAフィルムを4cm角に切り出し、分光光度計(株式会社日立ハイテクサイエンス社製「U-4100」)を用いて、波長200~780nmの範囲の吸光度を測定し、波長210nmにおける吸光度A1を求めた。
偏光フィルムを4cm角に切り出し、金枠に固定した後、60℃、90%RHに設定した恒温恒湿機内に100時間静置し、透明フィルムを得た。その後、分光光度計(株式会社日立ハイテクサイエンス社製「U-4100」)を用いて、上記透明フィルムの波長200~780nmの範囲の吸光度を測定し、波長210nmにおける吸光度A2を求めた。
PVAフィルムの平均厚みD1及び偏光フィルムの平均厚みD2は、接触式厚み計(株式会社小野測器社製リニアゲージセンサ「GS-3813」)を用いて測定した。
(a)光透過率Tsの測定
偏光フィルムから、長さ方向に3cm×幅方向に2cmの正方形のサンプルを2枚採取した。JIS Z8722:2009(物体色の測定方法)に準拠し、積分球付き分光光度計(日本分光株式会社製「V7100」)を用い、1枚のサンプルについて、長さ方向に対して45°傾けた場合の光透過率と-45°傾けた場合の光透過率を測定して、それらの平均値Ts1(%)を求めた。なお、測定は、C光源、2°視野の可視光領域の視感度補正をして行った。もう1枚のサンプルについても同様にして、45°傾けた場合の光透過率と-45°傾けた場合の光透過率を測定して、それらの平均値Ts2(%)を求めた。Ts1とTs2との平均値を偏光フィルムの光透過率Ts(%)とした。
以下の偏光度Vの測定においては、染色処理条件を調整して光透過率Tsが44.0%になるようサンプルを作製し、偏光度の測定を行った。
上記光透過率Tsの測定で採取した2枚のサンプルを、その長さ方向が平行になるように重ねて、長さ方向に対して45°傾けた場合の光透過率と-45°傾けた場合の光透過率を測定して、それらの平均値T∥(%)を求めた。次に、長さ方向が直交するように重ねて、長さ方向に対して45°傾けた場合の光透過率と-45°傾けた場合の光透過率を測定して、それらの平均値T⊥(%)を求め、下記式により偏光度V(%)を求めた。
V={(T∥-T⊥)/(T∥+T⊥)}1/2×100
求めた偏光度Vに基づき、以下の基準で偏光性能を判定した。なお、A、B、Cは実用上問題なく使用できるため良好と判断し、Dは不良と判断した。
A:透過率Ts44.0%のとき、偏光度Vが99.0%以上
B:透過率Ts44.0%のとき、偏光度Vが95.0%以上99.0%未満
C:透過率Ts44.0%のとき、偏光度Vが90.0%以上95.0%未満
D:透過率Ts44.0%のとき、偏光度Vが90.0%未満
(a)サンプル作製
偏光板を4cm角に切り出し、10cm角のガラス板(1mm厚)と10cm角に切り出した粘着剤シート(株式会社美舘イメージング社製「MCS70」;厚さ25μm)とを用いて、ガラス板/粘着剤シート/偏光板/粘着剤シート/ガラス板の順に積層し、ラミネーターを用いて圧着した。このとき、偏光板はガラス板の中央部に積層した。その後、真空ラミネーター(日清紡メカトロニクス株式会社製「1522N」)を用いて、50℃で10kPaの圧力を5分間かけて、更に圧着した。なお、得られた高温耐久試験用サンプルは、後述する光透過率の測定の方法により測定した光透過率が35~40%の範囲内のものであった。
作製した高温耐久試験用サンプルを105℃の乾燥機に250時間投入した。その後、後述する方法により、サンプルの光透過率を測定した。さらにその後、サンプルを115℃の乾燥機に70時間投入した。その後、後述する方法により、取り出したサンプルの光透過率を測定した。
高温耐久試験用サンプルの中央部について、積分球付き分光光度計(株式会社日立ハイテクサイエンス社製「U4100」)を用いて、偏光フィルムの吸収軸方向に対して45°傾けた場合の光透過率と-45°傾けた場合の光透過率を測定して、それらの平均値T(%)を求めた。
以下の基準で高温耐久性を判定した。なお、A、B、Cは実用上問題なく使用できるため良好と判断し、Dは不良と判断した。
A:高温耐久試験後の光透過率が20%以上
B:高温耐久試験後の光透過率が10%以上20%未満
C:高温耐久試験後の光透過率が1%以上10%未満
D:高温耐久試験後の光透過率が1%未満
酸捕捉剤A:高分子(分子量約1,000~5,000)のカルボジイミド化合物である「カルボジライトV-04」(日清紡ケミカル株式会社製、溶解度5g/水100g、カルボジイミド基当量339g/mol)
酸捕捉剤B:高分子(分子量約1,000~5,000)のカルボジイミド化合物である「カルボジライトV-02」(日清紡ケミカル株式会社製、溶解度100g/水100g、カルボジイミド基当量602g/mol)
酸捕捉剤C:高分子(分子量約1,000~5,000)のカルボジイミド化合物である「カルボジライトSV-02」(日清紡ケミカル株式会社製、溶解度100g/水100g、カルボジイミド基当量429g/mol)
酸捕捉剤D:N,N’-ジシクロヘキシルカルボジイミド(富士フィルム和光純薬株式会社製、溶解度1g未満/水100g)
