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WO2017110342A1 - Film de protection de plaque polarisante, son procédé de production, et plaque polarisante - Google Patents

Film de protection de plaque polarisante, son procédé de production, et plaque polarisante Download PDF

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Publication number
WO2017110342A1
WO2017110342A1 PCT/JP2016/084473 JP2016084473W WO2017110342A1 WO 2017110342 A1 WO2017110342 A1 WO 2017110342A1 JP 2016084473 W JP2016084473 W JP 2016084473W WO 2017110342 A1 WO2017110342 A1 WO 2017110342A1
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WIPO (PCT)
Prior art keywords
polarizing plate
protective film
ring
plate protective
general formula
Prior art date
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PCT/JP2016/084473
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English (en)
Japanese (ja)
Inventor
高木　隆裕
翔太 岩間
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to CN201680075206.8A priority Critical patent/CN108474892B/zh
Priority to JP2017557805A priority patent/JP6724930B2/ja
Publication of WO2017110342A1 publication Critical patent/WO2017110342A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

Definitions

  • the present invention relates to a polarizing plate protective film, a production method thereof, and a polarizing plate. More specifically, in the present invention, when a polarizing plate is bonded to a polarizer, the polarizing plate protective film is less prone to cracking even under use conditions where it is repeatedly exposed to a high temperature / low temperature environment such as a heat cycle test. Etc.
  • Liquid crystal display devices are conventionally used in desktop calculators and electronic watches. Furthermore, recently, it has come to be used regardless of the screen size from a mobile device such as a mobile phone to a large-sized television, and its application is spreading rapidly.
  • an organic electroluminescence (organic EL) display device has a tendency to increase in demand mainly for mobile use.
  • a pair of polarizing plates is usually arranged on the front and back of a liquid crystal cell to constitute a liquid crystal panel.
  • an organic EL panel having an antireflection function in which a polarizing plate, particularly an elliptical or circularly polarizing plate is disposed on the viewing side of the organic EL element is often used.
  • An elliptical or circularly polarizing plate is obtained by laminating a quarter-wave retardation plate (that is, a ⁇ / 4 plate) on a linear polarizing plate so that their slow axes intersect at a predetermined angle.
  • a polarizing plate (linear polarizing plate) widely used in the image display apparatus as described above is a liquid adhesive on both surfaces of a polarizer in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin film. And a transparent protective film, typically a triacetyl cellulose film.
  • An image display such as a liquid crystal cell or an organic EL element using a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive) as it is or in a form in which an optical layer such as a retardation film having optical characteristics is bonded as it is. It is bonded to the element to form a display panel and further an image display device.
  • the retardation film a film obtained by stretching and orienting a film made of a hydrogenated (hereinafter referred to as hydrogenated) norbornene resin having excellent performance in heat resistance, optical properties, transparency, electrical properties and the like. Widely used.
  • hydrogenated a hydrogenated norbornene resin having excellent performance in heat resistance, optical properties, transparency, electrical properties and the like. Widely used.
  • the film surface is bonded to a polarizer to produce a polarizing plate, and left in a high temperature environment.
  • a heat cycle test in which the film was left in a low temperature environment was repeatedly performed, the film sometimes cracked.
  • the polarizing plate protective film surface of the polarizing plate was bonded to the glass substrate, the polarizing plate sometimes peeled off from the glass substrate in a high temperature environment.
  • Patent Document 1 discloses that a hydrogenated norbornene resin and a rubber component are dissolved or dispersed in a solvent and cast ( A film formed by the (cast) method is disclosed. This is to improve the elongation by blending a rubber component with the hydrogenated norbornene resin.
  • the obtained film is inferior in optical properties such as parallel light transmittance, and cannot be used as a polarizing plate protective film.
  • the present inventor conducted a durability test (after exposure to high temperature conditions) in a state where a polarizing plate using a hydrogenated norbornene-based resin film as a polarizing plate protective film was bonded to a glass substrate of a liquid crystal cell with an adhesive. And leaving it at room temperature), it has been found that there is a problem that cracks occur in the polarizing plate protective film on the surface in contact with the air opposite to the liquid crystal cell after the durability test. Such a crack occurs even if the residual stress of the film is small.
  • Patent Document 3 describes that in order to improve cracks, it is important to prevent a decrease in the strength of the film under stress, and the change in tensile strength before and after the constant load tensile test is small. Although it is effective to add rubber, it is described that it is not sufficient to add rubber, and it is necessary to devise such as finely and uniformly finely dispersing rubber.
  • the present invention has been made in view of the above problems, and the problem to be solved is that when a polarizing plate protective film containing a hydrogenated norbornene resin is bonded to a polarizer to produce a polarizing plate, It is providing the polarizing plate protective film which can be set as the polarizing plate which is hard to produce a crack even if it implements a cycle test, and its manufacturing method. Moreover, it is providing the polarizing plate provided with the said polarizing plate protective film.
  • the present inventors have problems such as cracking and peeling when a polarizing plate protective film containing a hydrogenated norbornene-based resin is used for a polarizing plate.
  • a polarizing plate protective film containing a hydrogenated norbornene-based resin has been found to be due to the change in the contraction stress of the polarizer accompanying the change in the environmental temperature and that the above problem can be solved by incorporating a specific compound into the polarizing plate protective film and matching the polarizer film.
  • the present invention has been reached.
  • R ⁇ 1 > and R ⁇ 2 > represents a hydrogen atom, a methyl group, or a halogen atom each independently.
  • Ring A 1 , Ring A 2 and Ring A 3 each independently represent a benzene ring, cyclohexane ring, cyclohexene ring, naphthalene ring, tetrahydronaphthalene ring, decahydronaphthalene ring, anthracene ring or phenanthrene ring.
  • —CH ⁇ is —N ⁇
  • —CH 2 — may be substituted with —S— or —O—.
  • X, Y and Z are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, or a substituent. It represents an alkenyl group having 2 to 6 carbon atoms, a halogen atom, a cyano group or a group having a chemical structure represented by the following general formula (2).
  • L 1 , L 2 and L 3 each represent a bond, and each independently represents a single bond, —COO—, —OCO—, — (CH 2 ) d —, —CH ⁇ CH—, — (CH 2 ) e.
  • D to m and o each independently represents an integer of 1 to 8.
  • p to s each independently represents an integer of 1 to 3.
  • n represents 0 or 1.
  • a, b and c are the number of substituents in ring A 1 , ring A 2 and ring A 3 , respectively, where t is the number of 6-membered rings contained in each substituted monocyclic or condensed ring.
  • A, b and c each independently represent an integer of 2t + 2 or less, and when n is 0, at least one of a and b is 1 or more. When n is 1, at least one of a, b and c is 1 or more.
  • R 3 represents a hydrogen atom, a methyl group or a halogen atom.
  • the polymerizable compound having a chemical structure represented by the general formula (1) is contained in a range of 5 to 25% by mass with respect to the hydrogenated norbornene resin.
  • Polarizing plate protective film is contained in a range of 5 to 25% by mass with respect to the hydrogenated norbornene resin.
  • the polymerizable compound having a chemical structure represented by the general formula (1) is a compound having a chemical structure represented by the following general formula (3): Polarizing plate protective film.
  • X 1 and X 3 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an alkyl group having 1 to 8 carbon atoms which may have a substituent).
  • X 2 , X 4 , Y 1- Y 4 and Z 1 to Z 4 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms that may have a substituent, or an alkyl group having 1 to 8 carbon atoms that may have a substituent.
  • the polymerizable compound having a chemical structure represented by the general formula (1) is a compound having a chemical structure represented by the following general formula (4): Polarizing plate protective film.
