WO2020196482A1 - Film de retard et plaque de polarisation avec couche de retard - Google Patents

Film de retard et plaque de polarisation avec couche de retard Download PDF

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Publication number
WO2020196482A1
WO2020196482A1 PCT/JP2020/012911 JP2020012911W WO2020196482A1 WO 2020196482 A1 WO2020196482 A1 WO 2020196482A1 JP 2020012911 W JP2020012911 W JP 2020012911W WO 2020196482 A1 WO2020196482 A1 WO 2020196482A1
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Prior art keywords
retardation
film
retardation film
dihydroxy compound
polarizing plate
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PCT/JP2020/012911
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English (en)
Japanese (ja)
Inventor
歩夢 中原
清水　享
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202080024435.3A priority Critical patent/CN113661194A/zh
Priority to JP2021509434A priority patent/JP7323602B2/ja
Priority to KR1020217025599A priority patent/KR20210148083A/ko
Publication of WO2020196482A1 publication Critical patent/WO2020196482A1/fr
Priority to JP2023122144A priority patent/JP2023145609A/ja

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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Definitions

  • the present invention relates to a retardation film and a polarizing plate with a retardation layer.
  • an image display device (organic EL display device) equipped with an organic EL panel
  • the organic EL panel has a highly reflective metal layer, and tends to cause problems such as reflection of external light and reflection of the background. Therefore, it is known to prevent these problems by providing a retardation film.
  • a conventional retardation film is used in an image display device, whitening and / or cracks may occur with use, and the folding resistance may be insufficient.
  • the present invention has been made to solve the above-mentioned conventional problems, and an object thereof is a retardation film in which whitening and cracks are suppressed and has excellent folding resistance, and such a retardation film. It is an object of the present invention to provide a polarizing plate with a retardation layer including a film.
  • the retardation film in the embodiment of the present invention contains a polycarbonate resin, and Re (450) / Re (550) is 0.98 to 1.03, and Re (550) is 80 nm to 190 nm.
  • the polycarbonate resin contains a structural unit derived from a dihydroxy compound represented by the following formula (4).
  • the retardation film suppresses cracks in the deformability test.
  • the retardation film suppresses whitening and cracking in the sebum resistance test.
  • the retardation film has a MIT count of 500 or more.
  • the moisture permeability of the retardation film is less than 130g / m 2 ⁇ 24h.
  • the retardation change of the retardation film after storage for 500 hours under the conditions of a temperature of 65 ° C. and a humidity of 90% is 2.0% or less.
  • a polarizing plate with a retardation layer is provided.
  • the polarizing plate with a retardation layer includes a retardation layer and a polarizer, and the retardation layer is composed of the retardation film.
  • the polarizing plate with a retardation layer is used on the visual side of an image display device.
  • a resin film containing a predetermined polycarbonate-based resin having a Re (450) / Re (550) of 0.98 to 1.03 and an in-plane retardation of 80 nm to 190 nm.
  • Refractive index (nx, ny, nz) “Nx” is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow-phase axis direction), and “ny” is the in-plane direction orthogonal to the slow-phase axis (that is, the phase-advance axis direction). Is the refractive index of, and "nz” is the refractive index in the thickness direction.
  • In-plane phase difference (Re) “Re ( ⁇ )” is an in-plane phase difference measured with light having a wavelength of ⁇ nm at 23 ° C.
  • Re (550) is an in-plane phase difference measured with light having a wavelength of 550 nm at 23 ° C.
  • Phase difference in the thickness direction (Rth) is a phase difference in the thickness direction measured with light having a wavelength of ⁇ nm at 23 ° C.
  • Rth (550) is a phase difference in the thickness direction measured with light having a wavelength of 550 nm at 23 ° C.
  • the retardation film according to the embodiment of the present invention contains a polycarbonate resin.
  • the retardation film according to the embodiment of the present invention is typically a stretched film of a polycarbonate resin film.
  • the retardation film exhibits a flat wavelength dispersion characteristic in which the retardation value hardly changes depending on the wavelength of the measurement light.
  • the Re (450) / Re (550) of the retardation film is 0.98 to 1.03, preferably 0.99 to 1.03, and more preferably 1.00 to 1.03.
  • a polycarbonate resin capable of obtaining such Re (450) / Re (550) a retardation film in which whitening and cracks are suppressed in a sebum resistance test and is excellent in shape processability and folding resistance can be obtained. Can be obtained. Further, with such a wavelength dispersion characteristic, excellent antireflection characteristics can be realized in a wide band.
  • the retardation characteristic of the retardation film is preferably nx> ny ⁇ nz.
  • the in-plane retardation Re (550) of the retardation layer film is 80 nm to 190 nm, preferably 100 nm to 170 nm, and more preferably 120 nm to 150 nm. That is, the retardation film can function as a ⁇ / 4 plate.
  • the retardation film has an Nz coefficient of preferably 0.9 to 1.5, and more preferably 0.9 to 1.3.