酸捕捉剤E:塩酸1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド(富士フィルム和光純薬株式会社製、溶解度10g/水100g)
(1)PVAフィルムの製造
PVA(酢酸ビニルの単独重合体のけん化物であり、PVAの重合度は2,400で、PVAのけん化度は99.95モル%)とグリセリン(PVA100質量部に対して10質量部)と界面活性剤(PVA100質量部に対して0.03質量部)と水とを混合し、90℃で4時間溶解した後、PVA水溶液を得た。その後、酸捕捉剤として、酸捕捉剤AをPVA100質量部に対して10質量部添加し、85℃で30分間撹拌した。なお、表1に記載する酸捕捉剤の添加量とは、PVA100質量部に対する酸捕捉剤の固形分量(質量部)のことを示し、得られたPVAフィルム中の含有量に等しい。その後、PVA水溶液の脱泡のため、PVA水溶液を85℃で16時間保温した。
得られたPVAフィルムから、長さ方向9cm×幅方向10cmの試験片を採取した。当該試験片の長さ方向の両端を、延伸部分のサイズが長さ方向5cm×幅方向10cmとなるように延伸治具に固定し、温度30℃の水中に38秒間浸漬している間に24cm/分の延伸速度で元の長さの2.2倍に長さ方向に一軸延伸(1段目延伸)した。その後、当該試験片を、ヨウ素を0.03質量%及びヨウ化カリウムを3質量%の濃度で含有する温度30℃のヨウ素/ヨウ化カリウム水溶液中に60秒間浸漬している間に24cm/分の延伸速度で元の長さの3.3倍まで長さ方向に一軸延伸(2段目延伸)した。次いで当該試験片を、ホウ酸を3質量%及びヨウ化カリウムを3質量%の濃度で含有する温度30℃のホウ酸/ヨウ化カリウム水溶液中に約20秒間浸漬している間に24cm/分の延伸速度で元の長さの3.6倍まで長さ方向に一軸延伸(3段目延伸)した。続いて、当該試験片を、ホウ酸を4質量%及びヨウ化カリウムを約5質量%の濃度で含有する温度58℃のホウ酸/ヨウ化カリウム水溶液中に浸漬している間に24cm/分の延伸速度で元の長さの5.5倍まで長さ方向に一軸延伸(4段目延伸)した。その後、当該試験片を、ホウ酸を1.5質量%及びヨウ化カリウムを3質量%の濃度で含有するヨウ化カリウム水溶液中に10秒間浸漬して固定処理を行い、次いで後60℃の乾燥機で4分間乾燥して、偏光フィルム(平均厚み13μm)を得た。
得られた偏光フィルムから、長さ方向10cm、幅方向5cmの試験片を採取した。この試験片(偏光フィルム)の両面に、PVA系接着剤(PVAの3.5質量%水溶液)を用いてトリアセチルセルロースフィルムを貼り合わせ、60℃で10分間乾燥させることで、偏光板を製造した。なお、用いたPVA系接着剤におけるPVAは酢酸ビニルの単独重合体のけん化物であり、PVAの重合度は2,400で、PVAのけん化度は99.95モル%であった。
酸捕捉剤として、酸捕捉剤Bを用いたこと以外は実施例1と同様にして、PVAフィルム、偏光フィルム及び偏光板を製造した。実施例1と同様に、これらについて各評価を行った。結果を表1に示す。また、図1に得られたPVAフィルムの波長200~400nmの範囲の吸収スペクトルを示す。
酸捕捉剤として、酸捕捉剤Cを用いたこと以外は実施例1と同様にして、PVAフィルム、偏光フィルム及び偏光板を製造した。実施例1と同様に、これらについて各評価を行った。結果を表1に示す。また、図1に得られたPVAフィルムの波長200~400nmの範囲の吸収スペクトルを示す。
酸捕捉剤Aの含有量(添加量)をPVA100質量部に対して1質量部にしたこと以外は実施例1と同様にして、PVAフィルム、偏光フィルム及び偏光板を製造した。実施例1と同様に、これらについて各評価を行った。但し、115℃、70時間を加えた高温耐久性試験は行っていない。結果を表1に示す。
酸捕捉剤Aの含有量(添加量)をPVA100質量部に対して30質量部にしたこと以外は実施例1と同様にして、PVAフィルム、偏光フィルム及び偏光板を製造した。実施例1と同様に、これらについて各評価を行った。但し、115℃、70時間を加えた高温耐久性試験は行っていない。結果を表1に示す。なお、酸捕捉剤の添加量が多すぎたために、得られたPVAフィルム及び偏光フィルムの膜面が不良であった。
酸捕捉剤として、酸捕捉剤Dを用いたこと以外は実施例1と同様にして、PVAフィルム、偏光フィルム及び偏光板を製造した。実施例1と同様に、これらについて各評価を行った。但し、115℃、70時間を加えた高温耐久性試験は行っていない。結果を表1に示す。なお、酸捕捉剤Dは水溶性を有さずPVAとの相溶性が悪いために、得られたPVAフィルム及び偏光フィルムの膜面が不良であった。
酸捕捉剤として、酸捕捉剤Eを用いたこと以外は実施例1と同様にして、PVAフィルム、偏光フィルム及び偏光板を製造した。実施例1と同様に、これらについて各評価を行った。但し、115℃、70時間を加えた高温耐久性試験は行っていない。結果を表1に示す。なお、酸捕捉剤Eの分子量が小さく、偏光フィルム製造工程中で溶出しやすかったために、偏光フィルム中に残存したカルボジイミド化合物量が少なくなり、A2/D2の値が小さかった。
