WO2018079563A1 - Film stratifié et son procédé de production, plaque de polarisation, et dispositif d'affichage - Google Patents

Film stratifié et son procédé de production, plaque de polarisation, et dispositif d'affichage Download PDF

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Publication number
WO2018079563A1
WO2018079563A1 PCT/JP2017/038397 JP2017038397W WO2018079563A1 WO 2018079563 A1 WO2018079563 A1 WO 2018079563A1 JP 2017038397 W JP2017038397 W JP 2017038397W WO 2018079563 A1 WO2018079563 A1 WO 2018079563A1
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Prior art keywords
layer
laminated film
resin
unit
film
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PCT/JP2017/038397
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English (en)
Japanese (ja)
Inventor
浩成 摺出寺
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日本ゼオン株式会社
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Priority to CN201780063639.6A priority Critical patent/CN109843586B/zh
Priority to KR1020197011260A priority patent/KR102405800B1/ko
Priority to JP2018547694A priority patent/JP6891902B2/ja
Publication of WO2018079563A1 publication Critical patent/WO2018079563A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/03—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers with respect to the orientation of features
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to a laminated film, a manufacturing method thereof, a polarizing plate, and a display device.
  • a resin film is widely used, and as such a film, a laminated film including a plurality of layers is known (for example, Patent Document 1).
  • a laminated film can easily obtain desired physical properties, optical properties, and the like by appropriately selecting elements such as material and thickness of layers constituting the laminated film.
  • the laminated film may be used as a polarizer protective film in a polarizing plate including a polarizer and a polarizer protective film, for example.
  • a laminated film used for a polarizer protective film is required to have high peel strength when bonded to a polarizer and high adhesion between each layer constituting the laminated film.
  • the laminated film used for the polarizer protective film is required to have a small retardation in the in-plane direction.
  • the object of the present invention is to provide high peel strength when bonded to a polarizer, high adhesion between constituent layers, and low retardation in the in-plane direction, thereby protecting the polarizer protective film. And a polarizing plate having optical properties that are highly durable and useful for display devices, and a display device that has high durability and excellent display quality.
  • the present inventor has studied to solve the above problems. As a result, the present inventor has found that any of low retardation, adhesion and peel strength can be improved by employing a specific material in combination with a specific layer structure, and has completed the present invention. That is, the present invention is as follows.
  • thermoplastic resin A is Two or more polymer blocks [D] based on the unit [I]; Unit [II] or one or more polymer blocks [E] having as a main component a combination of unit [I] and unit [II]
  • the unit [I] is a cyclic hydrocarbon group-containing compound hydride unit,
  • the unit [II] is a chain hydrocarbon compound hydride unit
  • the thermoplastic resin B is a resin different from the thermoplastic resin A, The heat softening temperature Ts [A] of the thermoplastic resin A, the heat softening temperature Ts [B] of the thermoplastic resin B, the thickness t [A] of the A layer, the thickness t [B] of the B layer, and the lamination A laminated film in which the in-plane retardation Re (total)
  • thermoplastic resin A is a blend of two or more types of thermoplastic resins.
  • thermoplastic resin B is a resin including a polymer having an alicyclic structure.
  • a polarizing plate comprising the laminated film according to any one of [1] to [4] and a polarizer.
  • a display device comprising the laminated film according to any one of [1] to [4].
  • the laminated film of the present invention has high peel strength when bonded to a polarizer, high adhesion between the constituent layers, and low retardation in the in-plane direction, thereby providing a polarizer protective film. Can be usefully used. According to the production method of the present invention, such a laminated film of the present invention can be easily produced.
  • the polarizing plate of the present invention is highly durable and has optical characteristics that can be usefully used in a display device.
  • the display device of the present invention can be a display device having high durability and excellent display quality.
  • the cyclic hydrocarbon group is a hydrocarbon group containing a cyclic structure such as an aromatic ring, cycloalkane, or cycloalkene.
  • the chain hydrocarbon compound is a hydrocarbon compound that does not contain such a cyclic hydrocarbon group.
  • nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the film and giving the maximum refractive index.
  • ny represents the refractive index in the in-plane direction of the film and perpendicular to the nx direction.
  • nz represents the refractive index in the thickness direction of the film.
  • d represents the thickness of the film.
  • the retardation measurement wavelength is 532 nm unless otherwise specified.
  • the “polarizing plate” includes not only a rigid member but also a flexible member such as a resin film.
  • the “long” film means a film having a length of 5 times or more, preferably 10 times or more, and specifically a roll.
  • the upper limit of the length of the long film is not particularly limited, and can be, for example, 100,000 times or less with respect to the width.
  • the laminated film of the present invention includes an A layer made of a thermoplastic resin A and a B layer made of a thermoplastic resin B provided on at least one surface of the A layer.
  • the laminated film may include only one layer or two layers or more of each of the A layer and the B layer.
  • the laminated film has a layer configuration of (A layer) / (B layer).
  • a layer configuration of (B layer) / (A layer) / (B layer) may be mentioned. From the viewpoint of obtaining the advantageous effects of the present invention, a layer structure of (B layer) / (A layer) / (B layer) is preferable.
  • thermoplastic resin A has two or more polymer blocks [D] having a specific unit [I] and one having a specific unit [II] or a combination of the unit [I] and the unit [II].
  • a hydrogenated block copolymer [G] containing the above polymer block [E] is included.
  • the unit [I] is a cyclic hydride group-containing compound hydride unit. That is, the unit [I] has a structure obtained by polymerizing a cyclic hydrocarbon group-containing compound and hydrogenating the unsaturated bond if the unit obtained by the polymerization has an unsaturated bond. It is a structural unit. However, the unit [I] includes a unit obtained by any manufacturing method as long as it has the structure.
  • the unit [I] is preferably a structural unit having a structure obtained by polymerizing an aromatic vinyl compound and hydrogenating the unsaturated bond.
  • unit [Ia] includes a unit obtained by any manufacturing method as long as it has the structure.
  • a structural unit having a structure obtained by polymerizing styrene and hydrogenating the unsaturated bond may be referred to as a styrene hydride unit.