  • Nz coefficient is in such a range, an image display device having excellent dependence on the viewing angle of the reflectance and the reflected hue can be obtained.
  • the moisture permeability of the retardation film is preferably not more than 130g / m 2 ⁇ 24h, more preferably not more than 120g / m 2 ⁇ 24h.
  • the lower limit may be, for example, 1g / m 2 ⁇ 24h. If the moisture permeability of the retardation film is in such a range, it is possible to obtain an advantage that the change in retardation can be suppressed in a humid environment.
  • the retardation change of the retardation film after storage (humidification test) for 500 hours under the conditions of a temperature of 65 ° C. and a humidity of 90% is preferably 2.0% or less, more preferably 1.8% or less. Is.
  • the lower limit can be, for example, 0.01%.
  • the phase difference change (%) is represented by
  • Re 0 is the in-plane retardation (nm) of the retardation film before the start of the test
  • Re 500 is the in-plane retardation (nm) of the retardation film after the test. If the phase difference change of the retardation film is within such a range, it is possible to obtain an advantage that the hue change due to the phase difference at each location on the image display device is small and the occurrence of color unevenness on the display is suppressed. ..
  • the thickness of the retardation film can be appropriately set so as to function as a ⁇ / 4 plate.
  • the thickness is preferably 20 ⁇ m to 60 ⁇ m, more preferably 20 ⁇ m to 50 ⁇ m, and even more preferably 25 ⁇ m to 40 ⁇ m.
  • the absolute value of the photoelastic coefficient is preferably 2 ⁇ 10 -11 m 2 / N or less, more preferably 2.0 ⁇ 10 -13 m 2 / N to 1.5 ⁇ 10 -11 m 2. / N, more preferably from 1.0 ⁇ 10 -12 m 2 /N ⁇ 1.2 ⁇ 10 -11 m 2 / N.
  • the absolute value of the photoelastic coefficient is in such a range, the phase difference change is unlikely to occur when a shrinkage stress during heating occurs. As a result, thermal unevenness of the obtained image display device can be satisfactorily prevented.
  • the above retardation film has cracks suppressed in the deformability test. That is, the retardation film can be satisfactorily used even in applications requiring irregular shapes. Such an advantage can be obtained by including the specific polycarbonate resin described later in the retardation film.
  • the above retardation film has suppressed whitening and cracks in the sebum resistance test. That is, even when the retardation film is used, for example, on the visual side of an image display device and is continuously in contact with the user, it can retain good characteristics. This solves the problem recognized only when the retardation film is used for a long period of time on the visual side of an image display device, for example, and is an unexpectedly excellent effect. Such an advantage can be obtained by including the specific polycarbonate resin described later in the retardation film.
  • the retardation film has a MIT count of 500 or more. That is, the retardation film can exhibit excellent fold resistance even when used in a bendable (preferably foldable) image display device. Such an advantage can be obtained by stretching a resin film containing a specific polycarbonate resin described later under a specific stretching method and stretching conditions described later to form a retardation film.
  • the resin film retardation film is typically a stretched film of a polycarbonate resin film.
  • Polycarbonate resin contains at least a structural unit derived from a dihydroxy compound having a bond structure represented by the following structural formula (1), at least one bond in the molecular structure -CH 2 -O- It is produced by reacting a dihydroxy compound containing at least the dihydroxy compound having the above with a carbonic acid diester in the presence of a polymerization catalyst.
  • the dihydroxy compound having a bonding structure represented by the structural formula (1) includes a structure having two alcoholic hydroxyl groups and having a linking group ⁇ CH2-O— in the molecule, and is a polymerization catalyst. Any compound having any structure can be used as long as it is a compound capable of reacting with a carbonic acid diester to form polycarbonate in the presence of the compound, and a plurality of types may be used in combination. Further, as the dihydroxy compound used for the polycarbonate resin according to the present invention, a dihydroxy compound having no binding structure represented by the structural formula (1) may be used in combination.
  • the dihydroxy compound having a binding structure represented by the structural formula (1) is abbreviated as the dihydroxy compound (A), and the dihydroxy compound having no binding structure represented by the structural formula (1) is abbreviated as the dihydroxy compound (B).
  • the "linking group -CH 2 -O-" in the dihydroxy compounds (A), is meant the structure that constitutes the molecule bonded to each other with atoms other than hydrogen atoms.
  • this linking group at least an atom to which an oxygen atom can be bonded or an atom to which a carbon atom and an oxygen atom can be bonded at the same time is most preferably a carbon atom.
  • the number of "linking groups-CH 2- O-" in the dihydroxy compound (A) is preferably 1 or more, more preferably 2 to 4.
  • examples of the dihydroxy compound (A) include 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 9,9-bis (4- (2-hydroxyethoxy) -3).
