WO2018079563A1 - Laminated film and production method therefore, polarization plate, and display device - Google Patents
Laminated film and production method therefore, polarization plate, and display device Download PDFInfo
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- 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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- 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
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- 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
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- 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
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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
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- 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
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- 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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Abstract
Description
すなわち、本発明は、下記のとおりである。 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.
前記熱可塑性樹脂Aは、
単位[I]を主成分とする、2つ以上の重合体ブロック[D]と、
単位[II]、又は前記単位[I]及び前記単位[II]の組み合わせを主成分とする1つ以上の重合体ブロック[E]
を含む水素化ブロック共重合体[G]を含み、
前記単位[I]は、環式炭化水素基含有化合物水素化物単位であり、
前記単位[II]は、鎖状炭化水素化合物水素化物単位であり、
前記熱可塑性樹脂Bは、前記熱可塑性樹脂Aとは異なる樹脂であり、
前記熱可塑性樹脂Aの熱軟化温度Ts[A]、前記熱可塑性樹脂Bの熱軟化温度Ts[B]、前記A層の厚みt[A]、前記B層の厚みt[B]、前記積層フィルムの面内方向のレターデーションRe(total)、及び前記B層の面配向係数P[B]が、下記式(1)~(6)を満たす、積層フィルム。
(1)130℃≦Ts[A]≦145℃
(2)120℃≦Ts[B]≦145℃
(3)0≦Re(total)≦5nm
(4)20μm≦t[A]≦50μm
(5)1μm≦t[B]≦15μm
(6)1.0×10-5≦|P[B]|≦2.0×10-3
〔2〕 前記環式炭化水素基含有化合物が芳香族ビニル化合物であり、前記鎖状炭化水素化合物が鎖状共役ジエン系化合物である、〔1〕に記載の積層フィルム。
〔3〕 前記熱可塑性樹脂Aは、2種類以上の熱可塑性樹脂のブレンド物である、〔1〕又は〔2〕に記載の積層フィルム。
〔4〕 前記熱可塑性樹脂Bは脂環式構造を含有する重合体を含む樹脂である〔1〕~〔3〕のいずれか1項に記載の積層フィルム。
〔5〕 〔1〕~〔4〕のいずれか1項に記載の積層フィルムの製造方法であって、
前記熱可塑性樹脂Aからなるa層、及び前記a層の少なくとも一方の面上に設けられた熱可塑性樹脂Bからなるb層を備える延伸前フィルムを調製する工程、及び
前記延伸前フィルムを、少なくとも1の方向に延伸する延伸工程を含む、製造方法。
〔6〕 〔1〕~〔4〕のいずれか1項に記載の積層フィルムと偏光子とを備える偏光板。
〔7〕 〔1〕~〔4〕のいずれか1項に記載の積層フィルムを備える表示装置。 [1] A laminated film comprising 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 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]
A hydrogenated block copolymer [G] containing
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) of the 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.
(3) 0 ≦ Re (total) ≦ 5 nm
(4) 20 μm ≦ t [A] ≦ 50 μm
(5) 1 μm ≦ t [B] ≦ 15 μm
(6) 1.0 × 10 −5 ≦ | P [B] | ≦ 2.0 × 10 −3
[2] The laminated film according to [1], wherein the cyclic hydrocarbon group-containing compound is an aromatic vinyl compound, and the chain hydrocarbon compound is a chain conjugated diene compound.
[3] The laminated film according to [1] or [2], wherein the thermoplastic resin A is a blend of two or more types of thermoplastic resins.
[4] The laminated film according to any one of [1] to [3], wherein the thermoplastic resin B is a resin including a polymer having an alicyclic structure.
[5] A method for producing a laminated film according to any one of [1] to [4],
Preparing a pre-stretch film comprising a layer comprising the thermoplastic resin A, and a b layer comprising a thermoplastic resin B provided on at least one surface of the a layer; and at least the pre-stretch film, The manufacturing method including the extending | stretching process extended | stretched in 1 direction.
[6] A polarizing plate comprising the laminated film according to any one of [1] to [4] and a polarizer.
[7] A display device comprising the laminated film according to any one of [1] to [4].
本発明の積層フィルムは、熱可塑性樹脂AからなるA層、及びA層の少なくとも一方の面上に設けられた熱可塑性樹脂BからなるB層を備える。 [1. (Outline of laminated film)
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.
熱可塑性樹脂Aは、特定の単位[I]を有する、2つ以上の重合体ブロック[D]と、特定の単位[II]、又は単位[I]及び単位[II]の組み合わせを有する1つ以上の重合体ブロック[E]を含む水素化ブロック共重合体[G]を含む。 [2. Thermoplastic resin A]
The 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.
単位[I]は、環式炭化水素基含有化合物水素化物単位である。即ち、単位[I]は、環式炭化水素基含有化合物を重合し、さらに、かかる重合により得られた単位が不飽和結合を有していればその不飽和結合を水素化して得られる構造を有する構造単位である。ただし、単位[I]は、当該構造を有する限りにおいて、どのような製造方法で得られた単位をも含む。 [2.1. Unit [I]]
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.