  • the styrene hydride unit also includes a unit obtained by any production method as long as it has the structure. Examples of the unit [Ia] include structural units represented by the following structural formula (1).
  • R c represents an alicyclic hydrocarbon group.
  • R c include cyclohexyl groups such as cyclohexyl group; decahydronaphthyl groups and the like.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chain hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group or an imide group.
  • R 1 , R 2 and R 3 are preferably a hydrogen atom and a chain hydrocarbon group having 1 to 6 carbon atoms from the viewpoints of heat resistance, low birefringence and mechanical strength.
  • the chain hydrocarbon group is preferably a saturated hydrocarbon group, and more preferably an alkyl group.
  • a preferred specific example of the unit [Ia] is a structural unit represented by the following formula (1-1).
  • the structural unit represented by the formula (1-1) is a styrene hydride unit.
  • any of the stereoisomers of the unit [I] can be used as the unit [I]. Only one type of unit [I] may be used, or two or more types may be used in combination at any ratio.
  • Unit [II] is a structural unit having a structure obtained by polymerizing a chain hydrocarbon compound and hydrogenating the unsaturated bond if the unit obtained by such polymerization has an unsaturated bond. is there.
  • the unit [II] includes units obtained by any production method as long as it has the structure.
  • the unit [II] is preferably a structural unit having a structure obtained by polymerizing a diene compound and hydrogenating the unsaturated bond if the unit obtained by the polymerization has an unsaturated bond. is there.
  • unit [IIa] includes a unit obtained by any production method as long as it has the structure.
  • a structural unit having a structure obtained by polymerizing isoprene and hydrogenating the unsaturated bond may be referred to as an isoprene hydride unit.
  • the isoprene hydride unit also includes a unit obtained by any production method as long as it has the structure.
  • the unit [IIa] preferably has a structure obtained by polymerizing a conjugated diene compound such as a chain conjugated diene compound and hydrogenating the unsaturated bond.
  • a conjugated diene compound such as a chain conjugated diene compound
  • Examples thereof include a structural unit represented by the following structural formula (2) and a structural unit represented by the structural formula (3).
  • R 4 to R 9 are each independently a hydrogen atom, a chain hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an imide group, or a silyl group. Or a chain hydrocarbon group substituted with a polar group (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imide group, or silyl group).
  • R 4 to R 9 are preferably a hydrogen atom and a chain hydrocarbon group having 1 to 6 carbon atoms from the viewpoints of heat resistance, low birefringence, mechanical strength, and the like.
  • the chain hydrocarbon group is preferably a saturated hydrocarbon group, and more preferably an alkyl group.
  • R 10 to R 15 each independently represent a hydrogen atom, a chain hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group, a cyano group, an amide group, an imide group, or a silyl group. Or a chain hydrocarbon group substituted with a polar group (halogen atom, alkoxy group, hydroxyl group, ester group, cyano group, amide group, imide group, or silyl group).
  • R 10 to R 15 are preferably a hydrogen atom and a chain hydrocarbon group having 1 to 6 carbon atoms from the viewpoint of heat resistance, low birefringence, mechanical strength, and the like.
  • the chain hydrocarbon group is preferably a saturated hydrocarbon group, and more preferably an alkyl group.
  • unit [IIa] include structural units represented by the following formulas (2-1) to (2-3).
  • the structural units represented by the formulas (2-1) to (2-3) are isoprene hydride units.
  • any of the stereoisomers in the unit [II] can be used as the unit [II]. Only one type of unit [II] may be used, or two or more types may be used in combination at any ratio.
  • the hydrogenated block copolymer [G] preferably has a triblock molecular structure having one block [E] per molecule and two blocks [D] per molecule linked to both ends thereof. That is, the hydrogenated block copolymer [G] has one block [E] per molecule and one block [D1] per molecule having a unit [I] linked to one end of the block [E]. And a block [E] connected to the other end of the block [E] and having a unit [I], and a block [D2] per molecule is preferable.
  • the weight ratio (D1 + D2) / E are preferably within a specific range. Specifically, the weight ratio (D1 + D2) / E is preferably 70/30 or more, more preferably 82/18 or more, preferably 90/10 or less, more preferably 87/13 or less.
  • the weight ratio D1 of the block [D1] and the block [D2] is obtained from the viewpoint of easily obtaining a laminated film having the above characteristics.
  • / D2 is preferably within a specific range.
  • the weight ratio D1 / D2 is preferably 5 or more, more preferably 5.2 or more, particularly preferably 5.5 or more, preferably 8 or less, more preferably 7.8 or less, particularly preferably. Is 7.5 or less.
  • the weight average molecular weight Mw of the hydrogenated block copolymer [G] is preferably 50000 or more, more preferably 55000 or more, particularly preferably 60000 or more, preferably 80000 or less, more preferably 75000 or less, and particularly preferably 70000. It is as follows. When the weight average molecular weight Mw is in the above range, a laminated film having the above characteristics can be easily obtained. In particular, by reducing the weight average molecular weight, the retardation can be effectively reduced.
  • the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the hydrogenated block copolymer [G] is preferably 2.0 or less, more preferably 1.7 or less, and particularly preferably 1.5. Or less, preferably 1.0 or more.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the weight average molecular weight Mw and the number average molecular weight Mn of the hydrogenated block copolymer [G] can be measured as values in terms of polystyrene by gel permeation chromatography using tetrahydrofuran as a solvent.
  • the block [D1] and the block [D2] are preferably independently composed of only the unit [I], but may include arbitrary units other than the unit [I].
  • Examples of arbitrary structural units include structural units based on vinyl compounds other than the unit [I].
  • the content of any structural unit in the block [D] is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less.
  • the block [E] is preferably composed only of the unit [II], but may include any unit other than the unit [II].
  • Examples of arbitrary structural units include structural units based on vinyl compounds other than the unit [II].
  • the content of any structural unit in the block [E] is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 1% by weight or less.
  • the hydrogenated block copolymer [G] as the above-described triblock copolymer has low retardation. Therefore, the laminated film of the present invention including the A layer made of the resin A can easily obtain desired characteristics.