  • -Methylphenyl) fluorene 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9- Bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4-) As
  • Methylphenyl] sulfides as exemplified by bishydroxyalkoxyarylsulfones, 1,4-bishydroxyethoxybenzene, 1,3-bishydroxyethoxybenzene, 1,2-bishydroxyethoxybenzene, 1,3-bis [2- [4- (2-Hydroxyethoxy) phenyl] propyl] benzene, 1,4-bis [2- [4- (2-hydroxyethoxy) phenyl] propyl] benzene, 4,4'-bis (2-) Hydroxyethoxy) biphenyl, 1,3-bis [4- (2-hydroxyethoxy) phenyl] Examples thereof include compounds having a cyclic ether structure such as -5,7-dimethyladamantane, anhydrous sugar alcohol represented by the dihydroxy compound represented by the following formula (4), and spiroglycol represented by the following general formula (6). These may be used alone or in combination of two or more.
  • dihydroxy compounds (A) may be used alone or in combination of two or more.
  • examples of the dihydroxy compound represented by the above formula (4) include isosorbide, isomannide, and isoidet having a stereoisomeric relationship, and one of these may be used alone or two or more. May be used in combination.
  • isosorbide obtained by dehydration condensation of sorbitol, which is abundant as a resource and is produced from various readily available starches, is easy to obtain and produce, and has optical properties. Most preferable from the viewpoint of moldability.
  • isosorbide is preferably used as the dihydroxy compound (A).
  • the dihydroxy compound (B) which is a dihydroxy compound other than the dihydroxy compound (A)
  • the dihydroxy compound (B) for example, an alicyclic dihydroxy compound, an aliphatic dihydroxy compound, an oxyalkylene glycol, an aromatic dihydroxy compound, and diols having a cyclic ether structure are used as the dihydroxy compound as a constituent unit of the polycarbonate. It can be used together with the dihydroxy compound (A), for example, the dihydroxy compound represented by the formula (4).
  • the alicyclic dihydroxy compound that can be used in the present invention is not particularly limited, but a compound having a 5-membered ring structure or a 6-membered ring structure is usually used. Further, the 6-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. Since the alicyclic dihydroxy compound has a 5-membered ring or 6-membered ring structure, the heat resistance of the obtained polycarbonate can be increased.
  • the number of carbon atoms contained in the alicyclic dihydroxy compound is usually 70 or less, preferably 50 or less, and more preferably 30 or less. The larger this value, the higher the heat resistance, but the synthesis becomes difficult, the purification becomes difficult, and the cost becomes high. The smaller the number of carbon atoms, the easier it is to purify and obtain.
  • alicyclic dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure that can be used in the present invention include alicyclic dihydroxy compounds represented by the following general formulas (II) or (III). Be done.
  • R 1 and R 2 each represent a cycloalkylene group having 4 to 20 carbon atoms.
  • R 1 is the following general formula (IIa) (in the formula, R 3 has 1 to 1 carbon atoms. Includes various isomers represented by 12 alkyl groups or hydrogen atoms). Specific examples thereof include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol.
  • R 1 is the following general formula (IIb) (in the formula). , N represents 0 or 1) and includes various isomers represented by).
  • R 1 is the following general formula (IIc) (in the formula, in the formula).
  • m includes various isomers represented by 0 or 1). Specific examples thereof include 2,6-decalin dimethanol, 1,5-decalin dimethanol, and 2,3-decalin dimethanol.
  • norbornane dimethanol which is an alicyclic dihydroxy compound represented by the above general formula (II)
  • various isomers in which R 1 is represented by the following general formula (IId) in the general formula (II) are used. Include. Specific examples of such a substance include 2,3-norbornane dimethanol, 2,5-norbornane dimethanol and the like.
  • the adamantane dimethanol which is an alicyclic dihydroxy compound represented by the general formula (II), includes various isomers in which R 1 is represented by the following general formula (IIe) in the general formula (II). Specific examples of such a substance include 1,3-adamantane dimethanol and the like.
  • R 2 is the following general formula (IIIa) (in the formula, R 3 has 1 to 1 carbon atoms. Includes various isomers represented by 12 alkyl groups or hydrogen atoms. Specific examples of such a product include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol and the like.
  • R 2 is the following general formula (IIIb) (in the formula, n). Indicates 0 or 1) and includes various isomers represented by).
  • R 2 is the following general formula (IIIc) (in the formula, m is 0). , Or various isomers represented by 1). Specifically, 2,6-decalin diol, 1,5-decalin diol, 2,3-decalin diol and the like are used as such.
  • the norbornane diol which is an alicyclic dihydroxy compound represented by the general formula (III), in the general formula (III), includes various isomers where R 2 is represented by the following general formula (IIId). Specifically, 2,3-norbornanediol, 2,5-norbornanediol and the like are used as such.
  • the adamantane diol which is an alicyclic dihydroxy compound represented by the general formula (III), in the general formula (III), includes various isomers where R 2 is represented by the following general formula (IIIe). Specifically, 1,3-adamantane diol and the like are used as such substances.
  • cyclohexanedimethanol, tricyclodecanedimethanol, adamantandiol, and pentacyclopentadecanedimethanol are particularly preferable, and are easily available and easy to handle. From this point of view, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecanedimethanol are preferable.