  • R 1 , R 2 , X 1 , X 2 , X 3, X 4 , Y 1 to Y 4 , Z 1 to Z 4 , A 1 , A 2 and A 3 are the same as those in the general formula (3)
  • R 1 , R 2 , X 1 , X 2 , X 3 , X 4 , Y 1 to Y 4 , Z 1 to Z 4 , A 1 , A 2 and A 3 are the same as those in the general formula ( It is synonymous with f in 1).)
  • the polymerizable compound having a chemical structure represented by the general formula (1) is a compound having a chemical structure represented by the following general formula (5): Polarizing plate protective film.
  • R 1 , R 2 , X 1 , X 2 , X 3 , X 4 , Y 1 to Y 4 , A 1 and A 2 are R 1 , R 2 , X 1 in the general formula (4)). , X 2, X 3, X 4, Y 1 ⁇ Y 4, the same meanings as a 1 and a 2.)
  • the polarizing plate protective film according to any one of items 1 to 6 is bonded to a polarizer in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin.
  • Polarizer in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin.
  • a polarizing plate protective film containing a hydrogenated norbornene-based resin is bonded to a polarizer by the above means of the present invention to produce a polarizing plate
  • the polarizing plate is hardly cracked even if a heat cycle test is performed. It is possible to provide a polarizing plate protective film and a method for producing the same. Moreover, the polarizing plate provided with the said polarizing plate protective film can be provided.
  • the present inventors have problems such as cracking and peeling when a polarizing plate protective film containing a hydrogenated norbornene-based resin is used for a polarizing plate. Is caused by a change in the contraction stress of the polarizer accompanying a change in the environmental temperature, and the polarizer protective film contains a specific compound, and the polarizer film can be expanded and contracted by the temperature change. It was found that the above problems can be solved by combining them.
  • the contraction stress of the polarizer is very large.
  • the contraction stress becomes 20 N per 10 mm width.
  • a large contraction stress of the polarizer leads to an increase in the contraction stress of the polarizing plate. Therefore, it is preferable that the contraction stress is small in order to prevent the occurrence of cracks.
  • the polarizing plate protective film is present in a state where it is adhered to the polarizer, and a large shrinkage force is always applied under the condition of being left at 90 ° C. as described above. It is known that when the above is reproduced by a constant load tensile test, the strength of the polarizing plate protective film decreases.
  • the adjacent polarizers are thermally contracted, and at the same time, the film strength is lowered and cracks are enlarged. Further, in the absorption axis direction of the polarizer, the polarizer is thermally expanded in the same manner as the hydrogenated norbornene resin film, and it is considered that the larger the difference in this portion, the larger the crack.
  • the present inventors have been able to prevent a decrease in strength by including a compound having a chemical structure represented by the general formula (1) in a polarizing plate protective film containing a hydrogenated norbornene resin. It is assumed that this is due to the following mechanism.
  • the rings A1, A2, and A3 in the chemical structure represented by the general formula (1) are subjected to rotation restriction by L1, L2, and L3, and a rigid planar structure is formed by arranging the rings.
  • This rigid planar structure is mixed and arranged in parallel with the casting direction of the hydrogenated norbornene resin, and is densely oriented between the norbornene resins.
  • bonded with the both ends of a rigid planar structure couple
  • the polarizing plate protective film of the present invention is a polarizing plate protective film containing a norbornene-based resin, wherein the norbornene-based resin is a hydrogenated norbornene-based resin and has a chemical structure represented by the general formula (1). It contains the polymerizable compound which has this. This feature is a technical feature common to or corresponding to the claimed invention.
  • the polymerizable compound having the chemical structure represented by the general formula (1) is in the range of 5 to 25% by weight based on the hydrogenated norbornene resin. It is preferable that it is contained within.
  • the polymerizable compound having the chemical structure represented by the general formula (1) is a compound having the chemical structure represented by the general formula (3). It is preferable that it is a compound which has a chemical structure represented by the said General formula (4), or a compound which has a chemical structure represented by the said General formula (5).
  • the tensile strength of the polarizing plate protective film before and after the constant load tensile test is preferably 0.6 or more.
  • the method for producing a polarizing plate protective film of the present invention includes a step of preparing a dope prepared by dissolving at least the hydrogenated norboornene resin and the polymerizable compound in a solvent, and casting the dope on a support.
  • the production method has an aspect including a step of forming a casting film and a step of peeling the casting film from the support.
  • the polarizing plate protective film of the present invention can be suitably used for a polarizing plate by being bonded to a polarizer in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin.
  • the polarizing plate protective film of the present invention is a polarizing plate protective film containing a norbornene-based resin, wherein the norbornene-based resin is a hydrogenated norbornene-based resin and has a chemical structure represented by the general formula (1). It contains the polymerizable compound which has this.
  • the “hydrogenated norbornene-based resin” used in the present invention refers to a norbornene derivative (monomer) alone, or the norbornene derivative and an unsaturated cyclic compound copolymerizable therewith, using a metathesis polymerization catalyst.
  • the hydrogenated norbornene-based resin is preferably a resin derived from a norbornene monomer having a chemical structure represented by the following general formula (I).
  • the resin derived from the norbornene monomer having the chemical structure represented by the general formula (I) is polymerized using the norbornene monomer having the chemical structure represented by the general formula (I) as a component. It represents that the resin is derived.
  • A, B, X and Y are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group, a hydroxy group, an ester group, a cyano group, an amide group, an imide group
  • the copolymerizable monomer copolymerizable with the norbornene monomer represented by the general formula (I) is not particularly limited, and examples thereof include cyclic olefin monomers having no norbornene skeleton.
  • Examples of the cyclic olefin monomer having no norbornene skeleton include cyclooctadiene, cyclooctene, cyclohexene, cyclododecene, cyclododecatriene and the like.
  • the norbornene monomer or copolymerizable monomer it is preferable to give a certain moisture permeability to the resin obtained by having a polar group other than a halogen atom in the monomer structure.
  • a method for polymerizing a norbornene monomer represented by the general formula (I) or a norbornene monomer represented by the general formula (I) and a copolymerizable monomer copolymerizable therewith for example, conventionally known methods such as ring-opening metathesis polymerization and addition polymerization can be employed.
  • the norbornene-based resin When the norbornene-based resin has an unsaturated bond in the molecule, it is preferably saturated by hydrogenation, and the hydrogenation rate is preferably 95% or more, more preferably 99% or more. When the hydrogenation rate is less than 95%, the obtained polarizing plate protective film is inferior in light resistance and heat deterioration resistance.
  • the number average molecular weight in terms of polystyrene of the norbornene resin is preferably 10,000 to 1,000,000. If it is less than 10,000, the mechanical strength of the resulting polarizing plate protective film may be insufficient. Conversely, if it exceeds 1,000,000, melt extrusion moldability may be significantly reduced. More preferably, it is 15,000 to 700,000.
  • the polarizing plate protective film of the present invention is characterized by containing a polymerizable compound having a chemical structure represented by the following general formula (1).
  • R ⁇ 1 > and R ⁇ 2 > represents a hydrogen atom, a methyl group, or a halogen atom each independently.
  • Ring A 1 , Ring A 2 and Ring A 3 each independently represent a benzene ring, cyclohexane ring, cyclohexene ring, naphthalene ring, tetrahydronaphthalene ring, decahydronaphthalene ring, anthracene ring or phenanthrene ring.
  • —CH ⁇ is —N ⁇
  • —CH 2 — may be substituted with —S— or —O—.
  • X, Y and Z are each independently an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 8 carbon atoms which may have a substituent, or a substituent. It represents an alkenyl group having 2 to 6 carbon atoms, a halogen atom, a cyano group or a group having a chemical structure represented by the following general formula (2).