同様に、本願においては、例えばスチレンを重合し、その不飽和結合を水素化して得られる構造を有する構造単位を、スチレン水素化物単位と呼ぶことがある。スチレン水素化物単位も、当該構造を有する限りにおいて、どのような製造方法で得られた単位をも含む。
単位[Ia]の例としては、以下の構造式(1)で表される構造単位が挙げられる。 The unit [I] is preferably a structural unit having a structure obtained by polymerizing an aromatic vinyl compound and hydrogenating the unsaturated bond. Hereinafter, such a unit may be referred to as “unit [Ia]”. However, the unit [Ia] includes a unit obtained by any manufacturing method as long as it has the structure.
Similarly, in the present application, for example, 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).
単位[II]は、鎖状炭化水素化合物を重合し、さらに、かかる重合により得られた単位が不飽和結合を有していればその不飽和結合を水素化して得られる構造を有する構造単位である。ただし、単位[II]は、当該構造を有する限りにおいて、どのような製造方法で得られた単位をも含む。 [2.2. Unit [II]]
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. However, the unit [II] includes units obtained by any production method as long as it has the structure.
同様に、本願においては、例えばイソプレンを重合し、その不飽和結合を水素化して得られる構造を有する構造単位を、イソプレン水素化物単位と呼ぶことがある。イソプレン水素化物単位も、当該構造を有する限りにおいて、どのような製造方法で得られた単位をも含む。 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. Hereinafter, such a unit may be referred to as “unit [IIa]”. However, the unit [IIa] includes a unit obtained by any production method as long as it has the structure.
Similarly, in the present application, for example, 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.
水素化ブロック共重合体[G]は、1分子あたり1つのブロック[E]と、その両端に連結された1分子当たり2つのブロック[D]とを有するトリブロック分子構造を有することが好ましい。すなわち、水素化ブロック共重合体[G]は、1分子あたり1つのブロック[E]と;ブロック[E]の一端に連結され、単位[I]を有する、1分子あたり1つのブロック[D1]と;ブロック[E]の他端に連結され、単位[I]を有する、1分子あたり1つのブロック[D2]と;を含むトリブロック共重合体であることが好ましい。 [2.3. Hydrogenated block copolymer [G]]
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.
水素化ブロック共重合体[G]の製造方法は、特に限定されず任意の製造方法を採用しうる。水素化ブロック共重合体[G]は、例えば、単位[I]及び単位[II]に対応する単量体を用意し、これらを重合させ、得られた重合体[F]を水素化することにより製造しうる。 [2.4. Method for producing hydrogenated block copolymer [G]]
The manufacturing method of hydrogenated block copolymer [G] is not specifically limited, Arbitrary manufacturing methods can be employ | adopted. 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.
溶媒は、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。
溶媒は、通常、全単量体100重量部に対して200~10,000重量部となるような割合で用いられる。 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. Among these, 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.
第二工程:かかるブロック[d1]の一端において、鎖状炭化水素化合物を含有するモノマー組成物(e)を重合させて、ブロック[E]に対応するブロック[e]を形成し、ジブロックの重合体を形成する工程。
第三工程:かかるジブロックの重合体の、ブロック[e]側の末端において、環式炭化水素基含有化合物を含有するモノマー組成物(d2)を重合させて、トリブロック共重合体[F]を得る工程。ただし、モノマー組成物(d1)とモノマー組成物(d2)とは、同一でも異なっていてもよい。 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. However, the monomer composition (d1) and the monomer composition (d2) may be the same or different.
均一系触媒の例としては、ニッケル、コバルト、又は鉄の化合物と有機金属化合物(例えば、有機アルミニウム化合物、有機リチウム化合物)とを組み合わせた触媒;並びにロジウム、パラジウム、白金、ルテニウム、及びレニウム等の有機金属錯体触媒が挙げられる。ニッケル、コバルト、又は鉄の化合物の例としては、これらの金属のアセチルアセトン塩、ナフテン酸塩、シクロペンタジエニル化合物、及びシクロペンタジエニルジクロロ化合物が挙げられる。有機アルミニウム化合物の例としては、トリエチルアルミニウム、トリイソブチルアルミニウム等のアルキルアルミニウム;ジエチルアルミニウムクロリド、エチルアルミニウムジクロリド等のハロゲン化アルミニウム;並びにジイソブチルアルミニウムハイドライド等の水素化アルキルアルミニウムが挙げられる。
有機金属錯体触媒の例としては、例えば、上記各金属のγ-ジクロロ-π-ベンゼン錯体、ジクロロ-トリス(トリフェニルホスフィン)錯体、ヒドリド-クロロ-トリフェニルホスフィン)錯体等の金属錯体が挙げられる。
水素化触媒の使用量は、重合体100重量部に対して、通常0.01重量部以上、好ましくは0.05重量部以上、より好ましくは0.1重量部以上であり、通常100重量部以下、好ましくは50重量部以下、より好ましくは30重量部以下である。 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. Examples of 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.
Examples of 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. An organometallic complex catalyst is mentioned. Examples of nickel, cobalt, or iron compounds include acetylacetone salts, naphthenates, cyclopentadienyl compounds, and cyclopentadienyl dichloro compounds of these metals. Examples of 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.