  • tricyclodecanedimethanol is preferably used as the dihydroxy compound (B).
  • Examples of the aliphatic dihydroxy compound that can be used in the present invention include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, and 1,2-butanediol. Examples include diol, 1,5-heptanediol, and 1,6-hexanediol.
  • Examples of oxyalkylene glycols that can be used in the present invention include diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol.
  • diols having a cyclic ether structure examples include spiroglycols and dioxane glycols.
  • the above-exemplified compound is an example of an alicyclic dihydroxy compound, an aliphatic dihydroxy compound, an oxyalkylene glycol, an aromatic dihydroxy compound, and a diol having a cyclic ether structure that can be used in the present invention. It is not limited. One or more of these compounds can be used together with the dihydroxy compound represented by the formula (4).
  • the ratio of the dihydroxy compound (A), for example, the dihydroxy compound represented by the formula (4) to all the dihydroxy compounds constituting the polycarbonate resin according to the present invention is not particularly limited, but is preferably 10 mol% or more, more preferably 40 mol. % Or more, more preferably 60 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less. If the content ratio of the structural unit derived from other dihydroxy compounds is too large, the performance such as optical characteristics may be deteriorated.
  • the dihydroxy compound (A) with respect to all the dihydroxy compounds constituting the polycarbonate for example, the dihydroxy compound represented by the formula (4) and the alicyclic dihydroxy compound
  • the total ratio is not particularly limited, but is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more.
  • the content ratio of the dihydroxy compound (A) for example, the structural unit derived from the dihydroxy compound represented by the formula (4) and the structural unit derived from the alicyclic dihydroxy compound in the polycarbonate resin according to the present invention.
  • the number of structural units derived from the dihydroxy compound represented by the formula (4) is larger than the above range and the number of structural units derived from the alicyclic dihydroxy compound is smaller, coloring becomes easier, and conversely, the dihydroxy represented by the formula (4). If the number of structural units derived from the compound is small and the number of structural units derived from the alicyclic dihydroxy compound is large, the molecular weight tends to be difficult to increase.
  • the dihydroxy compound (A) with respect to all the dihydroxy compounds constituting the polycarbonate, for example, is represented by the formula (4).
  • the total ratio of the dihydroxy compound and each of these dihydroxy compounds is not particularly limited and can be selected at any ratio.
  • the content ratio of the dihydroxy compound (A), for example, the structural unit derived from the dihydroxy compound represented by the formula (4) and the structural unit derived from each of these dihydroxy compounds is not particularly limited, and can be selected at an arbitrary ratio. it can.
  • Method for producing a retardation film includes stretching a resin film.
  • the resin film is a film formed from the polycarbonate resin described in Section B above.
  • the retardation film can be made by biaxial stretching.
  • the biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching.
  • the stretching ratio in the longitudinal direction is preferably more than 1.0 times and 2.0 times or less, and more preferably 1.1 times to 1.5 times.
  • the draw ratio in the width direction is preferably 1.6 times to 2.2 times, more preferably 1.8 times to 2.0 times.
  • the stretching temperature of the resin film is preferably Tg-30 ° C to Tg + 30 ° C, more preferably Tg-15 ° C to Tg + 15 ° C, and even more preferably Tg-10 ° C to Tg + 10 ° C.
  • Tg is the glass transition temperature of the constituent material of the film.
  • the present invention includes a polarizing plate with a retardation layer having the retardation film.
  • the polarizing plate with a retardation layer according to the embodiment of the present invention includes a polarizing plate and a retardation layer composed of the retardation film.
  • the polarizing plate includes a polarizer, a first protective layer arranged on one side of the polarizer, and a second protective layer arranged on the other side of the polarizer.
  • the angle formed by the absorption axis of the polarizing element of the polarizing plate and the slow axis of the retardation film can be appropriately set according to the application and purpose. In one embodiment, the angle is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and even more preferably about 45 °.
  • an isotropic base material with a conductive layer or a conductive layer may be provided.
  • the conductive layer or the isotropic base material with the conductive layer is typically provided on the outside of the polarizing plate (on the side opposite to the retardation layer).
  • the polarizing plate with a retardation layer can be applied to a so-called inner touch panel type input display device in which a touch sensor is incorporated between an image display cell and the polarizing plate. ..
  • the polarizing plate with a retardation layer of the present invention may be single-wafered or elongated.
  • the term "long” means an elongated shape having a length sufficiently long with respect to the width, and for example, an elongated shape having a length of 10 times or more, preferably 20 times or more with respect to the width. Including.
  • the long-shaped polarizing plate with a retardation layer can be wound in a roll shape.
  • the polarizing plate and the retardation layer are also elongated.
  • the polarizer preferably has an absorption axis in the longitudinal direction.
  • the retardation layer is preferably a diagonally stretched film having a slow axis in a direction forming an angle of, for example, 40 ° to 50 ° with respect to the elongated direction. If the polarizer and the retardation layer have such a configuration, a polarizing plate with a retardation layer can be produced by roll-to-roll.