  • L 1 , L 2 and L 3 each represent a bond, and each independently represents a single bond, —COO—, —OCO—, — (CH 2 ) d —, —CH ⁇ CH—, — (CH 2 ) e.
  • D to m and o each independently represents an integer of 1 to 8.
  • p to s each independently represents an integer of 1 to 3.
  • n represents 0 or 1.
  • a, b and c are the number of substituents in ring A 1 , ring A 2 and ring A 3 , respectively, where t is the number of 6-membered rings contained in each substituted monocyclic or condensed ring.
  • A, b and c each independently represent an integer of 2t + 2 or less, and when n is 0, at least one of a and b is 1 or more. When n is 1, at least one of a, b and c is 1 or more.
  • examples of the halogen atom represented by R 1 , R 2 , X, Y, and Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkyl group having 1 to 8 carbon atoms which may have a substituent represented by X, Y and Z include methyl, chloromethyl, trifluoromethyl, cyanomethyl, ethyl, dichloroethyl, propyl, isopropyl and butyl , Sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary Heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl and the like.
  • alkoxy group having 1 to 8 carbon atoms which may have a substituent examples include methyloxy, chloromethyloxy, trifluoromethyl Oxy, cyanomethyloxy, ethyloxy, dichloroethyloxy, propyl Xy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, Isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy and the like.
  • alkenyl group having 2 to 6 carbon atoms which may have a substituent examples include vinyl, 1-methylethenyl, propenyl, butenyl, isobutenyl, Examples include pentenyl, hexenyl and the like.
  • examples of the halogen atom represented by R 3 include those exemplified as R 1 and the like.
  • ring A 2 or ring A 3 is a condensed ring
  • position 1 of the naphthalene ring When CH 2 ⁇ CR 1 —COO group is attached to L 2 , L 1 is located at the 5-position, and when CH 2 ⁇ CR 1 —COO group is attached at the 2 position, L 1 is located at 6 position, so that CH 2 ⁇ CR The 1- COO group and L 1 are bonded to ring A 1 at a parallel position.
  • ring A 1 is a decahydronaphthalene ring or a tetrahydronaphthalene ring
  • ring A 1 is a tetrahydronaphthalene ring
  • ring A 1 is an anthracene ring
  • L 1 is attached to the 2-position with a CH 2 ⁇ CR 1 —COO group per the 6-position, L 1 is in the 7th position, and when a CH 2 ⁇ CR 1 —COO group is attached in the 3rd position, L 1 is in the 8th position.
  • ring A 1 is a phenanthrene ring
  • L 1 is attached in the 6-position
  • L 1 as that attached to the 8-position, in ring a 1
  • CH 2 CR 1 -COO group and L 1 and Is bonded to ring A 1 so that the molecular structure of the polymerizable compound can be kept linear.
  • examples of the polymerizable compound according to the present invention having the chemical structure represented by the general formula (1) include a polymerizable compound having a chemical structure represented by the following general formula (3).
  • the polymerizable compound of the general formula (3) has a large rotation restriction on the molecular structure. Therefore, the effect of preventing cracks of the present invention is large and more preferable.
  • X 1 and X 3 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, or an alkyl group having 1 to 8 carbon atoms which may have a substituent).
  • X 2 , X 4 , Y 1- Y 4 and Z 1 to Z 4 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms that may have a substituent, or an alkyl group having 1 to 8 carbon atoms that may have a substituent.
  • R 1 , R 2 , X 1 , X 2 , X 3, X 4 , Y 1 to Y 4 , Z 1 to Z 4 , A 1 , A 2 and A 3 are the same as those in the general formula (3)
  • R 1 , R 2 , X 1 , X 2 , X 3 , X 4 , Y 1 to Y 4 , Z 1 to Z 4 , A 1 , A 2 and A 3 are the same as those in the general formula ( It is synonymous with f in 1).
  • the polymeric compound represented by following General formula (5) can also be mentioned.
  • the polymerizable compound of the general formula (5) has a small molecular structure and an effect of increasing the density. Therefore, the effect of preventing cracks of the present invention is large and more preferable.
  • R 1 , R 2 , X 1 , X 3 , X 2 , X 4 , Y 1 to Y 4 , A 1 and A 2 are R 1 , R 2 , X 1 in the general formula (4)).
  • X 2 , X 3 , X 4 , Y 1 to Y 4 , A 1 and A 2 are R 1 , R 2 , X 1 in the general formula (4).
  • X 2 , X 3 , X 4 , Y 1 to Y 4 , A 1 and A 2 Specific examples of the polymerizable compound having the chemical structure represented by the general formula (1) include the following compound No. 1 to 29 may be mentioned. However, the present invention is not limited by the following compounds.
  • the polymerizable compound having the chemical structure represented by the general formula (4) can be produced, for example, according to the following reaction scheme.
  • the polarizing plate protective film of the present invention contains the polymerizable compound having the chemical structure represented by the general formula (1) in a range of 5 to 25% by mass with respect to the hydrogenated norbornene resin. Is preferable from the viewpoint of expression of the effects of the present invention.
  • the polymerizable compound having the chemical structure represented by the general formula (1) is further contained within a range of 10 to 20% by mass with respect to the hydrogenated norbornene resin. Within such a range, it is easy to perform control for adjusting the expansion and contraction due to the temperature change of the polarizing plate protective film to the polarizer film.
  • the polarizing plate protective film of the present invention can contain various additives for the purpose of imparting various functions.
  • Additives that can be applied to the present invention are not particularly limited, and are, for example, ultraviolet absorbers, plasticizers, deterioration inhibitors, matting agents, retardation increasing agents, and chromatic dispersion improvement within the range that does not impair the object effects of the present invention.
  • An agent or the like can be used.
  • the polarizing plate protective film of the present invention can contain an ultraviolet absorber.
  • ultraviolet absorbers examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like, but less benzotriazole compounds Compounds are preferred. Further, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 and polymer ultraviolet absorbers described in JP-A-6-148430 are preferably used. As an ultraviolet absorber, from the viewpoint of preventing deterioration of a polarizer and an organic EL element, it has an excellent ability to absorb ultraviolet light having a wavelength of 370 nm or less, and from the viewpoint of display properties of the organic EL element, it absorbs visible light having a wavelength of 400 nm or more. It is preferable to have few characteristics.
  • benzotriazole-based ultraviolet absorber examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t -Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butyl Phenyl) -5-chlorobenzotriazole, 2- [2′-hydroxy-3 ′-(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2 -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy- '-T-butyl-5'-methylphenyl) -5-
  • TINUVIN 109 As commercially available products, “TINUVIN 109”, “TINUVIN 171”, “TINUVIN 326”, “TINUVIN 328” (registered trademark) manufactured by BASF Japan Ltd.) It can be preferably used.
  • the addition amount of the ultraviolet absorber is preferably in the range of 0.1 to 5.0% by mass, and more preferably in the range of 0.5 to 5.0% by mass with respect to the cellulose derivative.
  • a polarizing plate protective film is poor in flexibility, and when the film is subjected to bending stress or shear stress, the film is likely to be cracked.
  • a crack is easy to enter into a cut part and it is easy to generate
  • the polarizing plate protective film can contain a plasticizer.
  • plasticizer examples include phthalic acid esters, trimellitic acid esters, aliphatic dibasic acid esters, orthophosphoric acid esters, acetic acid esters, polyester epoxidized esters, ricinoleic acid esters. , Polyolefin, and polyethylene glycol compounds.
  • plasticizer that can be used for the polarizing plate protective film of the present invention, it is preferable to select from a compound having a normal temperature, a normal pressure, a liquid, and a boiling point of 200 ° C. or higher.