酸捕捉剤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、偏光フィルム及び偏光板を製造した。実施例1と同様に、これらについて各評価を行った。結果を表1に示す。また、図1に得られたPVAフィルムの波長200~400nmの範囲の吸収スペクトルを示す。
酸捕捉剤Aの含有量(添加量)をPVA100質量部に対して0.01質量部にしたこと以外は実施例1と同様にして、PVAフィルム、偏光フィルム及び偏光板を製造した。実施例1と同様に、これらについて各評価を行った。結果を表1に示す。
Claims (13)
- ポリビニルアルコールを含み、波長210nmにおける吸光度A1と平均厚みD1(mm)とが下記式(1)を満たすポリビニルアルコールフィルム。
A1/D1≧9 ・・・(1) - 上記吸光度A1と上記平均厚みD1(mm)とが下記式(2)を満たす、請求項1に記載のポリビニルアルコールフィルム。
9≦A1/D1≦80 ・・・(2) - 酸捕捉剤を含む、請求項1又は2に記載のポリビニルアルコールフィルム。
- ポリビニルアルコールと酸捕捉剤とを含み、上記ポリビニルアルコール100質量部に対する上記酸捕捉剤の含有量が0.1質量部以上であるポリビニルアルコールフィルム。
- 上記酸捕捉剤が有機化合物である、請求項3又は4に記載のポリビニルアルコールフィルム。
- 上記酸捕捉剤が、少なくとも1個のカルボジイミド基を有するカルボジイミド化合物である、請求項5に記載のポリビニルアルコールフィルム。
- 上記酸捕捉剤が水溶性である、請求項3~6のいずれか1項に記載のポリビニルアルコールフィルム。
- 上記酸捕捉剤が高分子である、請求項7に記載のポリビニルアルコールフィルム。
- 上記ポリビニルアルコールのけん化度が90モル%以上である、請求項1~8のいずれか1項に記載のポリビニルアルコールフィルム。
- 偏光板製造用である、請求項1~9のいずれか1項に記載のポリビニルアルコールフィルム。
- 請求項1~10のいずれか1項に記載のポリビニルアルコールフィルムから形成された偏光フィルム。
- ポリビニルアルコールを含み、60℃、90%RH雰囲気下に100時間静置した後の波長210nmにおける吸光度A2と平均厚みD2(mm)とが下記式(3)を満たす偏光フィルム。
A2/D2≧9 ・・・(3) - 請求項11又は12に記載の偏光フィルムと、セルロースエステル系樹脂を含む保護フィルムとを有する偏光板。
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020217027380A KR102898692B1 (ko) | 2019-03-14 | 2020-03-10 | 폴리비닐알코올 필름, 편광 필름, 및 편광판 |
| CN202080021119.0A CN113544555B (zh) | 2019-03-14 | 2020-03-10 | 聚乙烯醇膜、偏振膜和偏振板 |
| JP2021505095A JP7345541B2 (ja) | 2019-03-14 | 2020-03-10 | ポリビニルアルコールフィルム、偏光フィルム、及び偏光板 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019047344 | 2019-03-14 | ||
| JP2019-047344 | 2019-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020184587A1 true WO2020184587A1 (ja) | 2020-09-17 |
Family
ID=72426642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2020/010392 Ceased WO2020184587A1 (ja) | 2019-03-14 | 2020-03-10 | ポリビニルアルコールフィルム、偏光フィルム、及び偏光板 |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7345541B2 (ja) |
| KR (1) | KR102898692B1 (ja) |
| CN (1) | CN113544555B (ja) |
| TW (1) | TWI907345B (ja) |
| WO (1) | WO2020184587A1 (ja) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021206073A1 (ja) * | 2020-04-08 | 2021-10-14 | 日東電工株式会社 | 偏光フィルム |
| WO2021210342A1 (ja) * | 2020-04-14 | 2021-10-21 | 日東電工株式会社 | 偏光膜および偏光フィルム |
| 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 |