  • the polarizing plate with a retardation layer has an adhesive layer as the outermost layer on the image display cell side, and can be attached to the image display cell. Further, it is preferable that a release film is temporarily attached to the image display cell side of the pressure-sensitive adhesive layer until a polarizing plate with a retardation layer is used. By temporarily attaching the release film, the pressure-sensitive adhesive layer can be protected and rolls can be formed.
  • the polarizing plate typically has a polarizing element and a protective layer arranged on at least one side of the polarizing element.
  • the resin film forming the polarizer may be a single-layer resin film or a laminated body having two or more layers.
  • the polarizer composed of a single-layer resin film include a hydrophilic polymer film such as a polyvinyl alcohol (PVA) -based film, a partially formalized PVA-based film, and an ethylene / vinyl acetate copolymer system partially saponified film.
  • a hydrophilic polymer film such as a polyvinyl alcohol (PVA) -based film, a partially formalized PVA-based film, and an ethylene / vinyl acetate copolymer system partially saponified film.
  • PVA polyvinyl alcohol
  • a partially formalized PVA-based film ethylene / vinyl acetate copolymer system partially saponified film
  • examples thereof include those which have been dyed and stretched with a bicolor substance such as iodine or a bicolor dye, and polyene-based oriented films such as a dehydrated product of PVA and a dehydrogenated product of polyvinyl chloride.
  • the dyeing with iodine is performed, for example, by immersing a PVA-based film in an aqueous iodine solution.
  • the draw ratio of the uniaxial stretching is preferably 3 to 7 times. Stretching may be performed after the dyeing treatment or while dyeing. Moreover, you may dye after stretching.
  • the PVA-based film is subjected to a swelling treatment, a cross-linking treatment, a washing treatment, a drying treatment and the like. For example, by immersing the PVA-based film in water and washing it with water before dyeing, it is possible not only to clean the dirt on the surface of the PVA-based film and the blocking inhibitor, but also to swell the PVA-based film to prevent uneven dyeing. Can be prevented.
  • the polarizer obtained by using the laminate include a laminate of a resin base material and a PVA-based resin layer (PVA-based resin film) laminated on the resin base material, or a resin base material and the resin.
  • PVA-based resin film PVA-based resin film
  • examples thereof include a polarizer obtained by using a laminate with a PVA-based resin layer coated and formed on a base material. Details of the method for producing such a polarizer are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. The description of the patent document is incorporated herein by reference. The entire description of the publication is incorporated herein by reference.
  • the thickness of the polarizer is preferably 1 ⁇ m to 25 ⁇ m, more preferably 3 ⁇ m to 10 ⁇ m, and even more preferably 3 ⁇ m to 8 ⁇ m.
  • the thickness of the polarizer is in such a range, curling during heating can be satisfactorily suppressed, and good appearance durability during heating can be obtained.
  • the protective layer is formed of any suitable protective film that can be used as a film to protect the polarizer.
  • the material that is the main component of the protective film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone.
  • TAC triacetyl cellulose
  • polyester-based polyvinyl alcohol-based
  • polycarbonate-based polyamide-based
  • polyimide-based polyimide-based
  • polyethersulfone-based polysulfone
  • examples thereof include transparent resins such as polyester-based, polystyrene-based, polycarbonate-based, polyolefin-based, (meth) acrylic-based, and acetate-based.
  • thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone, or ultraviolet curable resins can also be mentioned.
  • glassy polymers such as siloxane-based polymers can also be mentioned.
  • the polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used.
  • a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain.
  • the polymer film can be, for example, an extruded product of the above resin composition.
  • the inner protective layer is optically isotropic.
  • optically isotropic means that the in-plane retardation Re (550) is 0 nm to 10 nm and the thickness direction retardation Rth (550) is -10 nm to +10 nm.
  • the protective layer may be made of any suitable material as long as it is isotropic to the optical body. The material can be appropriately selected from the materials mentioned above with respect to the protective layer.
  • the thickness of the protective layer is preferably 10 ⁇ m to 100 ⁇ m.
  • the protective layer may be laminated on the polarizer via an adhesive layer (specifically, an adhesive layer or an adhesive layer), or may be laminated in close contact with the polarizer (without an adhesive layer). Good. If necessary, a surface treatment layer such as a hard coat layer, an antiglare layer, and an antireflection layer can be formed on the protective layer arranged on the outermost surface of the polarizing plate with a retardation layer.
  • the polarizing plate with a retardation layer can be used on the visual side of an image display device. Further, the retardation layer in the polarizing plate with a retardation layer may be arranged on the viewing side or on the display cell side. When the retardation layer in the polarizing plate with the retardation layer is arranged on the visual side, whitening and cracks can be suppressed in the sebum resistance test. When the retardation layer in the polarizing plate with a retardation layer is arranged on the display cell side, excellent reflectance can be obtained.
  • the measurement method and evaluation method for each characteristic are as follows.