Examples of organometallic complex catalysts include metal complexes such as γ-dichloro-π-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.
水素化率は、通常90%以上、好ましくは95%以上、より好ましくは97%以上である。水素化率を高くすることにより、水素化ブロック共重合体[G]の低複屈折性及び熱安定性等を高めることができる。水素化率は1H-NMRにより測定できる。 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.
熱可塑性樹脂Aは、水素化ブロック共重合体[G]のみからなってもよいが、水素化ブロック共重合体[G]以外に任意の成分を含んでいてもよい。
任意の成分としては、例えば、無機微粒子;酸化防止剤、熱安定剤、紫外線吸収剤、近赤外線吸収剤等の安定剤;滑剤、可塑剤等の樹脂改質剤;染料や顔料等の着色剤;及び帯電防止剤が挙げられる。これらの任意の成分としては、1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。ただし、本発明の効果を顕著に発揮させる観点からは、任意の成分の含有割合は少ないことが好ましい。例えば、任意の成分の合計の割合は、水素化ブロック共重合体[G]の100重量部に対して、10重量部以下が好ましく、5重量部以下がより好ましく、3重量部以下が更に好ましい。 [2.5. Any component other than hydrogenated block copolymer [G]]
The 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. As 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. For example, 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]. .
熱可塑性樹脂Aは、水素化ブロック共重合体[G]として、1種類のみの共重合体を含んでもよいが、2種類以上の共重合体を含んでもよい。 [2.6. Blend)
The 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.
熱可塑性樹脂Bは、熱可塑性樹脂Aとは異なる樹脂である。熱可塑性樹脂A及びBは、少なくとも熱軟化温度が異なる点において互いに相違する。熱可塑性樹脂Bとしては、本発明の要件を満たす積層フィルムを与えうる任意の樹脂を採用しうる。特に、脂環式構造を含有する重合体を含む樹脂のうち、所望の特性を有するものを適宜選択して用いうる。 [3. Thermoplastic resin B]
The 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. As the thermoplastic resin B, any resin capable of providing a laminated film satisfying the requirements of the present invention can be adopted. In particular, among resins containing a polymer containing an alicyclic structure, those having desired characteristics can be appropriately selected and used.
上記の脂環式構造含有重合体は、例えば特開2002-321302号公報に開示されている重合体から選ばれる。 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. Among these, 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.
本発明の積層フィルムは、その熱可塑性樹脂Aの熱軟化温度Ts[A]、熱可塑性樹脂Bの熱軟化温度Ts[B]、A層の厚みt[A]、B層の厚みt[B]、積層フィルムの面内方向のレターデーションRe(total)、及びB層の面配向係数P[B]が、下記式(1)~(6)を満たす。
(1)130℃≦Ts[A]≦145℃
(2)120℃≦Ts[B]≦145℃
(3)0≦Re(total)≦5nm
(4)20μm≦t[A]≦50μm
(5)1μm≦t[B]≦15μm
(6)1.0×10-5≦|P[B]|≦2.0×10-3 [4. (Dimensions and characteristics of laminated film)
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.
(3) 0 ≦ Re (total) ≦ 5 nm
(4) 20 μm ≦ t [A] ≦ 50 μm
(5) 1 μm ≦ t [B] ≦ 15 μm
(6) 1.0 × 10 −5 ≦ | P [B] | ≦ 2.0 × 10 −3
本発明の積層フィルムは、A層及びB層に加えて、任意の層を備えうる。任意の層の例としては、表面硬度を高めるハードコート層、フィルムの滑り性を良くするマット層、反射防止層等が挙げられる。 [5. Any layer)
The laminated film of the present invention may include an arbitrary layer in addition to the A layer and the B layer. Examples of 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.
本発明の積層フィルムの製造方法は、特に限定されず、任意の製造方法を採用しうる。例えば、樹脂A及び樹脂Bを調製し、これらを所望の形状に成形することにより、本発明の積層フィルムを製造しうる。樹脂A及び樹脂Bを成形するための成形方法の好ましい例としては、共押出による溶融押出成形が挙げられる。かかる溶融押出成形を行うことにより、所望の各層厚みを有する積層フィルムを効率的に製造することができる。 [6. Method for producing laminated film]
The manufacturing method of the laminated film of this invention is not specifically limited, Arbitrary manufacturing methods can be employ | adopted. For example, the laminated film of the present invention can be produced by preparing Resin A and Resin B and molding them into a desired shape. Preferable examples of 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.
本発明の積層フィルムは、液晶表示装置などの表示装置において、他の層を保護する保護フィルムとして好適に用いうる。中でも、本発明の積層フィルムは、偏光子保護フィルムとして好適であり、表示装置の内側偏光子保護フィルムとして特に好適である。 [7. Application of laminated film: Polarizing plate]
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. Especially, the laminated | 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.
以下の説明において、量を表す「%」及び「部」は、別に断らない限り重量基準である。また、以下に説明する操作は、別に断らない限り、常温及び常圧の条件において行った。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.
In the following description, “%” and “part” representing amounts are based on weight unless otherwise specified. In addition, the operations described below were performed under normal temperature and normal pressure conditions unless otherwise specified.