  • the manufacturing method of hydrogenated block copolymer [G] is not specifically limited, Arbitrary manufacturing methods can be employ
  • the hydrogenated block copolymer [G] is prepared, for example, by preparing monomers corresponding to the unit [I] and the unit [II], polymerizing them, and hydrogenating the obtained polymer [F]. Can be produced.
  • an aromatic vinyl compound can be used as the monomer corresponding to the unit [I].
  • examples include styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, ⁇ -propyl styrene, ⁇ -isopropyl styrene, ⁇ -t-butyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 2 , 4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, and 4-phenylstyrene Vinylcyclohexanes such as vinylcyclohexane and 3-methylisopropenylcyclohexane; and 4-vinylcyclohe
  • Examples of monomers corresponding to the unit [II] include chain conjugated dienes such as butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. Can be mentioned. These monomers may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • anionic polymerization can be usually employed.
  • the polymerization may be performed by any of bulk polymerization and solution polymerization. Among these, solution polymerization is preferable in order to continuously perform the polymerization reaction and the hydrogenation reaction.
  • Examples of the solvent used in the polymerization reaction include aliphatic hydrocarbon solvents such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, And alicyclic hydrocarbon solvents such as decalin; and aromatic hydrocarbon solvents such as benzene and toluene.
  • an aliphatic hydrocarbon solvent and an alicyclic hydrocarbon solvent are preferable because they can be used as they are as an inert solvent for the hydrogenation reaction.
  • a solvent may be used individually by 1 type and may be used combining two or more types by arbitrary ratios. The solvent is usually used at a ratio of 200 to 10,000 parts by weight with respect to 100 parts by weight of the total monomers.
  • a polymerization initiator is usually used.
  • polymerization initiators include monoorganolithiums such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium; and dilithiomethane, 1,4-diobane, and 1,4-dilithiol Examples thereof include polyfunctional organolithium compounds such as 2-ethylcyclohexane.
  • a polymerization initiator may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • Examples of the method include a production method including the following first to third steps.
  • the material called “monomer composition” includes not only a mixture of two or more substances but also a material composed of a single substance.
  • First step A step of polymerizing the monomer composition (d1) containing a cyclic hydrocarbon group-containing compound to form a block [d1] corresponding to the block [D1].
  • Second step At one end of the block [d1], the monomer composition (e) containing a chain hydrocarbon compound is polymerized to form a block [e] corresponding to the block [E].
  • Forming a polymer Third step: At the terminal on the block [e] side of the diblock polymer, the monomer composition (d2) containing the cyclic hydrocarbon group-containing compound is polymerized to obtain a triblock copolymer [F]. Obtaining.
  • the monomer composition (d1) and the monomer composition (d2) may be the same or different.
  • a polymerization accelerator and a randomizer can be used in order to prevent an excessively long chain of one component in each block.
  • a Lewis base compound can be used as a randomizer.
  • Lewis base compounds include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, and ethylene glycol methyl phenyl ether; tetramethylethylenediamine, trimethylamine, triethylamine, and pyridine.
  • Tertiary amine compounds such as potassium-t-amyl oxide and alkali metal alkoxide compounds such as potassium-t-butyl oxide; and phosphine compounds such as triphenylphosphine.
  • phosphine compounds such as triphenylphosphine.
  • One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the polymerization temperature is not limited as long as the polymerization proceeds, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and is usually 200 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
  • the polymer [F] can be recovered from the reaction mixture by any method if necessary.
  • the recovery method include a steam stripping method, a direct desolvation method, and an alcohol coagulation method.
  • the polymer can be used as it is without recovering the polymer from the polymerization solution.
  • Hydrogenation can be performed, for example, using a suitable hydrogenation catalyst. More specifically, hydrogenation is performed using a hydrogenation catalyst containing at least one metal selected from the group consisting of nickel, cobalt, iron, rhodium, palladium, platinum, ruthenium, and rhenium in an organic solvent. sell.
  • the hydrogenation catalyst may be a heterogeneous catalyst or a homogeneous catalyst.
  • a hydrogenation catalyst may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
  • the heterogeneous catalyst may be used as it is as a metal or a metal compound, or may be used by being supported on an appropriate carrier.
  • the carrier include activated carbon, silica, alumina, calcium carbide, titania, magnesia, zirconia, diatomaceous earth, and silicon carbide.
  • the amount of the catalyst supported on the carrier is usually 0.01% by weight or more, preferably 0.05% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less.
  • homogeneous catalysts include catalysts combining nickel, cobalt, or iron compounds with organometallic compounds (eg, organoaluminum compounds, organolithium compounds); and rhodium, palladium, platinum, ruthenium, rhenium, etc.
  • organometallic complex catalyst is mentioned.
  • nickel, cobalt, or iron compounds include acetylacetone salts, naphthenates, cyclopentadienyl compounds, and cyclopentadienyl dichloro compounds of these metals.
  • organoaluminum compounds include alkylaluminums such as triethylaluminum and triisobutylaluminum; aluminum halides such as diethylaluminum chloride and ethylaluminum dichloride; and alkylaluminum hydrides such as diisobutylaluminum hydride.
  • organometallic complex catalysts include metal complexes such as ⁇ -dichloro- ⁇ -benzene complexes, dichloro-tris (triphenylphosphine) complexes, hydrido-chloro-triphenylphosphine) complexes of the above metals. .
  • the amount of the hydrogenation catalyst used is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and usually 100 parts by weight with respect to 100 parts by weight of the polymer. Hereinafter, it is preferably 50 parts by weight or less, more preferably 30 parts by weight or less.
  • the reaction temperature during the hydrogenation reaction is usually 10 ° C. to 250 ° C., but is preferably 50 ° C. or more, more preferably, because the hydrogenation rate can be increased and the polymer chain scission reaction can be reduced. It is 80 degreeC or more, Preferably it is 200 degrees C or less, More preferably, it is 180 degrees C or less.
  • the pressure during the reaction is usually 0.1 MPa to 30 MPa, but in addition to the above reasons, from the viewpoint of operability, it is preferably 1 MPa or more, more preferably 2 MPa or more, preferably 20 MPa or less, more preferably 10 MPa or less.
  • the hydrogenation rate is usually 90% or more, preferably 95% or more, more preferably 97% or more. By increasing the hydrogenation rate, the low birefringence and thermal stability of the hydrogenated block copolymer [G] can be enhanced.