| KR20250133316A (ko) | 2022-12-26 | 2025-09-05 | 주식회사 쿠라레 | 폴리비닐알코올 필름 및 편광자 |
| WO2025205952A1 (ja) * | 2024-03-26 | 2025-10-02 | 三菱ケミカル株式会社 | 偏光フィルム及びその製造方法、並びに偏光板 |
| JP2026002709A (ja) * | 2024-06-20 | 2026-01-08 | 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、それを含む光学フィルム及びその製造方法 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI771225B (zh) * | 2021-11-16 | 2022-07-11 | 長春石油化學股份有限公司 | 聚乙烯醇薄膜、包含其之偏光薄膜及其製造方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011108350A1 (ja) * | 2010-03-03 | 2011-09-09 | コニカミノルタオプト株式会社 | 偏光板の製造方法、それを用いた偏光板、及び液晶表示装置 |
| JP2014102353A (ja) * | 2012-11-19 | 2014-06-05 | Nitto Denko Corp | 偏光板および画像表示装置、ならびにそれらの製造方法 |
| WO2017065259A1 (ja) * | 2015-10-16 | 2017-04-20 | 株式会社Adeka | 樹脂組成物およびこれを用いた光学フィルム |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101258549B1 (ko) * | 2009-05-14 | 2013-05-02 | 가부시키가이샤 지로 코포레토 프란 | 편광자 보호 필름, 편광판 및 액정 표시 소자 |
| CN102604294A (zh) | 2012-03-13 | 2012-07-25 | 朱春英 | Pva拉伸薄膜及其制备方法 |
| TWI686630B (zh) * | 2014-10-08 | 2020-03-01 | 日商可樂麗股份有限公司 | 偏光薄膜及其製造方法 |
| KR101839672B1 (ko) * | 2015-02-12 | 2018-03-16 | 스미또모 가가꾸 가부시키가이샤 | 편광 필름 및 그것을 포함하는 편광판 |
| JP7195039B2 (ja) * | 2015-10-16 | 2022-12-23 | 株式会社Adeka | 樹脂組成物およびこれを用いた光学フィルム |
| JP2018025764A (ja) | 2016-07-29 | 2018-02-15 | 住友化学株式会社 | 光学積層体 |
| CN113544230B (zh) | 2019-03-14 | 2024-02-23 | 株式会社可乐丽 | 粘接剂和偏振板 |
| JP2020180229A (ja) | 2019-04-25 | 2020-11-05 | 日本精機株式会社 | 粘着剤組成物及びそれを用いた液晶表示パネル |
-
2020
- 2020-03-10 KR KR1020217027380A patent/KR102898692B1/ko active Active
- 2020-03-10 JP JP2021505095A patent/JP7345541B2/ja active Active
- 2020-03-10 CN CN202080021119.0A patent/CN113544555B/zh active Active
- 2020-03-10 WO PCT/JP2020/010392 patent/WO2020184587A1/ja not_active Ceased
- 2020-03-13 TW TW109108328A patent/TWI907345B/zh active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011108350A1 (ja) * | 2010-03-03 | 2011-09-09 | コニカミノルタオプト株式会社 | 偏光板の製造方法、それを用いた偏光板、及び液晶表示装置 |
| JP2014102353A (ja) * | 2012-11-19 | 2014-06-05 | Nitto Denko Corp | 偏光板および画像表示装置、ならびにそれらの製造方法 |
| WO2017065259A1 (ja) * | 2015-10-16 | 2017-04-20 | 株式会社Adeka | 樹脂組成物およびこれを用いた光学フィルム |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021206073A1 (ja) * | 2020-04-08 | 2021-10-14 | 日東電工株式会社 | 偏光フィルム |