〔重量平均分子量及び数平均分子量の測定方法〕
重合体の重量平均分子量及び数平均分子量は、ゲル・パーミエーション・クロマトグラフィー(GPC)システム(東ソー社製「HLC-8320」)を用いて、ポリスチレン換算値として測定した。測定の際、カラムとしてはHタイプカラム(東ソー社製)を用い、溶媒としてはテトラヒドロフランを用いた。また、測定時の温度は、40℃であった。 〔Evaluation methods〕
[Method for measuring weight average molecular weight and number average molecular weight]
The weight average molecular weight and number average molecular weight of the polymer were measured as polystyrene equivalent values using a gel permeation chromatography (GPC) system (“HLC-8320” manufactured by Tosoh Corporation). In the measurement, an H type column (manufactured by Tosoh Corporation) was used as the column, and tetrahydrofuran was used as the solvent. Moreover, the temperature at the time of measurement was 40 degreeC.
重合体の水素化率は、オルトジクロロベンゼン-d4を溶媒として、145℃で、1H-NMR測定により測定した。 [Method for Measuring Hydrogenation Rate of Hydrogenated Block Copolymer [G]]
The hydrogenation rate of the polymer was measured by 1 H-NMR measurement at 145 ° C. using orthodichlorobenzene-d 4 as a solvent.
各層の厚みは、次のようにして測定した。
測定対象のフィルムを、ミクロトーム(大和光機社製「RV-240」)を用いてスライスした。スライスしたフィルムの切断面を、偏光顕微鏡(オリンパス社製「BX51」)で観察し、その厚みを測定した。 [Method for measuring thickness of each layer]
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.
測定対象のフィルムを5mm×20mmの形状に切り出し試料とした。測定装置として、TMA/SS7100(エスアイアイ・ナノテクノロジー株式会社製)を用いた。TMA(熱機械的分析)測定において、試料の長手方向に50mNの張力を加えた状態で、温度を変化させた。線膨張が3%変化した時の温度(℃)を、軟化温度とした。 [Measurement method of thermal softening temperature Ts]
A film to be measured was cut into a 5 mm × 20 mm shape and used as a sample. As a measuring device, TMA / SS7100 (manufactured by SII Nanotechnology Inc.) was used. In TMA (thermomechanical analysis) measurement, the temperature was changed with a tension of 50 mN applied in the longitudinal direction of the sample. The temperature (° C.) when the linear expansion changed by 3% was defined as the softening temperature.
波長532nmで位相差測定装置(Axometric社製 製品名「Axoscan」)を用いて、積層フィルム全体の位相差Re(total)を測定した。また、メトリコン社製プリズムカプラ屈折率計Model2010を用いて波長532nmでのB層の屈折率nx、ny、nzを測定し、以下式に従ってB層の位相差Re[B]とB層の面配向係数P[B]を算出した。
Re[B]=(nx-ny)×d[B]
P[B]=(nx+ny)/2-nz
その後、積層フィルム全体の位相差Re(total)からB層の位相差Re[B]の差を求める事で、A層の位相差Re[A]を算出した。 [Measurement method of phase difference and plane orientation coefficient]
The 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.
Re [B] = (nx−ny) × d [B]
P [B] = (nx + ny) / 2−nz
Thereafter, the 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.
実施例及び比較例で得られた積層フィルムを20cm×20cmに裁断し、4辺をそれぞれ5cm手で引裂いた際、4辺全ての引裂きで、裂け目において層間の剥離が生じない場合を良好と判定した。 [Adhesion of each layer]
When the laminated films obtained in Examples and Comparative Examples were cut into 20 cm × 20 cm, and each of the four sides was torn by 5 cm by hand, it was judged that the case where no peeling occurred between the tears at all four sides and the layers were not separated. did.
偏光板の代わりのフィルムとして、ノルボルネン系重合体を含む樹脂からなる試験用フィルム(ガラス転移温度160℃、厚み100μm、日本ゼオン社製、延伸処理を施していないもの)を用意した。積層フィルム及び前記試験用フィルムの片面に、コロナ処理を施した。積層フィルムのコロナ処理を施した面、及び試験用フィルムのコロナ処理した面に接着剤を付着させ、接着剤を付着させた面同士を貼り合わせた。この際、接着剤としてはUV接着剤(CRBシリーズ(トーヨーケム社製)を用いた。これにより、積層フィルム及び試験用フィルムを備えるサンプルフィルムを得た。
その後、前記サンプルフィルムを15mmの幅に裁断して、積層フィルム側をスライドガラスの表面に粘着剤にて貼り合わせた。この際、粘着剤としては、両面粘着テープ(日東電工社製、品番「CS9621」)を用いた。
フォースゲージの先端に前記試験用フィルムを挟み、スライドガラスの表面の法線方向に引っ張ることにより、90度剥離試験を実施した。この際、試験用フィルムが剥れる際に測定された力は、積層フィルムと試験用フィルムとを剥離させるために要する力であるので、この力の大きさを剥離強度として測定した。
測定された剥離強度は、以下の基準で評価した。
A:剥離強度が6.0N/mm以上であるか、又は、剥離前に材料破壊が発生した。
B:剥離強度が1.5N/15mm以上6.0N/15mm未満である。
C:剥離強度が1.5N/15mm未満である。 [Measurement method of peel strength]
As a film instead of a polarizing plate, a test film (glass transition temperature 160 ° C., thickness 100 μm, 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. At this time, 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. At this time, 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. At this time, since the force measured when the test film peels is a force required to peel the laminated film and the test film, the magnitude of this force was measured as the peel strength.