  • Specific examples of the compound name include aliphatic dibasic acid ester, phthalic acid ester, and polyolefin compounds.
  • the addition amount of the plasticizer is preferably in the range of 0.5 to 40.0% by mass, and in the range of 1.0 to 30.0% by mass with respect to the hydrogenated norbornene resin. Is more preferable, and it is particularly preferably in the range of 3.0 to 20.0% by mass.
  • the added amount of the plasticizer is 0.5% by mass or more, the plasticizing effect is sufficient and the processability is improved.
  • the content is 40% by mass or less, separation and elution of the plasticizer can be suppressed when it is aged for a long time, and optical unevenness, contamination to other parts, and the like can be more reliably suppressed.
  • the polarizing plate protective film of the present invention can contain a deterioration inhibitor such as an antioxidant, a peroxide decomposer, a radical polymerization inhibitor, a metal deactivator, an acid scavenger, and amines. .
  • Examples of the deterioration preventing agent are described in JP-A-3-199201, JP-A-5-97073, JP-A-5-194789, JP-A-5-271471, JP-A-6-107854, and the like.
  • the addition amount of the deterioration preventing agent is effective for the addition of the deterioration preventing agent, and the dope (water) used for the production of the polarizing plate protective film from the viewpoint of suppressing the bleeding out of the deterioration preventing agent to the film surface.
  • the added norbornene resin solution is preferably in the range of 0.01 to 1% by mass, and more preferably in the range of 0.01 to 0.2% by mass.
  • BHT butylated hydroxytoluene
  • TBA tribenzylamine
  • the polarizing plate protective film of the present invention can contain fine particles as a matting agent.
  • Examples of the matting agent fine particles include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, and silicic acid. Examples thereof include magnesium and calcium phosphate.
  • these matting agent fine particles those containing silicon are preferable in terms of low turbidity (haze), and silicon dioxide is particularly preferable.
  • the fine particles of silicon dioxide preferably have a primary average particle size in the range of 1 to 20 nm and an apparent specific gravity of 70 g / liter or more.
  • the primary average particle size is more preferably in the range of 5 to 16 nm from the viewpoint of reducing the haze of the polarizing plate protective film.
  • the apparent specific gravity is more preferably in the range of 90 to 200 g / liter, and particularly preferably in the range of 100 to 200 g / liter. A larger apparent specific gravity is preferable because a high-concentration dispersion can be produced, and haze and aggregates are improved.
  • These fine particles usually form secondary particles having an average particle size in the range of 0.05 to 2.0 ⁇ m.
  • These secondary particles exist as aggregates of primary particles in the polarizing plate protective film, and form irregularities of 0.05 to 2.0 ⁇ m on the optical film surface.
  • the secondary average particle size is preferably in the range of 0.05 to 1.0 ⁇ m, more preferably in the range of 0.1 to 0.7 ⁇ m, and in the range of 0.1 to 0.4 ⁇ m. It is particularly preferred.
  • the primary particle size and the secondary particle size were determined by observing fine particles in the polarizing plate protective film with a scanning electron microscope and determining the diameter of a circle circumscribing the particles as the particle size. Also, 200 particles are observed at different locations, and the average value is taken as the average particle size.
  • silicon dioxide fine particles for example, commercially available products such as Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above, Nippon Aerosil Co., Ltd., trade name) may be used. it can.
  • Zirconium oxide fine particles are commercially available, for example, as Aerosil R976 and R811 (which are registered trademarks of Nippon Aerosil Co., Ltd.) and can be used.
  • Aerosil 200V and Aerosil R812V are fine particles of silicon dioxide having a primary average particle size of 20 nm or less and an apparent specific gravity of 70 g / liter or more, and while keeping the haze of the polarizing plate protective film low, friction This is particularly preferable because the effect of lowering the coefficient is great.
  • the matting agent fine particles are preferably prepared by the following method and applied to a polarizing plate protective film. That is, a matting agent fine particle dispersion prepared by stirring and mixing a solvent and matting agent fine particles is prepared in advance, and this matting agent fine particle dispersion is added to various additive solutions having a separately prepared hydrogenated norbornene resin concentration of less than 5% by mass. A method of mixing with the main hydrogenated norbornene resin dope after adding and dissolving with stirring is preferred.
  • the surface of the matting agent fine particles has been subjected to a hydrophobic treatment, when an additive having hydrophobicity is added, the additive is adsorbed on the surface of the matting agent fine particles, and the aggregate of the additive is used as a core. Is likely to occur. Therefore, by mixing the hydrophilic additive in advance with the matting agent fine particle dispersion and then mixing the hydrophobic additive, aggregation of the additive on the matting agent surface can be suppressed, and the haze can be suppressed. And a polarizing plate protective film with low light leakage in black display when incorporated in a liquid crystal display device is preferable.
  • an in-line mixer for mixing the matting agent fine particle dispersant with the additive solution and mixing with the hydrogenated norbornene resin dope.
  • concentration of silicon dioxide when the silicon dioxide fine particles are mixed and dispersed with a solvent or the like is preferably in the range of 5 to 30% by mass, and is preferably 10 to 25% by mass. It is more preferable that it be within the range, and it is particularly preferable that it be within the range of 15 to 20% by mass.
  • a higher dispersion concentration is preferable because turbidity with respect to the same amount of addition is reduced, and generation of haze and aggregates can be suppressed.
  • the addition amount of the matting agent in the final dope of the hydrogenated norbornene resin is preferably in the range of 0.001 to 1.0% by mass, and in the range of 0.005 to 0.5% by mass. More preferably, the content is in the range of 0.01 to 0.1% by mass.
  • the polarizing plate protective film of the present invention is preferably a polarizing plate protective film produced by a solution casting method or a melt casting method. Here, a manufacturing method by the solution casting method will be described.
  • Production of the polarizing plate protective film of the present invention is a step of preparing a dope by dissolving the hydrogenated norbornene-based resin and the polymerizable compound in a solvent, and casting the dope on an endless metal support that moves indefinitely. It is performed by a step, a step of drying the cast dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.
  • the process for preparing the dope will be described.
  • the concentration of the dissolved hydrogenated norbornene resin and the polymerizable compound in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration is too high, the load during filtration increases. Thus, the filtration accuracy is deteriorated.
  • the concentration at which these are compatible is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
  • the solvent used in the dope may be used alone or in combination of two or more, but it is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the hydrogenated norbornene resin.
  • a preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent.
  • the good solvent used in the present invention is not particularly limited, and examples thereof include organic halogen compounds such as methylene chloride, dioxolanes, acetone, methyl acetate, and methyl acetoacetate. Particularly preferred is methylene chloride or methyl acetate.
  • the poor solvent used in the present invention is not particularly limited, but for example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone and the like are preferably used.
  • the dope preferably contains 0.01 to 2% by mass of water.
  • the solvent used for dissolving the hydrogenated norbornene-based resin, the polymerizable compound, and the additive may be used by collecting the solvent removed from the film by drying in the film forming process and reusing it.
  • a general method for dissolving the hydrogenated norbornene resin when preparing the dope described above a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure.
  • the hydrogenated norbornene resin, the polymerizable compound, and the additive solution are filtered using an appropriate filter medium such as filter paper.
  • the absolute filtration accuracy is small in order to remove insoluble matters, but there is a problem that the filter medium is likely to be clogged if the absolute filtration accuracy is too small.
  • a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is still more preferable.
  • the material of the filter medium there are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable.
  • a bright spot foreign material is placed in a crossed Nicols state with two polarizing plates, a polarizing plate protective film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. and means a point visible light leaks from the opposite side (foreign matter) in time, it is preferable diameter is bright points at 0.01mm or more and 200 / cm 2 or less.