  • (1) In-plane retardation and wavelength dispersion characteristics The retardation films obtained in Examples and Comparative Examples were cut into lengths of 4 cm and widths of 4 cm and used as measurement samples.
  • the in-plane phase difference Re (550) was measured using the product name "Axoscan” manufactured by Axometrics.
  • Re (450) was also measured, and Re (450) / Re (550) was calculated.
  • Humidity Permeability The retardation films obtained in Examples and Comparative Examples have an area of 1 m 2 in an atmosphere of a temperature of 40 ° C.
  • the retardation film or polarizing plate with a retardation layer obtained in Examples and Comparative Examples is irradiated with a CO 2 laser at an energy of 3 Kw in the flow direction of the film and in the direction perpendicular to the flow direction. It was cut to obtain a measurement sample of 200 mm ⁇ 200 mm. The cut part was observed using a laser microscope, and was marked with ⁇ if there were no cracks, and x if there were cracks and / or could not be cut.
  • Skin oil resistance test The retardation film or polarizing plate with a retardation layer obtained in Examples and Comparative Examples is cut out to a size of 5 cm ⁇ 5 cm, and an adhesive is attached to one surface with a hand roller to obtain an adhesive surface.
  • the MIT test was conducted in accordance with JIS P 8115. Specifically, the retardation films obtained in Examples and Comparative Examples were cut out to a length of 15 cm and a width of 1.5 cm and used as measurement samples.
  • the laminate was mounted on an organic EL panel, and the reflectance was measured by a spectrophotometric system. Those having a reflectance of 2.0% or less were evaluated as ⁇ , and those having a reflectance of more than 2.0% were evaluated as x.
  • (8) Dimensional shrinkage rate The polarizing plate with a retardation layer obtained in Examples and Comparative Examples was cut into a width of 100 mm and a length of 100 mm (test piece), and the four corners were scratched with a cloth and the central portion of the cross scratch 4 The length (mm) before heating in the longitudinal direction (MD direction) and the width direction (TD direction) of the points was measured by a CNC coordinate measuring machine (LEGEX774 manufactured by Mitutoyo Co., Ltd.).
  • Heat shrinkage rate (%) [[Length before heating (mm) -Length after heating (mm)] / Length before heating (mm)] x 100 Those having a heat shrinkage rate of 0% to 0.5% were evaluated as ⁇ , and those having a heat shrinkage rate of 0.5% or more were evaluated as x.
  • Example 1 Preparation of resin film Isosorbide (hereinafter sometimes abbreviated as "ISB") 81.98 parts by mass, tricyclodecanedimethanol (hereinafter sometimes abbreviated as “TCDDM”) 47.19 parts by mass, diphenyl 175.1 parts by mass of carbonate (hereinafter sometimes abbreviated as "DPC”) and 0.979 parts by mass of a 0.2% by mass aqueous solution of cesium carbonate as a catalyst were put into a reaction vessel, and the reaction was carried out in a nitrogen atmosphere.
  • the heating tank temperature was heated to 150 ° C., and the raw materials were dissolved while stirring as necessary (about 15 minutes).
  • the pressure was changed from normal pressure to 13.3 kPa, and the generated phenol was extracted from the reaction vessel while raising the heating tank temperature to 190 ° C. in 1 hour.
  • the pressure inside the reaction vessel is set to 6.67 kPa, the heating tank temperature is raised to 230 ° C. in 15 minutes, and the generated phenol is generated. It was taken out of the reaction vessel. Since the stirring torque of the stirrer increased, the temperature was raised to 250 ° C. in 8 minutes, and the pressure in the reaction vessel was brought to 0.200 kPa or less in order to remove the generated phenol.
  • the unstretched polycarbonate resin film was subjected to preheat treatment and simultaneous biaxial stretching using a simultaneous biaxial stretching machine to obtain a retardation film.
  • the preheating temperature was 138.5 ° C.
  • the stretching temperature was 138.5 ° C.
  • the stretching ratio in the longitudinal direction was 1.2 times
  • the stretching ratio in the width direction was 1.9 times.
  • Wavelength dispersion value of the obtained retardation film was 1.025
  • the in-plane retardation Re (550) is 135 nm
  • the moisture permeability is 110g / m 2 ⁇ 24h
  • the phase difference change 1.5% Met The obtained retardation film was subjected to the evaluations (4) to (6) above. The results are shown in Table 1.
  • Example 2 A retardation film was obtained in the same manner as in Example 1 except that the stretching temperature was 137.5 ° C. Wavelength dispersion value of the obtained retardation film was 1.022, the in-plane retardation Re (550) is 140 nm, the moisture permeability is 88g / m 2 ⁇ 24h, the phase difference change is 0.9% Met. The obtained retardation film was subjected to the evaluations (4) to (7) above. The results are shown in Table 1.
  • Example 3 A retardation film was obtained in the same manner as in Example 1 except that the stretching temperature was 137 ° C. Wavelength dispersion value of the obtained retardation film was 1.022, the in-plane retardation Re (550) is 144 nm, the moisture permeability is 82g / m 2 ⁇ 24h, the phase difference change is 0.8% Met. The obtained retardation film was subjected to the evaluations (4) to (7) above. The results are shown in Table 1.