The measured peel strength was evaluated according to the following criteria.
A: The peel strength was 6.0 N / mm or more, or material destruction occurred before peeling.
B: Peel strength is 1.5 N / 15 mm or more and less than 6.0 N / 15 mm.
C: Peel strength is less than 1.5 N / 15 mm.
前記の剥離強度の測定方法では、偏光板の代わりに特定の試験用フィルムを用いている。このように、偏光板の代わりに試験用フィルムを用いて剥離強度の測定を行うことの妥当性を検証するため、実施例1で得られた位相差フィルム積層体について、発明者は以下の実験を行った。
試験用フィルムの代わりに、特開2005-70140号公報の実施例1に従って、偏光フィルムの片方の表面に位相差フィルム積層体を貼り合わせ、偏光フィルムのもう片方の表面にはトリアセチルセルロースフィルムを貼り合わせ、90度剥離試験を実施した。すなわち、まず、特開2005-70140号公報の実施例1に記載の偏光フィルム及び接着剤を用意した。用意した偏光フィルムの片方の表面に、位相差フィルム積層体のコロナ処理を施した面を、前記の接着剤を介して貼り合わせた。また、偏光フィルムのもう片方の表面には、前記の接着剤を介してトリアセチルセルロースフィルムを貼り合わせた。その後、80℃で7分間乾燥させて接着剤を硬化させて、サンプルフィルムを得た。得られたサンプルフィルムについて90度剥離試験を行った。
前記の実験の結果、偏光板の代わりに試験用フィルムを用いた場合と同様の結果が得られた。したがって、偏光板の代わりに試験用フィルムを用いた下記の実施例及び比較例の結果は、妥当なものである。 (Supplementary method for measuring peel strength)
In the measurement method of the peel strength, a specific test film is used instead of the polarizing plate. Thus, in order to verify the validity of measuring the peel strength using a test film instead of a polarizing plate, the inventors conducted the following experiment on the retardation film laminate obtained in Example 1. Went.
Instead of the test film, according to Example 1 of JP-A-2005-70140, a retardation film laminate is bonded to one surface of the polarizing film, and a triacetyl cellulose film is attached to the other surface of the polarizing film. Bonding and 90 degree peeling test were carried out. That is, first, a polarizing film and an adhesive described in Example 1 of JP-A-2005-70140 were prepared. A surface of the retardation film laminate subjected to corona treatment was bonded to one surface of the prepared polarizing film via the adhesive. In addition, 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.
(P1-1)ブロック共重合体[F1]の製造
攪拌装置を備え、内部が十分に窒素置換された反応器に、脱水シクロヘキサン270部、脱水スチレン75部及びジブチルエーテル7.0部を入れた。全容を60℃で攪拌しながら、n-ブチルリチウム(15%シクロヘキサン溶液)5.6部を加えて重合を開始させた。引続き全容を60℃で60分間攪拌した。反応温度は、反応停止まで60℃を維持した。この時点(重合第1段階)で反応液をガスクロマトグラフィー(以下、「GC」と記載することがある。)及びGPCにより分析した結果、重合転化率は99.4%であった。 [Production Example 1]
(P1-1) Production of Block Copolymer [F1] A reactor equipped with a stirrer and sufficiently purged with nitrogen inside was charged with 270 parts of dehydrated cyclohexane, 75 parts of dehydrated styrene and 7.0 parts of dibutyl ether. . While stirring the whole volume at 60 ° C., 5.6 parts of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, the whole volume was stirred at 60 ° C. for 60 minutes. The reaction temperature was maintained at 60 ° C. until the reaction was stopped. At this time (first stage of polymerization), the reaction solution was analyzed by gas chromatography (hereinafter sometimes referred to as “GC”) and GPC. As a result, the polymerization conversion rate was 99.4%.
その後、更に、反応液に脱水スチレン10部を、30分間に亘って連続的に添加し、添加終了後そのまま30分攪拌した。この時点(重合第3段階)で、反応液をGC及びGPCにより分析した結果、重合転化率はほぼ100%であった。 Next, 15 parts of dehydrated isoprene was continuously added to the reaction solution over 40 minutes, and stirring was continued for 30 minutes as it was after the addition was completed. At this time (second stage of polymerization), the reaction solution was analyzed by GC and GPC. As a result, the polymerization conversion was 99.8%.
Thereafter, 10 parts of dehydrated styrene was continuously added to the reaction solution over 30 minutes, and stirred for 30 minutes as it was after completion of the addition. At this time (the third stage of polymerization), the reaction solution was analyzed by GC and GPC. As a result, the polymerization conversion was almost 100%.