  • it is 100 pieces / cm 2 or less, still more preferably 50 pieces / m 2 or less, still more preferably 0 to 10 pieces / cm 2 . Further, it is preferable that the number of bright spots of 0.01 mm or less is small.
  • the dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration.
  • the increase in the difference (referred to as differential pressure) is small and preferable.
  • the preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.
  • the filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.
  • the metal support in the casting process is preferably a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
  • the cast width can be 1 to 4 m.
  • the surface temperature of the metal support in the casting step is ⁇ 50 ° C. to less than the boiling point of the solvent, and a higher temperature is preferable because the web drying speed can be increased. May deteriorate.
  • the support temperature is preferably 0 to 40 ° C. ⁇ 0 to 50 ° C., more preferably 5 to 30 ° C.
  • the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent.
  • the method for controlling the temperature of the metal support is not particularly limited, but there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support.
  • the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass.
  • the amount of residual solvent is defined by the following formula.
  • Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.
  • the web is peeled off from the metal support and further dried to make the residual solvent amount 1% by mass or less, more preferably 0.1% by mass or less. Particularly preferred is 0 to 0.01% by mass or less.
  • a roll drying method (a method in which a plurality of rolls arranged at the top and bottom are alternately passed through the web for drying) or a tenter method for drying while transporting the web is employed.
  • any appropriate surface treatment may be applied to the surface of the polarizing plate protective film (outside polarizing plate protective film) disposed outside of the polarizing plate protective film.
  • the surface treatment include an antiglare treatment, a diffusion treatment (antiglare treatment), an antireflection treatment (antireflection treatment), a hard coat treatment, and an antistatic treatment.
  • Any appropriate method can be used as the anti-glare treatment method.
  • the surface reflection light can be formed by an appropriate method such as embossing, sand blasting, etching, or the like by providing a fine uneven structure on the surface.
  • polarizing plate protective film of the present invention a film made of a hydrogenated norbornene resin is used, but an unstretched film or a uniaxially stretched film may be used.
  • the degree of orientation of the resin increases.
  • the tensile elastic modulus increases, and the weakness against the impact of the blade during cutting, which is one of the causes of crack generation, is improved.
  • the linear expansion coefficient of this film also falls by orienting. Orientation is caused by cast film formation, and due to the solvent diffusion process, the shrinkage force acting on the film (web) on the film formation belt and the conveyance tension in film conveyance are generated. ⁇ Measurement of orientation> The orientation coefficient of the polarizing plate protective film was measured according to the following method.
  • the measurement of the orientation coefficient employs a uniaxial orientation coefficient (orientation coefficient fxy).
  • the orientation coefficient fxy can be obtained according to the following equation. For details of fxy, see P.A. A. Flumoy, and W.C. J. et al. Reference can be made to Schaffers, Spectrochimica Acta, 22, 5 (1966).
  • fxy (Dxy-1) / (Dxy + 2).
  • fxz (Dxz-1) / (Dxz + 2).
  • (Dxz + 2) / (Dxz-1) fxy represents an orientation coefficient in the in-plane direction.
  • fxz represents an orientation coefficient in the film thickness direction.
  • Dxy and Dxz represent infrared dichroic ratios, and all of the values are 1.00 for a completely spatially isotropic non-oriented sample.
  • it is necessary to examine the direction of the moment of molecular vibration, but it is usually sufficient to select the vibration mode parallel to the molecular axis and the mode perpendicular to the molecular axis and calculate these as 0 ° and 90 °, respectively. Information about orientation can be obtained.
  • the orientation coefficient is 0 in the case of non-orientation, 1.0 in the case of being completely oriented in the observation direction, and -0.5 in the case of being orthogonal to the observation direction.
  • the infrared dichroic ratio was measured using attenuated total reflection infrared spectroscopy (ATR-IR method). For specific calculation methods, see J.H. P. Hobbs, C.I. S. P. Sung (JP Hobbs, C. S. P. Sung, K. Krishan, and, S. Hill, Macromolecules, 16, 193 (1983)).
  • the infrared dichroic ratio was obtained by measuring the intensity of a peak derived from the ethylene chain CC stretching vibration of the hydrogenated norbornene resin skeleton (the strongest peak appearing between 1273 cm-1 ⁇ 10 cm-1).
  • the peak intensity is obtained by connecting the wave number of the peak top (assumed to be xcm-1), the point having the smallest absorbance in x to x + 50 cm-1 and the point having the smallest absorbance in x to x-50 cm-1. Using this as a baseline, the peak intensity from this was measured and determined.
  • the specific orientation coefficient fxy in the present invention was measured using the polarization ATR method under the following measurement conditions.
  • NICOLET380 manufactured by Thermo Prism: Germanium Pressure between prism and sample: 30 cN ⁇ m Area of jig for pressing sample against prism: 1 cm 2 Incident angle: 45 ° Number of reflections: 1 time Resolution: 4 cm -1 Data interpolation: 0.5cm -1
  • the refractive index of the sample was calculated as 1.477 in the cellulose derivative of the present invention.
  • the prism (germanium) was 4.00. Vertically polarized light and horizontally polarized light were incident on an incident surface composed of light incident on the sample surface and reflected light using a wire grid polarizer, and an FTIR-ATR spectrum was measured.
  • the above measurement was performed by setting the MD direction as the x axis, the vertical direction (width direction TD) as the y axis, and the thickness direction as the z axis.
  • the linear expansion coefficient ⁇ of the polarizing plate protective film is preferably 4.5 ⁇ 10 ⁇ 5 / ° C. or less (PVA value), more preferably ⁇ 5.0 ⁇ 10 ⁇ 5 to 4.5 ⁇ 10 ⁇ 5. a / ° C., more preferably from -4.5 ⁇ 10 -5 ⁇ 4.0 ⁇ 10 -5 / °C.
  • the difference between the linear expansion coefficient in the transmission axis direction of the polarizer and the linear expansion coefficient ⁇ of the polarizing plate protective film is more than 0 and 4 ⁇ 10 ⁇ 5 / ° C., more preferably 0.5 ⁇ 10 ⁇ 5 to 4.0 ⁇ 10 ⁇ 5 / ° C.
  • the difference between the linear expansion coefficient in the transmission axis direction of the polarizer and the linear expansion coefficient ⁇ of the polarizing plate protective film is within the above range, a polarizing plate having excellent crack durability can be obtained.
  • polarizer any appropriate polarizer can be used as the polarizer used in the present invention.
  • dichroic substances such as iodine and dichroic dyes are adsorbed on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • polyene-based oriented films such as a uniaxially stretched product, a polyvinyl alcohol dehydrated product and a polyvinyl chloride dehydrochlorinated product.
  • a polarizer obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol film and uniaxially stretching is particularly preferable because of its high polarization dichroic ratio.
  • the thickness of these polarizers is not particularly limited and is generally about 1 to 80 ⁇ m.
  • a polarizer uniaxially stretched by adsorbing iodine to a polyvinyl alcohol film can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. . If necessary, it may contain boric acid, zinc sulfate, zinc chloride or the like, or may be immersed in an aqueous solution such as potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. *
  • Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching.
  • the film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • the polarizer used in the present invention preferably satisfies 0.030 ⁇ Rpva ⁇ 0.040.
  • Rpva nx ⁇ ny.
  • Rpva is more preferably 0.030 ⁇ Rpva ⁇ 0.039, and particularly preferably 0.030 ⁇ Rpva ⁇ 0.035. It is estimated that such characteristics are satisfied by increasing the amount of crystals that do not contribute to orientation in the polarizer (typically, low orientation).