  • the hydrogenation rate can be measured by 1 H-NMR.
  • thermoplastic resin A may consist of only the hydrogenated block copolymer [G], but may contain any component other than the hydrogenated block copolymer [G].
  • Optional components include, for example, inorganic fine particles; stabilizers such as antioxidants, heat stabilizers, ultraviolet absorbers, near infrared absorbers; resin modifiers such as lubricants and plasticizers; colorants such as dyes and pigments And antistatic agents.
  • these arbitrary components one type may be used alone, or two or more types may be used in combination at an arbitrary ratio. However, from the viewpoint of remarkably exhibiting the effects of the present invention, it is preferable that the content of any component is small.
  • the total proportion of the optional components is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably 3 parts by weight or less, with respect to 100 parts by weight of the hydrogenated block copolymer [G]. .
  • thermoplastic resin A may include only one type of copolymer as the hydrogenated block copolymer [G], but may include two or more types of copolymers.
  • the thermoplastic resin A can be a blend of two or more thermoplastic resins. That is, the thermoplastic resin A can be a blended product obtained by blending a plurality of types of thermoplastic resins each containing a different hydrogenated block copolymer [G]. Such a blend can be formed into a pellet blend formed by molding each of a plurality of types of thermoplastic resins as pellets and mixing the plurality of types of pellets.
  • thermoplastic resin B is a resin different from the thermoplastic resin A.
  • the thermoplastic resins A and B are different from each other at least in terms of different thermal softening temperatures.
  • thermoplastic resin B any resin capable of providing a laminated film satisfying the requirements of the present invention can be adopted.
  • resins containing a polymer containing an alicyclic structure those having desired characteristics can be appropriately selected and used.
  • the alicyclic structure-containing polymer is a polymer having an alicyclic structure in the repeating unit, and a polymer having an alicyclic structure in the main chain and a polymer having an alicyclic structure in the side chain. Any of these can be used.
  • the alicyclic structure-containing polymer includes a crystalline resin and an amorphous resin, but an amorphous resin is preferable from the viewpoint of obtaining the desired effect of the present invention and the manufacturing cost.
  • Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of thermal stability.
  • the number of carbon atoms constituting the repeating unit of one alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 6 to 15.
  • the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight. That's it.
  • the alicyclic structure-containing polymer includes (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) a vinyl alicyclic hydrocarbon.
  • examples thereof include polymers and hydrides thereof. Among these, from the viewpoints of transparency and moldability, norbornene polymers and hydrides thereof are more preferable.
  • Examples of the norbornene polymer include a ring-opening polymer of a norbornene monomer, a ring-opening copolymer of a norbornene monomer and another monomer capable of ring-opening copolymerization, and a hydride thereof; an addition polymer of a norbornene monomer, norbornene Examples thereof include addition copolymers with other monomers copolymerizable with the monomers.
  • a ring-opening polymer hydride of a norbornene monomer is particularly preferable from the viewpoint of transparency.
  • the above alicyclic structure-containing polymer is selected from, for example, polymers disclosed in JP-A No. 2002-321302.
  • the alicyclic structure-containing polymer has a glass transition temperature of preferably 80 ° C. or higher, more preferably 100 ° C. to 250 ° C.
  • An alicyclic structure-containing polymer having a glass transition temperature in such a range is less susceptible to deformation and stress during use at high temperatures and is excellent in durability.
  • the molecular weight of the alicyclic structure-containing polymer is converted to polyisoprene measured by gel permeation chromatography (hereinafter abbreviated as “GPC”) using cyclohexane (toluene when the resin is not dissolved) as a solvent.
  • the weight average molecular weight (Mw) in terms of polystyrene (when the solvent is toluene) is usually 10,000 to 100,000, preferably 25,000 to 80,000, more preferably 25,000 to 50,000. is there. When the weight average molecular weight is in such a range, the mechanical strength and moldability of the base film are highly balanced.
  • the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the alicyclic structure-containing polymer is usually 1 to 10, preferably 1 to 4, and more preferably 1.2 to 3.5. .
  • the resin containing the alicyclic structure-containing polymer may be composed only of the alicyclic structure-containing polymer, but may contain any compounding agent as long as the effects of the present invention are not significantly impaired.
  • the ratio of the alicyclic structure-containing polymer in the resin containing the alicyclic structure-containing polymer is preferably 70% by weight or more, more preferably 80% by weight or more.
  • the resin containing the alicyclic structure-containing polymer Since various products are commercially available as the resin containing the alicyclic structure-containing polymer, those having desired characteristics can be appropriately selected and used as the resin B. Examples of such commercially available products include a product group having a trade name “ZEONOR” (manufactured by Nippon Zeon Co., Ltd.).
  • the laminated film of the present invention has a heat softening temperature Ts [A] of the thermoplastic resin A, a heat softening temperature Ts [B] of the thermoplastic resin B, a thickness t [A] of the A layer, and a thickness t [B of the B layer. ], Re (total) in the in-plane direction of the laminated film, and the plane orientation coefficient P [B] of the B layer satisfy the following formulas (1) to (6). (1) 130 ° C. ⁇ Ts [A] ⁇ 145 ° C. (2) 120 ° C. ⁇ Ts [B] ⁇ 145 ° C.
  • Ts [A] is 130 ° C. or higher, preferably 135 ° C. or higher, 145 ° C. or lower, preferably 142 ° C. or lower.
  • Ts [B] is 120 ° C. or higher, preferably 123 ° C. or higher, 145 ° C. or lower, preferably 137 ° C., more preferably 135 ° C. or lower.
  • the retardation Re (total) in the in-plane direction of the laminated film is 5 nm or less, preferably 4 nm or less.
  • the lower limit of Re (total) is ideally 0 nm.
  • the thickness t [A] of the A layer is 20 ⁇ m or more, preferably 22 ⁇ m or more, and 50 ⁇ m or less, preferably 40 ⁇ m or less.
  • the thickness t [B] of the B layer is 1 ⁇ m or more, preferably 1.4 ⁇ m or more, 15 ⁇ m or less, preferably 14.0 ⁇ m or less, more preferably 4 ⁇ m or less, and even more preferably 3.5 ⁇ m or less.