(P1-1)で得た重合体溶液を、攪拌装置を備えた耐圧反応器に移送し、水素化触媒として、珪藻土担持型ニッケル触媒(製品名「E22U」、ニッケル担持量60%、日揮触媒化成社製)4.0部、及び脱水シクロヘキサン30部を添加して混合した。反応器内部を水素ガスで置換し、さらに溶液を攪拌しながら水素を供給し、温度190℃、圧力4.5MPaにて6時間水素化反応を行った。
水素化反応により得られた反応溶液には、水素化ブロック共重合体[G1]が含まれていた。水素化ブロック共重合体のMw[G1]は71,800、分子量分布Mw/Mnは1.30、水素化率はほぼ100%であった。 (P1-2) Production of hydrogenated block copolymer [G1] 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.) and 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%.
次いで、上記溶液を、円筒型濃縮乾燥器(製品名「コントロ」、日立製作所社製)を用いて、温度260℃、圧力0.001MPa以下で処理し、溶液からシクロヘキサン、キシレン及びその他の揮発成分を除去し、溶融した樹脂を得た。これをダイからストランド状に押出し、冷却し、ペレタイザーによりペレットに成形した。これにより、水素化ブロック共重合体[G1]を含む、樹脂[G1]のペレット95部を製造した。
得られた樹脂[G1]における水素化ブロック共重合体[G1]は、Mw[G1]=68,500、Mw/Mn=1.30、Ts=139℃であった。 After completion of the hydrogenation reaction, 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.
Next, 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. And a molten resin was obtained. This was extruded from a die into a strand, cooled, and formed into pellets by a pelletizer. As a result, 95 parts of a pellet of the resin [G1] containing the hydrogenated block copolymer [G1] was produced.
Hydrogenated block copolymer [G1] in the obtained resin [G1] was Mw [G1] = 68,500, Mw / Mn = 1.30, and Ts = 139 ° C.
(P2-1)ブロック共重合体[F2]の製造
攪拌装置を備え、内部が十分に窒素置換された反応器に、脱水シクロヘキサン270部、脱水スチレン70部及びジブチルエーテル7.0部を入れた。全容を60℃で攪拌しながら、n-ブチルリチウム(15%シクロヘキサン溶液)5.6部を加えて重合を開始させた。引続き全容を60℃で60分間攪拌した。反応温度は、反応停止まで60℃を維持した。この時点(重合第1段階)で反応液をGC及びGPCにより分析した結果、重合転化率は99.4%であった。 [Production Example 2]
(P2-1) Production of block copolymer [F2] A reactor equipped with a stirrer and sufficiently purged with nitrogen inside was charged with 270 parts of dehydrated cyclohexane, 70 parts of dehydrated styrene and 7.0 parts of dibutyl ether. . While stirring the whole volume at 60 ° C., 5.6 parts of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, the whole volume was stirred at 60 ° C. for 60 minutes. The reaction temperature was maintained at 60 ° C. until the reaction was stopped. As a result of analyzing the reaction solution by GC and GPC at this time (first stage of polymerization), the polymerization conversion rate was 99.4%.
その後、更に、反応液に脱水スチレン10部を、30分間に亘って連続的に添加し、添加終了後そのまま30分攪拌した。この時点(重合第3段階)で、反応液をGC及びGPCにより分析した結果、重合転化率はほぼ100%であった。 Next, 20 parts of dehydrated isoprene was continuously added to the reaction solution over 40 minutes, and stirring was continued for 30 minutes as it was after the addition was completed. At this time (second stage of polymerization), the reaction solution was analyzed by GC and GPC. As a result, the polymerization conversion was 99.8%.
Thereafter, 10 parts of dehydrated styrene was continuously added to the reaction solution over 30 minutes, and stirred for 30 minutes as it was after completion of the addition. At this time (the third stage of polymerization), the reaction solution was analyzed by GC and GPC. As a result, the polymerization conversion was almost 100%.
(P2-1)で得た重合体溶液を、攪拌装置を備えた耐圧反応器に移送し、水素化触媒として、珪藻土担持型ニッケル触媒(製品名「E22U」、ニッケル担持量60%、日揮触媒化成社製)4.0部、及び脱水シクロヘキサン30部を添加して混合した。反応器内部を水素ガスで置換し、さらに溶液を攪拌しながら水素を供給し、温度190℃、圧力4.5MPaにて6時間水素化反応を行った。
水素化反応により得られた反応溶液には、水素化ブロック共重合体[G2]が含まれていた。水素化ブロック共重合体[G2]のMw[G2]は72,800、分子量分布Mw/Mnは1.30、水素化率はほぼ100%であった。 (P2-2) Production of Hydrogenated Block Copolymer [G2] The polymer solution obtained in (P2-1) 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.) and 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 [G2]. Mw [G2] of the hydrogenated block copolymer [G2] was 72,800, the molecular weight distribution Mw / Mn was 1.30, and the hydrogenation rate was almost 100%.