  • Rpva is a polarizer in such a range, it can have excellent dimensional stability and optical durability in a high temperature and high humidity environment. As a result, even when the polarizer is used for a polarizing plate provided with a polarizing plate protective film only on one side of the polarizer, the dimensional change and the deterioration of the optical characteristics are unlikely to occur, and the practically acceptable dimensional stability and optical Durability can be achieved.
  • the polarizer used in the present invention has a dichroic ratio DR of preferably 160 or more, more preferably 160 to 220, particularly preferably 170 to 210, and most preferably 175 to 185.
  • a liquid crystal panel and a liquid crystal display device with high front contrast can be obtained by using the polarizing plate of the present invention.
  • Such a liquid crystal panel and a liquid crystal display device are suitable for television applications, for example.
  • the dichroic ratio DR can be obtained from the following equation.
  • Dichroic ratio DR log (0.919 / k 2 ) / log (0.919 / k 1 )
  • k 1 is the transmission axis of the transmittance of the polarizer
  • k 2 is the absorption axis direction of the transmittance of the polarizer
  • the constant 0.919 is the interfacial reflectance.
  • the polarizer used in the present invention has a transmittance (single transmittance) Ts of preferably 42% or more, more preferably 42. It is in the range of -44.0%, particularly preferably in the range of 42.5-43.0%.
  • Ts a transmittance (single transmittance) Ts of preferably 42% or more, more preferably 42. It is in the range of -44.0%, particularly preferably in the range of 42.5-43.0%.
  • the transmittance Ts is in such a range, a liquid crystal panel or a liquid crystal display device with high luminance can be obtained by using the polarizing plate of the present invention.
  • Such a liquid crystal panel and a liquid crystal display device are suitable for television applications, for example.
  • permeability of a polarizing plate can be calculated
  • Transmittance (k 1 + k 2 ) / 2 ⁇ 100 [%]
  • k 1 is the transmittance in the transmission axis direction of the polarizer
  • k 2 is the transmittance in the absorption axis direction of the polarizer.
  • the polarizer used in the present invention may be a polarizer mainly composed of a polyvinyl alcohol (PVA) resin containing a dichroic substance such as iodine or a dichroic dye.
  • PVA polyvinyl alcohol
  • the iodine content of the polarizer used in the present invention is preferably 1.8 to 5.0 mass%, more preferably 2.0 to 4.0 mass%.
  • the boric acid content of the polarizer used in the present invention is preferably 0.5 to 3.0% by mass, more preferably 1.0 to 2.8% by mass, and particularly preferably in terms of boron. Is 1.5 to 2.6% by mass.
  • a polarizer having excellent dimensional stability and optical durability in a humidified environment can be obtained without increasing the amount of boric acid.
  • the polarizer used in the present invention may preferably further contain potassium.
  • the potassium content is preferably 0.2 to 1.0% by mass, more preferably 0.3 to 0.9% by mass, and particularly preferably 0.4 to 0.8% by mass.
  • FIG. 1 is a schematic cross-sectional view of a polarizing plate according to a preferred embodiment of the present invention.
  • the polarizing plate 101 includes a polarizer 10 and polarizing plate protective films 20 and 30 disposed on both surfaces of the polarizer 10.
  • the polarizer 10 and the polarizing plate protective films 20 and 30 are bonded to each other through an arbitrary adhesive layer (not shown).
  • the linear expansion coefficient ⁇ of the polarizing plate protective film 20 with respect to the direction parallel to the transmission axis of the polarizer 10 (hereinafter also simply referred to as the linear expansion coefficient ⁇ ) is smaller than the linear expansion coefficient in the transmission axis direction of the polarizer.
  • the stretching direction of the film in the manufacturing process coincides with the absorption axis direction. Therefore, the direction of the transmission axis, which is the direction orthogonal to the absorption axis of the polarizer, tends to be very brittle and easy to tear.
  • the linear expansion coefficient ⁇ of at least one of the polarizing plate protective films 20 and 30 is smaller than the linear expansion coefficient in the transmission axis direction of the polarizer. Both linear expansion coefficients ⁇ may be smaller than the linear expansion coefficient in the transmission axis direction of the polarizer.
  • the linear expansion coefficient ⁇ of the polarizing plate protective film outside the polarizing plate 101 is a value smaller than the linear expansion coefficient in the transmission axis direction of the polarizer.
  • the polarizing plate protective films 20 and 30 may be polarizing plate protective films having the same material and the same linear expansion coefficient ⁇ , and different polarizing plate protective films may be used.
  • Polarizers generally tend to expand as the temperature increases.
  • a polarizing plate protective film having a property of expanding as the temperature is lowered is preferably used. Therefore, when the temperature of the environment in which the polarizing plate of the present invention is placed increases, the difference in dimensional change in the transmission axis direction of the polarizer between the polarizer and the polarizing plate protective film increases, and such a polarizing plate protective film By using, crack durability can be improved.
  • the conventional polarizing plate in order to suppress the occurrence of stress at the interface between the polarizer and the polarizing plate protective film, the difference in coefficient of linear expansion between the polarizer and the protective film is reduced, and the difference in dimensional change with temperature change is reduced. Designed to be smaller.
  • the crack durability can be further improved by setting the linear expansion coefficient ⁇ of the polarizing plate protective film to a value smaller than the linear expansion coefficient in the transmission axis direction of the polarizer.
  • the polarizing plate of the present invention can be obtained by arranging the polarizing plate protective film so as to be small.
  • the polarizing plate of the present invention may further have other layers.
  • the other layers include an antireflection layer, an antistatic layer, a retardation layer, a brightness enhancement film layer, and an adhesive layer.
  • the polarizing plate of the present invention is bonded to a liquid crystal cell via the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer preferably has a storage elastic modulus at 23 ° C. of 8.0 ⁇ 10 4 or more and less than 1.0 ⁇ 10 7 , and is 1.0 ⁇ 10 5 to 8.0 ⁇ 10 6. More preferred. Any other appropriate layer may be selected depending on the purpose and application, the configuration of the liquid crystal display device in which the polarizing plate of the present invention is used, and the number, type, position, arrangement, and the like are appropriately set. obtain.
  • the liquid crystal display device of the present invention includes a liquid crystal cell and the polarizing plate of the present invention disposed on at least one side of the liquid crystal cell.
  • the polarizing plate of the present invention it is possible to provide a liquid crystal display device in which deterioration of display performance due to generation of cracks is suppressed.
  • the liquid crystal cell driving modes include vertical alignment (VA) mode, twisted nematic (TN) mode, in-plane switching (IPS) mode, vertical alignment electric field control birefringence (ECB) mode, and optical compensation birefringence. (OCB) mode etc. are mentioned.
  • the liquid crystal display device may be a transmissive type that irradiates light from the back side of the liquid crystal panel to view the screen, or a reflective type that irradiates light from the viewing side of the liquid crystal panel to view the screen. good.
  • the liquid crystal display device may be a transflective type having both transmissive and reflective properties.
  • the liquid crystal display device of the present invention is used for any appropriate application.
  • Applications include, for example, personal computer monitors, notebook computers, copy machines and other office automation equipment, mobile phones, watches, digital cameras, personal digital assistants (PDAs), portable devices such as portable game machines, video cameras, televisions, microwave ovens, etc.
  • the infrared absorption spectrum (IR) measurement result of the obtained white solid was as follows, and it was confirmed that the white solid was an acrylic ester that was the target product.
  • Example 1 Polyizing plate protective film (hereinafter, simply referred to as “protective film”)]
  • Fine particle addition liquid 1 The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.
  • a main dope having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Hydrogenated norbornene resin I was charged into a pressure dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope was prepared by filtration using 244.
  • the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 100%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m.