  • the thickness ranges described above are the thickness ranges of one A layer each.
  • the thickness ranges described above are the thickness ranges of one B layer.
  • the plane orientation coefficient P [B] of the B layer is 1.0 ⁇ 10 ⁇ 5 or more, preferably 1.5 ⁇ 10 ⁇ 5 or more, while 2.0 ⁇ 10 ⁇ 3 or less, preferably 1.5 ⁇ . 10 ⁇ 3 or less.
  • the laminated film of the present invention is useful as a polarizer protective film by adopting the specific materials described above as materials constituting the A layer and the B layer and satisfying the formulas (1) to (6). It can be set as a laminated film. Specifically, the material having the specific thermoplastic resin A described above is adopted as the material constituting the A layer, and the surface orientation coefficient in the specific range mentioned above is given as the material constituting the B layer.
  • the resins A and B those having the thermal softening temperatures Ts [A] and Ts [B] in the specific range described above are adopted, and the thicknesses of the A layer and the B layer are (4) to ( By having the range of 5), while having a low Re (total) as defined in (3), the peel strength when bonded to the polarizer is high, the adhesion between each layer is high, and the surface A laminated film having a small inward retardation can be obtained.
  • a resin containing an alicyclic structure-containing polymer is adopted as the resin B constituting the B layer, when a laminated film satisfying the above-described condition is formed, the adhesion between the layers is high. In addition, it is possible to easily obtain a laminated film having both good and other characteristics.
  • the laminated film comprises two or more of any one or more of the A layer and the B layer
  • any one or more of the set of adjacent A and B layers satisfies the requirements described above
  • the group at least the effect of the present invention can be obtained.
  • all the sets satisfy the requirements described above.
  • the laminated film has a layer structure of (B layer) / (A layer) / (B ′ layer)
  • the effects of the present invention such as high adhesion can be obtained at least between the layers of the group.
  • both sets satisfy the formulas (1) to (6).
  • the thermal softening temperature Ts of each resin can be measured by TMA (thermomechanical analysis) measurement.
  • TMA thermomechanical analysis
  • a film to be measured is cut into a 5 mm ⁇ 20 mm shape as a sample, and the temperature is adjusted in a state in which a tension of 50 mN is applied in the longitudinal direction of the sample using TMA / SS7100 (manufactured by SII NanoTechnology Inc.)
  • the temperature (° C.) when the linear expansion changes by 3% can be measured as the softening temperature.
  • the thickness of each layer can be measured by microscopic observation. Specifically, the thickness of each layer can be measured by slicing the laminated film using a microtome and observing the cut surface. The cut surface can be observed, for example, with a polarizing microscope (for example, “BX51” manufactured by Olympus).
  • a polarizing microscope for example, “BX51” manufactured by Olympus.
  • the retardation of the laminated film can be measured using a retardation measuring device at a wavelength of 532 nm.
  • a retardation measuring device for example, the product name “Axoscan” (manufactured by Axometric) may be used.
  • the laminated film of the present invention can have good adhesion.
  • the adhesion mentioned here is the adhesion between each layer constituting the laminated film.
  • the adhesion can be evaluated as good when no delamination occurs between the tears.
  • multilayer film of this invention can make a thing with high peeling strength at the time of bonding with a polarizer.
  • the laminated film of the present invention is usually a transparent layer and transmits visible light.
  • the specific light transmittance can be appropriately selected according to the use of the laminated film.
  • the light transmittance at a wavelength of 420 nm to 780 nm is preferably 85% or more, more preferably 88% or more.
  • the laminated film of the present invention may include an arbitrary layer in addition to the A layer and the B layer.
  • the optional layer include a hard coat layer that increases the surface hardness, a mat layer that improves the slipping property of the film, and an antireflection layer.
  • the manufacturing method of the laminated film of this invention is not specifically limited, Arbitrary manufacturing methods can be employ
  • the laminated film of the present invention can be produced by preparing Resin A and Resin B and molding them into a desired shape.
  • the molding method for molding the resin A and the resin B include melt extrusion molding by coextrusion. By performing such melt extrusion molding, a laminated film having a desired thickness can be efficiently produced.
  • the temperature of the resin at the time of melt extrusion molding by co-extrusion is not particularly limited and is a temperature at which each resin can be melted and is suitable for molding.
  • the temperature can be set as appropriate.
  • the higher temperature Ts [H] of Ts [A] and Ts [B] can be set as a reference. More specifically, it is preferably (Ts [H] +70) ° C. or higher, more preferably (Ts [H] +80) ° C. or higher, while preferably (Ts [H] +180) ° C. or lower, more preferably It is (Ts [H] +150) degrees C or less.
  • a laminated film as such a stretched film is specifically: a layer composed of a thermoplastic resin A, and a layer b composed of a thermoplastic resin B provided on at least one surface of the a layer.
  • a step of preparing a film; and a pre-stretching film can be produced by a production method comprising a stretching step of stretching in at least one direction.
  • the above-described stretching treatment makes it possible to easily manufacture a laminated film having a small thickness, a large area, and good quality, so that the manufacturing efficiency can be improved.
  • the stretching conditions for producing a stretched film as a laminated film can be appropriately adjusted so that the above-described laminated film is obtained.
  • the stretching performed in the stretching process can be uniaxial stretching, biaxial stretching, or other stretching.
  • the stretching direction can be set in any direction.
  • the stretching direction may be any of the longitudinal direction of the film, the width direction, and other oblique directions.
  • the angle formed by the two stretching directions when biaxial stretching is performed can usually be an angle orthogonal to each other, but is not limited thereto, and may be an arbitrary angle.
  • Biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching.
  • the stretching temperature can be set based on the higher temperature Ts [H] of Ts [A] and Ts [B]. Specifically, it is preferably (Ts [H] +10) ° C. or more, more preferably (Ts [H] +13) ° C. or more, while preferably (Ts [H] +50) ° C. or less, more preferably ( Ts [H] +45) ° C. or lower.