次いで、上記溶液を、円筒型濃縮乾燥器(製品名「コントロ」、日立製作所社製)を用いて、温度260℃、圧力0.001MPa以下で処理し、溶液からシクロヘキサン、キシレン及びその他の揮発成分を除去し、溶融した樹脂を得た。これをダイからストランド状に押出し、冷却し、ペレタイザーによりペレットに成形した。これにより、水素化ブロック共重合体[G2]を含む、樹脂[G2]のペレット95部を製造した。
得られた樹脂[G2]における水素化ブロック共重合体[G2]は、Mw[G2]=69,500、Mw/Mn=1.30、Ts=138℃であった。 After completion of the hydrogenation reaction, 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.
Next, 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. And a molten resin was obtained. This was extruded from a die into a strand, cooled, and formed into pellets by a pelletizer. As a result, 95 parts of a pellet of the resin [G2] containing the hydrogenated block copolymer [G2] was produced.
Hydrogenated block copolymer [G2] in the obtained resin [G2] had Mw [G2] = 69,500, Mw / Mn = 1.30, and Ts = 138 ° C.
(トリブロック共重合体水素化物(G3)の製造)
国際公開2014/077267号の参考例1の「・ブロック共重合体水素化物[2-a]の合成」に記載された方法に従って、スチレン25部、イソプレン50部及びスチレン25部をこの順に重合して、トリブロック共重合体水素化物(G3)(重量平均分子量Mw=48,200;分子量分布Mw/Mn=1.04;主鎖及び側鎖の炭素-炭素不飽和結合、並びに、芳香環の炭素-炭素不飽和結合の水素化率ほぼ100%)のペレットを製造した。 [Production Example 3]
(Production of triblock copolymer hydride (G3))
According to the method described in “Synthesis of Block Copolymer Hydride [2-a]” in Reference Example 1 of International Publication No. 2014/077267, 25 parts of styrene, 50 parts of isoprene and 25 parts of styrene were polymerized in this order. Triblock copolymer hydride (G3) (weight average molecular weight Mw = 48,200; molecular weight distribution Mw / Mn = 1.04; carbon-carbon unsaturated bonds in the main chain and side chain, and aromatic ring Pellets having a carbon-carbon unsaturated bond hydrogenation rate of approximately 100% were produced.
(1-1.樹脂フィルムの製造)
目開き3μmのリーフディスク形状のポリマーフィルターを備える、ダブルフライト型単軸押出機(スクリューの直径D=50mm、スクリューの長さLとスクリューの直径Dとの比L/D=28)を用意した。この単軸押出機に、熱可塑性樹脂Aとして、製造例1で得たペレット状の樹脂[G1]を導入し、溶融させて、フィードブロックを介して単層ダイに供給した。単軸押出機への樹脂Aの導入は、単軸押出機に装填されたホッパーを介して行った。また、前記の単層ダイのダイスリップの表面粗さ(算術平均粗さRa)は、0.1μmであった。さらに、樹脂Aの押出機出口温度は、260℃であった。 [Example 1]
(1-1. Production of resin film)
A double flight type single screw extruder (screw diameter D = 50 mm, screw length L to screw diameter D ratio L / D = 28) equipped with a leaf disk-shaped polymer filter with a mesh opening of 3 μm was prepared. . Into this single-screw extruder, 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. Moreover, the surface roughness (arithmetic mean roughness Ra) of the die slip of the single-layer die was 0.1 μm. Furthermore, the extruder A exit temperature of the resin A was 260 ° C.
(1-1)で得た3層構造の樹脂フィルムの両端をトリミングして、幅を1300mmとし、長尺の積層フィルムを得た。
得られた積層フィルムは、樹脂BからなるB層、樹脂AからなるA層、及び樹脂BからなるB’層をこの順に備える、2種3層のフィルムであった。この積層フィルムの総厚みは、40.0μmであった。B層/A層/B’層の各層厚みは、2.0μm/36.0μm/2.0μmであった。積層フィルムの面内方向のレターデーションRe(total)は3.7nmであった。B層及びB’層の面配向係数P[B]は2.6×10-4であった。各層の密着性は良好であり、剥離強度は、材料破壊により測定不可であり、従ってAと判定された。 (1-2. Production and evaluation of laminated film)
Both ends of the resin film having the three-layer structure obtained in (1-1) were trimmed to obtain a long laminated film having a width of 1300 mm.
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 μm. Each layer thickness of B layer / A layer / B ′ layer was 2.0 μm / 36.0 μm / 2.0 μm. 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.
下記の変更点以外は、実施例1と同じ操作により、積層フィルムを製造し評価した。
・製造例1で得たペレット状の樹脂[G1]に代えて、製造例2で得たペレット状の樹脂[G2]を用いた。 [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.
下記の変更点以外は、実施例1と同じ操作により、積層フィルムを製造し評価した。
・熱可塑性樹脂Bとして、樹脂B1に代えて、脂環式構造含有重合体を含む樹脂B2(日本ゼオン社製、熱軟化温度128℃)を用いた。
・樹脂A及び樹脂Bの押出の条件を変更し、それにより積層フィルムの総厚み40.0μm、B層/A層/B’層の各層厚み3.0μm/34.0μm/3.0μmとした。 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 μm, and each layer thickness of B layer / A layer / B ′ layer was 3.0 μm / 34.0 μm / 3.0 μm. .