| WO2021210342A1 (ja) * | 2020-04-14 | 2021-10-21 | 日東電工株式会社 | 偏光膜および偏光フィルム |
| 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 |
| KR20250133316A (ko) | 2022-12-26 | 2025-09-05 | 주식회사 쿠라레 | 폴리비닐알코올 필름 및 편광자 |
| WO2025205952A1 (ja) * | 2024-03-26 | 2025-10-02 | 三菱ケミカル株式会社 | 偏光フィルム及びその製造方法、並びに偏光板 |
| JP2026002709A (ja) * | 2024-06-20 | 2026-01-08 | 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、それを含む光学フィルム及びその製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202045557A (zh) | 2020-12-16 |
| JPWO2020184587A1 (ja) | 2020-09-17 |
| KR20210139234A (ko) | 2021-11-22 |
| CN113544555A (zh) | 2021-10-22 |
| CN113544555B (zh) | 2024-12-27 |
| TWI907345B (zh) | 2025-12-11 |
| KR102898692B1 (ko) | 2025-12-15 |
| JP7345541B2 (ja) | 2023-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7345541B2 (ja) | ポリビニルアルコールフィルム、偏光フィルム、及び偏光板 | |
| CN104640912B (zh) | 聚乙烯醇膜和偏振膜 | |
| CN104204046B (zh) | 聚乙烯醇系聚合物膜和偏光膜 | |
| JP7394112B2 (ja) | 接着剤及び偏光板 | |
| KR102595403B1 (ko) | 편광 필름, 편광판, 및 그들의 제조 방법 | |
| KR102232980B1 (ko) | 광학 필름 제조용 원반 필름 | |
| TWI686630B (zh) | 偏光薄膜及其製造方法 | |
| JP2022008895A (ja) | 偏光フィルムの製造方法 | |
| KR102582196B1 (ko) | 편광 필름, 편광판, 및 그들의 제조 방법 | |
| JP5931125B2 (ja) | 偏光フィルムの製造方法 | |
| JP7328992B2 (ja) | ポリビニルアルコールフィルム及びそれを用いた偏光フィルムの製造方法 | |
| JP7583745B2 (ja) | ポリビニルアルコールフィルム及び偏光フィルム | |
| JP5606704B2 (ja) | 偏光フィルムの製造方法 | |
| KR20150091493A (ko) | 적층 필름 | |
| JP7839743B2 (ja) | 偏光フィルムの製造方法及び偏光フィルム | |
| JP2023056678A (ja) | ポリビニルアルコールフィルム、ポリビニルアルコールフィルムの製造方法、延伸フィルム及び偏光フィルム | |
| JP7093349B2 (ja) | 原反フィルム、延伸光学フィルムの製造方法、及び延伸光学フィルム | |
| JP7561262B2 (ja) | 偏光フィルム及びその製造方法 | |
| KR20170108013A (ko) | 필름 | |
| JP7627120B2 (ja) | 偏光子およびその製造方法 | |
| WO2024257822A1 (ja) | 偏光フィルム、偏光板および偏光板の製造方法 | |
| JP2025096399A (ja) | ポリビニルアルコールフィルム及びその製造方法 | |
| WO2025205952A1 (ja) | 偏光フィルム及びその製造方法、並びに偏光板 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20769715 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 2021505095 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 20769715 Country of ref document: EP Kind code of ref document: A1 |
|
| WWG | Wipo information: grant in national office |
Ref document number: 202080021119.0 Country of ref document: CN |