  • Ts [H] +10 ° C. or more
  • Ts [H] +13) ° C. or more while preferably (Ts [H] +50) ° C. or less, more preferably ( Ts [H] +45) ° C. or lower.
  • the draw ratio is preferably 1.1 times or more, more preferably 1.15 times or more, particularly preferably 1.2 times or more, preferably 2.5 times or less, more preferably 2.25 times or less, particularly Preferably it is 2 times or less.
  • the draw ratio falls within the above temperature range, a stretched film as a laminated film having the above characteristics can be easily obtained.
  • the magnification in each of the two stretching directions can be within this range.
  • the laminated film of the present invention can be suitably used as a protective film for protecting other layers in a display device such as a liquid crystal display device.
  • multilayer film of this invention are suitable as a polarizer protective film, and are especially suitable as an inner side polarizer protective film of a display apparatus.
  • the polarizing plate of the present invention includes a polarizer and the laminated film described above.
  • the laminated film can function as a polarizer protective film.
  • the polarizing plate of the present invention may further include an adhesive layer for bonding them between the laminated film and the polarizer.
  • the polarizer is not particularly limited, and any polarizer can be used.
  • the polarizer include those obtained by adsorbing a material such as iodine or a dichroic dye on a polyvinyl alcohol film and then stretching the material.
  • the adhesive constituting the adhesive layer include those using various polymers as a base polymer. Examples of such base polymers include acrylic polymers, silicone polymers, polyesters, polyurethanes, polyethers, and synthetic rubbers.
  • the polarizing plate of the present invention can usually comprise one layer of polarizer and two layers of protective films provided on both sides thereof. Of these two protective films, both may be the laminated film of the present invention, and only one of them may be the laminated film of the present invention.
  • a liquid crystal display device including a light source and a liquid crystal cell and having polarizing plates on both the light source side and the display surface side of the liquid crystal cell, It is particularly preferable to provide the laminated film of the invention. By having such a configuration, it is possible to easily configure a liquid crystal display device having a good display quality with small light leakage and color unevenness at an oblique viewing angle.
  • liquid crystal display device suitable for providing the polarizing plate of the present invention examples include an in-plane switching (IPS) mode, a vertical alignment (VA) mode, a multi-domain vertical alignment (MVA) mode, and a continuous spin wheel alignment (CPA).
  • IPS in-plane switching
  • VA vertical alignment
  • MVA multi-domain vertical alignment
  • CPA continuous spin wheel alignment
  • HAN hybrid alignment nematic
  • TN twisted nematic
  • STN super twisted nematic
  • OBC optical compensated bend
  • a liquid crystal display device having an IPS mode liquid crystal cell is particularly preferable because the laminated film of the present invention has remarkable effects of suppressing light leakage at an oblique viewing angle and suppressing color unevenness.
  • the laminated film when it has two B layers, it may be expressed by adding “′” to one symbol for distinction. For example, when a laminated film has two B layers, one of them may be expressed as a B ′ layer for distinction.
  • the thickness of each layer was measured as follows.
  • the film to be measured was sliced using a microtome (“RV-240” manufactured by Daiwa Koki Co., Ltd.).
  • the cut surface of the sliced film was observed with a polarizing microscope (OLYMPUS "BX51”), and the thickness was measured.
  • phase difference Re (total) of the entire laminated film was measured using a phase difference measuring device (product name “Axoscan” manufactured by Axometric) at a wavelength of 532 nm. Further, the refractive index nx, ny, nz of the B layer at a wavelength of 532 nm was measured using a prism coupler refractometer Model 2010 manufactured by Metricon Co., and the phase difference Re [B] of the B layer and the plane orientation of the B layer according to the following equations The coefficient P [B] was calculated.
  • phase difference Re [A] of the A layer was calculated by obtaining the difference of the phase difference Re [B] of the B layer from the phase difference Re (total) of the entire laminated film.
  • a test film (glass transition temperature 160 ° C., thickness 100 ⁇ m, manufactured by Nippon Zeon Co., Ltd., which has not been subjected to stretching treatment) made of a resin containing a norbornene-based polymer was prepared.
  • One side of the laminated film and the test film was subjected to corona treatment.
  • An adhesive was attached to the corona-treated surface of the laminated film and the corona-treated surface of the test film, and the surfaces to which the adhesive was attached were bonded together.
  • a UV adhesive (CRB series (manufactured by Toyochem Co., Ltd.)) was used as the adhesive, thereby obtaining a sample film including a laminated film and a test film. Thereafter, the sample film was cut into a width of 15 mm, and the laminated film side was bonded to the surface of the slide glass with an adhesive.
  • a double-sided adhesive tape (manufactured by Nitto Denko Corporation, product number “CS9621”) was used as the adhesive.
  • a 90 degree peel test was performed by sandwiching the test film at the tip of a force gauge and pulling it in the normal direction of the surface of the slide glass.
  • the measured peel strength was evaluated according to the following criteria.
  • a surface of the retardation film laminate subjected to corona treatment was bonded to one surface of the prepared polarizing film via the adhesive.
  • a triacetyl cellulose film was bonded to the other surface of the polarizing film via the adhesive. Then, it was made to dry for 7 minutes at 80 degreeC, the adhesive agent was hardened, and the sample film was obtained. The sample film obtained was subjected to a 90 degree peel test. As a result of the experiment, the same result as that obtained when the test film was used instead of the polarizing plate was obtained. Therefore, the results of the following examples and comparative examples using test films instead of polarizing plates are reasonable.
  • the polymer solution obtained in (P1-1) is transferred to a pressure-resistant reactor equipped with a stirrer, and diatomaceous earth-supported nickel is used as a hydrogenation catalyst.
  • 4.0 parts of a catalyst product name “E22U”, nickel loading 60%, manufactured by JGC Catalysts & Chemicals Co., Ltd.
  • 30 parts of dehydrated cyclohexane were added and mixed.
  • the inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution.
  • a hydrogenation reaction was performed at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours.
  • the reaction solution obtained by the hydrogenation reaction contained the hydrogenated block copolymer [G1].
  • the hydrogenated block copolymer had a Mw [G1] of 71,800, a molecular weight distribution Mw / Mn of 1.30, and a hydrogenation rate of almost 100%.