  • the peeled protective film was stretched 5% in the width direction using a tenter while applying heat at 180 ° C.
  • the residual solvent at the start of stretching was 30%.
  • drying was terminated while the drying zone was conveyed by a number of rolls.
  • the drying temperature was 130 ° C. and the transport tension was 90 N / m.
  • a protective film 101 having a dry film thickness of 20 ⁇ m was obtained.
  • the kind of hydrogenated norbornene-based resin the kind of polymerizable compound, the addition amount of the polymerizable compound, the plasticizer and the addition amount of the plasticizer as shown in Table 1, the same as the protective film 101 Polarizing plate protective films 102 to 123 were prepared.
  • plasticizer B 60 g of 1,6-hexanediol, 101 g of sebacic acid, 122 g of benzoic acid, and 0.191 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a quick cooling tube.
  • the temperature was gradually raised while stirring until it reached 230 ° C in an air stream. After dehydration condensation reaction for 15 hours, unreacted 1,2-propylene glycol was distilled off under reduced pressure at 200 ° C. after completion of the reaction to obtain a polyester as a plasticizer.
  • the acid value was 0.10 mg KOH / g, and the number average molecular weight was 600.
  • test piece dimensions are 20 mm wide x 150 mm long, measured at 23 ° C.-50% RH with a chuck distance of 100 mm and a tensile speed of 13.3 mm / min. The higher point strength was taken as the tensile strength.
  • the tensile strength before the constant load tensile test was evaluated as the breaking strength (MPa).
  • tensile strength ratio tensile strength after constant load tensile test (B) / tensile strength before constant load tensile test (A) was calculated.
  • the tensile strength ratio was evaluated as a breaking strength ratio (before and after durability).
  • the storage elastic modulus of the protective film is 23 ° C. and 80 ° C. by a torsional shear method with a frequency of 1 Hz using a measuring instrument “RSA III” manufactured by TA Instruments, using a cylinder having a diameter of 8 mm and a thickness of 1 mm as a test piece.
  • Storage elastic modulus (G ′), loss elastic modulus (G ′′), and tan ⁇ were measured.
  • Punching defect occurrence rate (%) 100 ⁇ (n / m) ⁇ Orientation degree> Measured according to the method described above.
  • Example 2 [Polarizing plate 1] ⁇ Preparation of Polarizing Plate 301> A protective film 101 is bonded to one surface of the polarizer 1 (hereinafter referred to as the A surface side) via a PVA adhesive so as to be parallel to the transmission axis of the polarizer.
  • the following protective film 205 was bonded to the surface (hereinafter referred to as the B surface side) to obtain a polarizing plate 301.
  • polarizing plates 302 to 336 were produced in the same manner as the polarizing plate 301 except that a protective film and a polarizer were combined.
  • Protective film 201 Polyethylene naphthalate film, Teonex Q83 (trade name) (manufactured by Teijin DuPont), thickness: 40 ⁇ m)
  • Protective film 202 Polyimide film stretched film, Kapton (trade name) (manufactured by Toray) Thickness: 50 ⁇ m)
  • Protective film 203 Polyethylene terephthalate film, MRF50 (trade name) (manufactured by Mitsubishi Plastics), thickness: 50 ⁇ m)
  • Protective film 204 Polyethylene terephthalate film, MRF25 (trade name) (manufactured by Mitsubishi Plastics, Inc., thickness: 25 ⁇ m)
  • Protective film 205 Triacetylcellulose film, KC4UAW (trade name) (manufactured by Konica Minolta), thickness: 40 ⁇ m)
  • Protective film 206 Triacetylcellulose film, KC2UAW (trade name) (manufactured by Konica Minolta, Inc
  • a PVA resin film having a polymerization degree of 2400, a saponification degree of 99.7 mol%, and a thickness of 75 ⁇ m was prepared.
  • the film was stretched 3 times in the film conveying direction while being dyed in an aqueous iodine solution at 30 ° C., and then the total draw ratio was 4% by weight boric acid at 60 ° C. and 5% by weight potassium iodide aqueous solution.
  • the film was stretched to be 6 times the original length. Furthermore, the stretched film was washed by immersing it in a 2 mass% potassium iodide aqueous solution at 30 ° C. for several seconds.
  • the obtained stretched film was dried at 90 ° C. to obtain a polarizer 1.
  • the obtained polarizer 1 had a linear expansion coefficient in the transmission axis direction of 4.5 ⁇ 10 ⁇ 5 / ° C.
  • a polarizer 2 was obtained in the same manner as the polarizer 1 except that the total stretching ratio was 5 times the original length.
  • the obtained polarizer 2 had a linear expansion coefficient of 4.8 ⁇ 10 ⁇ 5 / ° C. in the transmission axis direction.
  • the polarizing plate punched out with a 10 cm square Thomson blade was placed in the test area of the thermal shock tester, and the temperature in the test area was lowered to ⁇ 40 ° C. over 30 minutes from room temperature. Next, the temperature in the test area was raised to 85 ° C. over 30 minutes, and then lowered again to ⁇ 40 ° C. over 30 minutes. The number of corners where defects such as cracks, cracks, and chips were detected after 20 cycles were repeated with this process of raising the temperature from ⁇ 40 ° C. to 85 ° C. and lowering the temperature to ⁇ 40 ° C. as one cycle. (N) was divided by the number of observed corners (m) and expressed as a percentage as follows.
  • the polarizing plate of the present invention did not generate cracks even after the heat shock acceleration test, and had good crack durability. As shown by the results in Tables 1 and 2, it can be seen that a polarizing plate protective film and a polarizing plate having a small crack generation rate are obtained in the sample of the present invention.
  • the present invention can be used as a polarizing plate protective film that can be made into a polarizing plate that hardly causes cracks even when a heat cycle test is performed when a polarizing plate is prepared by bonding to a polarizer. Can do. Moreover, it can utilize as a polarizing plate provided with the said polarizing plate protective film.

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  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Mathematical Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Graft Or Block Polymers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention vise à fournir un film de protection de plaque polarisante contenant une résine de norbornène qui, lorsqu'il est collé sur un polariseur pour produire une plaque polarisante, ne se fissure pas facilement même lorsqu'il est soumis à un essai de cycle thermique, et qui permet d'obtenir une plaque polarisante qui, lorsque le film de protection de plaque polarisante est collé sur un polariseur pour produire une plaque polarisante et la plaque polarisante est collée sur un substrat en verre, ne se décolle pas facilement du substrat en verre dans des environnements à haute température. La présente invention concerne également un procédé de production d'un tel film de protection de plaque polarisante. Ce film de protection de plaque polarisante contient une résine de norbornène et est caractérisé en ce que la résine de norbornène est une résine de norbornène hydrogénée et contient un composé polymérisable qui a une structure chimique spécifique.