  • Example 4 A retardation film was obtained in the same manner as in Example 1 except that the stretching temperature was 136.5 ° C. Wavelength dispersion value of the obtained retardation film was 1.021, the in-plane retardation Re (550) is 100 nm, the moisture permeability is 85g / m 2 ⁇ 24h, the phase difference change is 1.2% Met. The obtained retardation film was subjected to the evaluations (4) to (6) above. The results are shown in Table 1.
  • Example 5 A retardation film was obtained in the same manner as in Example 1 except that the stretching temperature was 139 ° C. Wavelength dispersion value of the obtained retardation film was 1.026, the in-plane retardation Re (550) is 155 nm, the moisture permeability is 81g / m 2 ⁇ 24h, the phase difference change is 0.9% Met. The obtained retardation film was subjected to the evaluations (4) to (7) above. The results are shown in Table 1.
  • Example 6 1. Preparation of Resin Film and Preparation of Phase Difference Film A retardation film was obtained in the same manner as in Example 1 except that the stretching temperature was set to 137 ° C. Wavelength dispersion value of the obtained retardation film was 1.020, the in-plane retardation Re (550) is 144 nm, the moisture permeability is 87g / m 2 ⁇ 24h, the phase difference change is 0.8% Met. The obtained retardation film was subjected to the evaluation of (7) above. The results are shown in Table 1.
  • polarizing plate As the resin base material, an amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 ⁇ m) having a Tg of about 75 ° C. was used, and one side of the resin base material was corona-treated. did. 100 parts by weight of PVA-based resin in which polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and acetacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosefimmer”) are mixed at a ratio of 9: 1.
  • a PVA aqueous solution (coating solution) was prepared by dissolving 13 parts by weight of potassium iodide in water.
  • a PVA-based resin layer having a thickness of 13 ⁇ m was formed by applying the above PVA aqueous solution to the corona-treated surface of the resin base material and drying at 60 ° C. to prepare a laminate.
  • the obtained laminate was uniaxially stretched 2.4 times in the longitudinal direction (longitudinal direction) in an oven at 130 ° C. (aerial auxiliary stretching treatment). Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C.
  • a cycloolefin-based film (manufactured by Nippon Zeon Co., Ltd., trade name "Zeonoa”) is bonded to the surface of the obtained polarizing element opposite to the resin base material via an ultraviolet curable adhesive as a protective layer. It was. Specifically, the curable adhesive was coated so as to have a total thickness of about 1.0 ⁇ m, and bonded using a roll machine. Then, a UV ray was irradiated from the cycloolefin film side to cure the adhesive. Next, the resin base material was peeled off to obtain a polarizing plate having a cycloolefin-based film (protective layer) / polarizer. The in-plane phase difference of the protective layer was 135 nm. The angle between the slow axis of the protective layer and the absorption axis of the polarizer was made substantially parallel.
  • Example 7 A retardation film was obtained in the same manner as in Example 1 except that the stretching temperature was 142 ° C. Wavelength dispersion value of the obtained retardation film was 1.020, the in-plane retardation Re (550) is 140 nm, the moisture permeability is 84g / m 2 ⁇ 24h, the phase difference change is 0.7% Met. Further, the obtained retardation film was subjected to the evaluation of (7) above. Next, using the obtained retardation film, a polarizing plate with a retardation layer was obtained in the same manner as in Example 6. The obtained polarizing plate with a retardation layer was subjected to the evaluations of (4), (5) and (8) above. The results are shown in Table 1.
  • Example 8 A retardation film was obtained in the same manner as in Example 1 except that the stretching temperature was 147 ° C. Wavelength dispersion value of the obtained retardation film was 1.020, the in-plane retardation Re (550) is 140 nm, the moisture permeability is 89g / m 2 ⁇ 24h, the phase difference change is 0.8% Met. Further, the obtained retardation film was subjected to the evaluation of (7) above. Next, using the obtained retardation film, a polarizing plate with a retardation layer was obtained in the same manner as in Example 6. The obtained polarizing plate with a retardation layer was subjected to the evaluations of (4), (5) and (8) above. The results are shown in Table 1.
  • Example 1 A retardation film was obtained in the same manner as in Example 1 except that the stretching temperature was 135 ° C. Wavelength dispersion value of the obtained retardation film was 1.021, the in-plane retardation Re (550) is 210 nm, the moisture permeability is 89g / m 2 ⁇ 24h, the phase difference change is 0.8% Met. The obtained retardation film was subjected to the evaluations (4) to (7) above. The results are shown in Table 1.