  • the reaction solution is filtered to remove the hydrogenation catalyst, and then the phenol-based antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate] (product name “AO60”, manufactured by ADEKA) 2.0 parts of xylene solution in which 0.3 part was dissolved was added and dissolved to obtain a solution.
  • the above solution is treated at a temperature of 260 ° C. and a pressure of 0.001 MPa or less using a cylindrical concentrating dryer (product name “Contro”, manufactured by Hitachi, Ltd.), and cyclohexane, xylene and other volatile components are removed from the solution.
  • the reaction solution is filtered to remove the hydrogenation catalyst, and then the phenol-based antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate] (product name “AO60”, manufactured by ADEKA) 2.0 parts of xylene solution in which 0.3 part was dissolved was added and dissolved to obtain a solution.
  • the above solution is treated at a temperature of 260 ° C. and a pressure of 0.001 MPa or less using a cylindrical concentrating dryer (product name “Contro”, manufactured by Hitachi, Ltd.), and cyclohexane, xylene and other volatile components are removed from the solution.
  • the pellet-shaped resin [G1] obtained in Production Example 1 was introduced as the thermoplastic resin A, melted, and supplied to the single-layer die through the feed block.
  • the introduction of the resin A into the single screw extruder was performed through a hopper loaded in the single screw extruder.
  • the surface roughness (arithmetic mean roughness Ra) of the die slip of the single-layer die was 0.1 ⁇ m.
  • the extruder A exit temperature of the resin A was 260 ° C.
  • the thermoplastic resin B a resin B1 containing an alicyclic structure-containing polymer (manufactured by Nippon Zeon Co., Ltd., heat softening temperature 136 ° C.) is introduced, dissolved, and fed through a feed block. To a single layer die. The extruder B temperature of resin B was 260 ° C.
  • Resin A and Resin B were discharged from a single-layer die in a molten state at 260 ° C. Thereby, a film-like resin including three layers of a layer made of the resin B, a layer made of the resin A, and a layer made of the resin B in this order was continuously formed (coextrusion molding step).
  • the discharged film-like resin was cast on a cooling roll. In casting, edge pinning was performed to fix the widthwise end of the film-like resin to the cooling roll, and the air gap amount was set to 50 mm. Thereby, the film-like resin was cooled to obtain a resin film having a three-layer structure.
  • the obtained laminated film was a two-type, three-layer film including a B layer made of resin B, an A layer made of resin A, and a B ′ layer made of resin B in this order.
  • the total thickness of this laminated film was 40.0 ⁇ m.
  • Each layer thickness of B layer / A layer / B ′ layer was 2.0 ⁇ m / 36.0 ⁇ m / 2.0 ⁇ m.
  • the in-plane retardation Re (total) of the laminated film was 3.7 nm.
  • the plane orientation coefficient P [B] of the B layer and the B ′ layer was 2.6 ⁇ 10 ⁇ 4 .
  • the adhesion of each layer was good, and the peel strength could not be measured due to material destruction, and was therefore determined as A.
  • Example 2 A laminated film was produced and evaluated by the same operation as in Example 1 except for the following changes. In place of the pellet-shaped resin [G1] obtained in Production Example 1, the pellet-shaped resin [G2] obtained in Production Example 2 was used.
  • Example 3 A laminated film was produced and evaluated by the same operation as in Example 1 except for the following changes. -As thermoplastic resin B, it replaced with resin B1 and used resin B2 (The Nippon Zeon company make, heat softening temperature 128 degreeC) containing an alicyclic structure containing polymer. -The extrusion conditions of Resin A and Resin B were changed, whereby the total thickness of the laminated film was 40.0 ⁇ m, and each layer thickness of B layer / A layer / B ′ layer was 3.0 ⁇ m / 34.0 ⁇ m / 3.0 ⁇ m. .
  • Example 4 A laminated film was produced and evaluated by the same operation as in Example 1 except for the following changes.
  • the pellet-shaped resin [G2] obtained in Production Example 2 was used.
  • -As thermoplastic resin B it replaced with resin B1 and used resin B2 (The Nippon Zeon company make, heat softening temperature 128 degreeC) containing an alicyclic structure containing polymer.
  • resin B1 and used resin B2 The Nippon Zeon company make, heat softening temperature 128 degreeC
  • -The extrusion conditions of Resin A and Resin B were changed, whereby the total thickness of the laminated film was 40.0 ⁇ m, and each layer thickness of B layer / A layer / B ′ layer was 3.0 ⁇ m / 34.0 ⁇ m / 3.0 ⁇ m. .
  • Example 5 A resin film having a three-layer structure was obtained by the same operation as (1-1) in Example 1.
  • the obtained resin film was continuously stretched in the film width direction.
  • the stretching was performed by using a tenter-type transverse stretching machine, holding both ends of the film with clips, and expanding the interval in the width direction of the clips.
  • the stretching conditions were a temperature of 160 ° C. and a stretching ratio of 1.5 times. After stretching, both ends of the film were trimmed to a width of 1330 mm to obtain a stretched long laminated film.
  • the obtained laminated film was a two-type, three-layer film including a B layer made of resin B, an A layer made of resin A, and a B ′ layer made of resin B in this order.
  • Each layer thickness of B layer / A layer / B ′ layer of this laminated film was 1.3 ⁇ m / 24.0 ⁇ m / 1.3 ⁇ m.
  • the in-plane retardation Re (total) of the laminated film was 3.0 nm.
  • B layer and the surface orientation coefficient P [B] of the B 'layer was 1.2 ⁇ 10 -3.
  • the adhesion of each layer was good and the peel strength was 3.4 N / 15 mm.
  • Example 6 A laminated film was produced and evaluated in the same manner as in Example 5 except for the following changes. In place of the pellet-shaped resin [G1] obtained in Production Example 1, the pellet-shaped resin [G2] obtained in Production Example 2 was used.
  • Example 7 A laminated film was produced and evaluated in the same manner as in Example 5 except for the following changes. -As thermoplastic resin B, it replaced with resin B1 and used resin B2 (The Nippon Zeon company make, heat softening temperature 128 degreeC) containing an alicyclic structure containing polymer. -The extrusion conditions for Resin A and Resin B were changed. However, the subsequent operation such as stretching was not changed, and the same operation as in Example 5 was performed. As a result, each layer thickness of layer B / layer A / layer B ′ of the laminated film was set to 2.0 ⁇ m / 22.7 ⁇ m / 2.0 ⁇ m.