PCT/JP2016/084473 2015-12-24 2016-11-21 Film de protection de plaque polarisante, son procédé de production, et plaque polarisante Ceased WO2017110342A1 (fr)

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CN201680075206.8A CN108474892B (zh) 2015-12-24 2016-11-21 偏振片保护膜、其制造方法及偏振片
JP2017557805A JP6724930B2 (ja) 2015-12-24 2016-11-21 偏光板保護フィルム、その製造方法及び偏光板

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JP (1) JP6724930B2 (fr)
CN (1) CN108474892B (fr)
TW (1) TW201734074A (fr)
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CN109490323A (zh) * 2017-09-13 2019-03-19 住友化学株式会社 缺陷检查装置、缺陷检查方法、圆偏振板或椭圆偏振板的制造方法及相位差板的制造方法
WO2019244915A1 (fr) * 2018-06-20 2019-12-26 日東電工株式会社 Film polarisant, film polarisant avec couche adhésive et dispositif d'affichage d'image
WO2019244916A1 (fr) * 2018-06-20 2019-12-26 日東電工株式会社 Film de polarisation, film de polarisation fournie par couche adhésive, et dispositif d'affichage d'image
CN111316144A (zh) * 2017-11-10 2020-06-19 住友化学株式会社 圆偏振板及显示装置
WO2021029396A1 (fr) * 2019-08-09 2021-02-18 三菱瓦斯化学株式会社 Composé, (co)polymère, composition et procédé de formation de motif
WO2021192568A1 (fr) * 2020-03-27 2021-09-30 日東電工株式会社 Film polarisant et dispositif d'affichage d'image
CN113466983A (zh) * 2020-03-31 2021-10-01 东友精细化工有限公司 偏光层叠体和包含其的图像显示装置
KR20220015508A (ko) * 2018-03-28 2022-02-08 닛토덴코 가부시키가이샤 편광자, 편광 필름, 적층 편광 필름, 화상 표시 패널, 및 화상 표시 장치
WO2022202427A1 (fr) * 2021-03-24 2022-09-29 太陽インキ製造株式会社 Composition de résine thermodurcissable, film sec, produit durci, circuit imprimé nu et composant électrique/électronique
JP2024171107A (ja) * 2023-05-29 2024-12-11 日東電工株式会社 偏光板

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WO2020158084A1 (fr) * 2019-01-31 2020-08-06 日東電工株式会社 Film de polyester et plaque de polarisation comprenant le film de polyester
KR102912232B1 (ko) * 2019-01-31 2026-01-15 닛토덴코 가부시키가이샤 폴리에스테르 필름 및 그 폴리에스테르 필름을 포함하는 편광판
JP7265882B2 (ja) * 2019-02-26 2023-04-27 日東電工株式会社 偏光フィルムの製造方法、易接着層付偏光子、偏光フィルム、光学フィルム、および画像表示装置
CN113943433B (zh) * 2021-11-23 2023-05-30 万华化学集团股份有限公司 一种高性能丙烯酸吸水树脂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1077321A (ja) * 1996-07-09 1998-03-24 Mitsubishi Chem Corp 樹脂組成物及びこれを活性エネルギー線により硬化させてなる部材
JP2005309255A (ja) * 2004-04-23 2005-11-04 Asahi Denka Kogyo Kk 配向性高分子
JP2009157160A (ja) * 2007-12-27 2009-07-16 Sekisui Chem Co Ltd 熱可塑性樹脂フィルム及びそれを用いた偏光板
JP2013076773A (ja) * 2011-09-29 2013-04-25 Nippon Shokubai Co Ltd 偏光子保護フィルム及びその利用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001272535A (ja) * 2000-03-24 2001-10-05 Sekisui Chem Co Ltd 偏光板保護フィルム及び偏光板
JP2003322721A (ja) * 2002-05-01 2003-11-14 Fuji Photo Film Co Ltd 光学フィルムおよびそれを用いた偏光板
JP2004067984A (ja) * 2002-06-11 2004-03-04 Sekisui Chem Co Ltd 樹脂組成物、光学フィルム及び偏光板
WO2004101478A1 (fr) * 2003-05-14 2004-11-25 Jsr Corporation Derive de norbornene, polymere de norbornene obtenu par (co)polymerisation a ouverture de noyau, et procede de production dudit polymere par (co)polymerisation a ouverture de noyau
JP2009227868A (ja) * 2008-03-24 2009-10-08 Fujifilm Corp 樹脂組成物およびフィルム
JP5657593B2 (ja) * 2011-03-31 2015-01-21 富士フイルム株式会社 積層フィルム、光学補償フィルム、偏光板、及び液晶表示装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1077321A (ja) * 1996-07-09 1998-03-24 Mitsubishi Chem Corp 樹脂組成物及びこれを活性エネルギー線により硬化させてなる部材
JP2005309255A (ja) * 2004-04-23 2005-11-04 Asahi Denka Kogyo Kk 配向性高分子
JP2009157160A (ja) * 2007-12-27 2009-07-16 Sekisui Chem Co Ltd 熱可塑性樹脂フィルム及びそれを用いた偏光板
JP2013076773A (ja) * 2011-09-29 2013-04-25 Nippon Shokubai Co Ltd 偏光子保護フィルム及びその利用

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CN109490323A (zh) * 2017-09-13 2019-03-19 住友化学株式会社 缺陷检查装置、缺陷检查方法、圆偏振板或椭圆偏振板的制造方法及相位差板的制造方法
CN111316144B (zh) * 2017-11-10 2023-01-06 住友化学株式会社 圆偏振板及显示装置
CN111316144A (zh) * 2017-11-10 2020-06-19 住友化学株式会社 圆偏振板及显示装置
KR20220015508A (ko) * 2018-03-28 2022-02-08 닛토덴코 가부시키가이샤 편광자, 편광 필름, 적층 편광 필름, 화상 표시 패널, 및 화상 표시 장치
KR102565143B1 (ko) 2018-03-28 2023-08-09 닛토덴코 가부시키가이샤 편광자, 편광 필름, 적층 편광 필름, 화상 표시 패널, 및 화상 표시 장치
JP2019219525A (ja) * 2018-06-20 2019-12-26 日東電工株式会社 偏光フィルム、粘着剤層付き偏光フィルム、及び画像表示装置
TWI724436B (zh) * 2018-06-20 2021-04-11 日商日東電工股份有限公司 偏光薄膜、附黏著劑層之偏光薄膜及影像顯示裝置
WO2019244916A1 (fr) * 2018-06-20 2019-12-26 日東電工株式会社 Film de polarisation, film de polarisation fournie par couche adhésive, et dispositif d'affichage d'image
JP2019219527A (ja) * 2018-06-20 2019-12-26 日東電工株式会社 偏光フィルム、粘着剤層付偏光フィルム、及び画像表示装置
WO2019244915A1 (fr) * 2018-06-20 2019-12-26 日東電工株式会社 Film polarisant, film polarisant avec couche adhésive et dispositif d'affichage d'image
JP7709679B2 (ja) 2019-08-09 2025-07-17 三菱瓦斯化学株式会社 化合物、（共）重合体、組成物、及びパターン形成方法
WO2021029396A1 (fr) * 2019-08-09 2021-02-18 三菱瓦斯化学株式会社 Composé, (co)polymère, composition et procédé de formation de motif
JPWO2021029396A1 (fr) * 2019-08-09 2021-02-18
JP2021157063A (ja) * 2020-03-27 2021-10-07 日東電工株式会社 偏光フィルム及び画像表示装置
WO2021192568A1 (fr) * 2020-03-27 2021-09-30 日東電工株式会社 Film polarisant et dispositif d'affichage d'image
JP7382264B2 (ja) 2020-03-27 2023-11-16 日東電工株式会社 偏光フィルム及び画像表示装置
JP2021162862A (ja) * 2020-03-31 2021-10-11 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. 偏光積層体及びそれを含む画像表示装置
CN113466983A (zh) * 2020-03-31 2021-10-01 东友精细化工有限公司 偏光层叠体和包含其的图像显示装置
WO2022202427A1 (fr) * 2021-03-24 2022-09-29 太陽インキ製造株式会社 Composition de résine thermodurcissable, film sec, produit durci, circuit imprimé nu et composant électrique/électronique
JP2024171107A (ja) * 2023-05-29 2024-12-11 日東電工株式会社 偏光板

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TW201734074A (zh) 2017-10-01
JP6724930B2 (ja) 2020-07-15
CN108474892B (zh) 2020-12-11
JPWO2017110342A1 (ja) 2018-10-18

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