  • Example 2 The same as in Example 1 except that a commercially available cycloolefin-based resin film (manufactured by Nippon Zeon Co., Ltd., trade name "Zeonoa”) was used as the resin film and stretched at a preheating temperature of 180 ° C. and a stretching temperature of 175 ° C. A retardation film was obtained. Wavelength dispersion value of the obtained retardation film was 1.01, in-plane retardation Re (550) is 135 nm, the moisture permeability is 29g / m 2 ⁇ 24h, the phase difference change is 0.8% Met. The obtained retardation film was subjected to the evaluations (4) to (7) above. The results are shown in Table 1.
  • Example 3 The rubbing treatment was performed by adjusting the rotation axis of the rubbing roller to be 45 ° counterclockwise with respect to the longitudinal direction of the triacetyl cellulose (TAC) film (manufactured by Fuji Film Co., Ltd.).
  • TAC triacetyl cellulose
  • the rubbing-treated TAC film was coated with a liquid crystal to obtain a liquid crystal-coated triacetyl cellulose (TAC) film.
  • a retardation film was obtained in the same manner as in Example 1 except that this liquid crystal coated TAC film was used as the resin film and no stretching was performed.
  • Wavelength dispersion value of the obtained retardation film was 1.09, in-plane retardation Re (550) is 132 nm, the moisture permeability is 330g / m 2 ⁇ 24h, the phase difference change is 4.0% Met.
  • the obtained retardation film was subjected to the evaluations (4) to (6) above. The results are shown in Table 1.
  • the obtained retardation film was subjected to the evaluation of (7) above.
  • the results are shown in Table 1.
  • a polarizing plate with a retardation layer was obtained in the same manner as in Example 6.
  • the obtained polarizing plate with a retardation layer was subjected to the evaluations of (4), (5) and (8) above. The results are shown in Table 1.
  • the retardation film of the embodiment of the present invention is excellent in all of the moisture permeability, the retardation change, the deformability test, the sebum resistance test and the MIT test. Further, it can be seen that when the retardation film of the embodiment of the present invention is provided on the panel side of the image display device, it exhibits excellent reflectance. Further, it can be seen that the polarizing plate with a retardation layer according to the embodiment of the present invention is excellent in all of the deformability test, the sebum resistance test and the dimensional change rate. It is presumed that this is realized by stretching a resin film containing a specific polycarbonate resin under a specific stretching method and stretching conditions.
  • the retardation film according to the embodiment of the present invention is suitably used for an image display device.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Polyesters Or Polycarbonates (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention concerne un film de retard dans lequel le blanchiment et la fissuration sont supprimés et qui présente une excellente endurance au pliage. Ce film de retard contient une résine de polycarbonate prescrite, le Re (450)/Re (550) est de 0,98-1,03, et le Re (550) est de 80 à 190 nm.
PCT/JP2020/012911 2019-03-27 2020-03-24 Film de retard et plaque de polarisation avec couche de retard WO2020196482A1 (fr)

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JP2021509434A JP7323602B2 (ja) 2019-03-27 2020-03-24 位相差フィルムおよび位相差層付偏光板
KR1020217025599A KR20210148083A (ko) 2019-03-27 2020-03-24 위상차 필름 및 위상차층 부착 편광판
JP2023122144A JP2023145609A (ja) 2019-03-27 2023-07-27 位相差フィルムおよび位相差層付偏光板

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050143554A1 (en) * 2003-12-31 2005-06-30 General Electric Company Aliphatic diol polycarbonates and their preparation
WO2008020636A1 (fr) * 2006-08-18 2008-02-21 Mitsubishi Gas Chemical Company, Inc. Résine de polycarbonate et film optique utilisant celle-ci
JP2014026266A (ja) * 2012-06-21 2014-02-06 Nitto Denko Corp 偏光板および有機ｅｌパネル
JP2014205829A (ja) * 2013-03-21 2014-10-30 三菱化学株式会社 樹脂組成物及びそれを用いたフィルム

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JP5448264B2 (ja) * 2009-11-19 2014-03-19 三菱化学株式会社 ポリカーボネート樹脂フィルム並びに透明フィルム
KR101713277B1 (ko) 2010-08-13 2017-03-08 삼성전자주식회사 반사 방지 필름 및 상기 반사 방지 필름을 채용한 접이식 디스플레이 장치
JP6784481B2 (ja) * 2015-07-13 2020-11-11 日東電工株式会社 有機ｅｌ表示装置用円偏光板および有機ｅｌ表示装置
JP6565577B2 (ja) 2015-10-15 2019-08-28 三菱ケミカル株式会社 ポリカーボネート樹脂、及びそれよりなる光学フィルム

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050143554A1 (en) * 2003-12-31 2005-06-30 General Electric Company Aliphatic diol polycarbonates and their preparation
WO2008020636A1 (fr) * 2006-08-18 2008-02-21 Mitsubishi Gas Chemical Company, Inc. Résine de polycarbonate et film optique utilisant celle-ci
JP2014026266A (ja) * 2012-06-21 2014-02-06 Nitto Denko Corp 偏光板および有機ｅｌパネル
JP2014205829A (ja) * 2013-03-21 2014-10-30 三菱化学株式会社 樹脂組成物及びそれを用いたフィルム

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