  • Example 8 A laminated film was produced and evaluated in the same manner as in Example 5 except for the following changes.
  • the pellet-shaped resin [G2] obtained in Production Example 2 was used.
  • -As thermoplastic resin B it replaced with resin B1 and used resin B2 (The Nippon Zeon company make, heat softening temperature 128 degreeC) containing an alicyclic structure containing polymer.
  • resin B1 and used resin B2 The Nippon Zeon company make, heat softening temperature 128 degreeC
  • -The extrusion conditions for Resin A and Resin B were changed. However, the subsequent operation such as stretching was not changed, and the same operation as in Example 5 was performed.
  • each layer thickness of layer B / layer A / layer B ′ of the laminated film was set to 2.0 ⁇ m / 22.7 ⁇ m / 2.0 ⁇ m.
  • Example 9 (9-1. Production of pellet blend)
  • thermoplastic resin A the pellet blend obtained in (9-1) was used in place of the pellet-shaped resin [G1] obtained in Production Example 1.
  • thermoplastic resin B it replaced with resin B1 and used resin B2 (The Nippon Zeon company make, heat softening temperature 128 degreeC) containing an alicyclic structure containing polymer.
  • resin B1 and used resin B2 The Nippon Zeon company make, heat softening temperature 128 degreeC
  • each layer thickness of layer B / layer A / layer B ′ of the laminated film was set to 9.4 ⁇ m / 23.0 ⁇ m / 9.4 ⁇ m.
  • the in-plane retardation Re (total) of the laminated film was 0.7 nm.
  • the plane orientation coefficient P [B] of the B layer and the B ′ layer was 1.0 ⁇ 10 ⁇ 4 .
  • the adhesion of each layer was good and the peel strength was 1.5 N / 15 mm.
  • Example 10 (10-1. Production of pellet blend)
  • thermoplastic resin A the pellet blend obtained in (10-1) was used in place of the pellet-shaped resin [G1] obtained in Production Example 1.
  • thermoplastic resin B it replaced with resin B1 and used resin B2 (The Nippon Zeon company make, heat softening temperature 128 degreeC) containing an alicyclic structure containing polymer.
  • resin B1 and used resin B2 The Nippon Zeon company make, heat softening temperature 128 degreeC
  • the thickness of each layer of layer B / layer A / layer B ′ of the laminated film was set to 5.1 ⁇ m / 30.6 ⁇ m / 5.1 ⁇ m.
  • the in-plane retardation Re (total) of the laminated film was 0.9 nm.
  • the plane orientation coefficient P [B] of the B layer and the B ′ layer was 1.4 ⁇ 10 ⁇ 4 .
  • the adhesion of each layer was good and the peel strength was 3.2 N / 15 mm.
  • Resin A was discharged from a single-layer die in a molten state at 260 ° C. Thereby, a film-like resin composed only of the layer made of the resin A was continuously formed (coextrusion molding step).
  • the discharged film-like resin was cast on a cooling roll. In casting, edge pinning was performed to fix the widthwise end of the film-like resin to the cooling roll, and the air gap amount was set to 50 mm. Thereby, the film-like resin was cooled to obtain a resin film having a single layer structure.
  • the obtained resin film having a single layer structure was continuously stretched in the film width direction.
  • the stretching was performed by using a tenter-type transverse stretching machine, holding both ends of the film with clips, and expanding the interval in the width direction of the clips.
  • the stretching conditions were a temperature of 160 ° C. and a stretching ratio of 1.5 times. After stretching, both ends of the film were trimmed to a width of 1330 mm to obtain a stretched long single layer film.
  • the obtained single-layer film was a one-layer film consisting only of the A layer made of the resin A.
  • the thickness of this laminated film was 27.0 ⁇ m.
  • the in-plane retardation Re (total) of the laminated film was 0.9 nm.
  • the peel strength was 0.16 N / 15 mm and was therefore determined as C.
  • Example 3 A laminated film was produced and evaluated by the same operation as in Example 7 (Comparative Example 3) or the same operation as in Example 8 (Comparative Example 4) except for the following changes.
  • B2 A resin containing an alicyclic structure-containing polymer, a heat softening temperature of 128 ° C., one of the product group of “ZEONOR” manufactured by Nippon Zeon.
  • B3 a resin containing an alicyclic structure-containing polymer, a heat softening temperature of 160 ° C., one of the product groups of “ZEONOR” manufactured by Nippon Zeon.
  • a laminated film satisfying the requirements of the present invention including the thermal softening temperature and thickness of each layer can be a laminated film excellent in both peel strength and adhesion.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Laminated Bodies (AREA)
  • Liquid Crystal (AREA)

Abstract

La présente invention concerne un film stratifié comprenant une couche A composée d'une résine thermoplastique A et une couche B composée d'une résine thermoplastique B, la résine A comprenant un copolymère bloc hydrogéné qui contient : au moins deux blocs polymères constitués principalement d'une unité spécifique [I] ; et un ou plusieurs blocs polymères constitués principalement soit d'une unité spécifique [II], soit d'une combinaison de l'unité [I] et de l'unité [II], la température de ramollissement thermique de la résine A, la température de ramollissement thermique de la résine B, l'épaisseur de la couche A, l'épaisseur de la couche B, le retard dans la direction dans le plan du film stratifié, et le coefficient d'orientation planaire de la couche B satisfaisant respectivement des exigences spécifiques.
PCT/JP2017/038397 2016-10-31 2017-10-24 Film stratifié et son procédé de production, plaque de polarisation, et dispositif d'affichage WO2018079563A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201780063639.6A CN109843586B (zh) 2016-10-31 2017-10-24 层叠膜及其制造方法、偏振片和显示装置
KR1020197011260A KR102405800B1 (ko) 2016-10-31 2017-10-24 적층 필름, 그 제조 방법, 편광판, 및 표시 장치
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TWI731188B (zh) 2021-06-21
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