下記の変更点以外は、実施例1と同じ操作により、積層フィルムを製造し評価した。
・製造例1で得たペレット状の樹脂[G1]に代えて、製造例2で得たペレット状の樹脂[G2]を用いた。
・熱可塑性樹脂Bとして、樹脂B1に代えて、脂環式構造含有重合体を含む樹脂B2(日本ゼオン社製、熱軟化温度128℃)を用いた。
・樹脂A及び樹脂Bの押出の条件を変更し、それにより積層フィルムの総厚み40.0μm、B層/A層/B’層の各層厚み3.0μm/34.0μm/3.0μmとした。 Example 4
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.
-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 μm, and each layer thickness of B layer / A layer / B ′ layer was 3.0 μm / 34.0 μm / 3.0 μm. .
実施例1の(1-1)と同じ操作により、3層構造の樹脂フィルムを得た。
得られた樹脂フィルムを、フィルム幅方向に連続的に延伸した。延伸には、テンター式横延伸機を用い、フィルムの両端部をクリップで把持し、クリップの幅方向の間隔を拡張することにより行った。延伸の条件は、温度160℃、延伸倍率1.5倍とした。延伸後、フィルムの両端をトリミングして、幅を1330mmとし、延伸された長尺の積層フィルムを得た。
得られた積層フィルムは、樹脂BからなるB層、樹脂AからなるA層、及び樹脂BからなるB’層をこの順に備える、2種3層のフィルムであった。この積層フィルムのB層/A層/B’層の各層厚みは、1.3μm/24.0μm/1.3μmであった。積層フィルムの面内方向のレターデーションRe(total)は3.0nmであった。B層及びB’層の面配向係数P[B]は1.2×10-3であった。各層の密着性は良好であり、剥離強度は3.4N/15mmであり、従ってBと判定された。 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 μm / 24.0 μm / 1.3 μm. 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.
下記の変更点以外は、実施例5と同じ操作により、積層フィルムを製造し評価した。
・製造例1で得たペレット状の樹脂[G1]に代えて、製造例2で得たペレット状の樹脂[G2]を用いた。 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.
下記の変更点以外は、実施例5と同じ操作により、積層フィルムを製造し評価した。
・熱可塑性樹脂Bとして、樹脂B1に代えて、脂環式構造含有重合体を含む樹脂B2(日本ゼオン社製、熱軟化温度128℃)を用いた。
・樹脂A及び樹脂Bの押出の条件を変更した。但し、その後の延伸等の操作は変更せず、実施例5と同じ操作とした。その結果、積層フィルムのB層/A層/B’層の各層厚み2.0μm/22.7μm/2.0μmとした。 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 μm / 22.7 μm / 2.0 μm.
下記の変更点以外は、実施例5と同じ操作により、積層フィルムを製造し評価した。
・製造例1で得たペレット状の樹脂[G1]に代えて、製造例2で得たペレット状の樹脂[G2]を用いた。
・熱可塑性樹脂Bとして、樹脂B1に代えて、脂環式構造含有重合体を含む樹脂B2(日本ゼオン社製、熱軟化温度128℃)を用いた。
・樹脂A及び樹脂Bの押出の条件を変更した。但し、その後の延伸等の操作は変更せず、実施例5と同じ操作とした。その結果、積層フィルムのB層/A層/B’層の各層厚み2.0μm/22.7μm/2.0μmとした。 Example 8
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.
-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 μm / 22.7 μm / 2.0 μm.
(9-1.ペレットブレンド物の製造)
製造例1で得たペレット状の樹脂[G1]と製造例3で得たペレット状の樹脂[G3]とを、ペレット状のまま[G1]:[G3]=8:2(重量比)の比率で混合した。これにより、ペレットブレンド物を得た。 Example 9
(9-1. Production of pellet blend)
The pellet-shaped resin [G1] obtained in Production Example 1 and the pellet-shaped resin [G3] obtained in Production Example 3 are in the form of pellets [G1]: [G3] = 8: 2 (weight ratio). Mixed in ratio. Thereby, a pellet blend was obtained.
下記の変更点以外は、実施例5と同じ操作により、積層フィルムを製造し評価した。
・熱可塑性樹脂Aとして、製造例1で得たペレット状の樹脂[G1]に代えて、(9-1)で得たペレットブレンド物を用いた。
・熱可塑性樹脂Bとして、樹脂B1に代えて、脂環式構造含有重合体を含む樹脂B2(日本ゼオン社製、熱軟化温度128℃)を用いた。
・樹脂A及び樹脂Bの押出の条件を変更した。但し、その後の延伸等の操作は変更せず、実施例5と同じ操作とした。その結果、積層フィルムのB層/A層/B’層の各層厚み9.4μm/23.0μm/9.4μmとした。積層フィルムの面内方向のレターデーションRe(total)は0.7nmであった。B層及びB’層の面配向係数P[B]は1.0×10-4であった。各層の密着性は良好であり、剥離強度は、1.5N/15mmであり、従ってBと判定された。 (9-2. Production and evaluation of laminated film)
A laminated film was produced and evaluated in the same manner as in Example 5 except for the following changes.
As the 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.
-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 9.4 μm / 23.0 μm / 9.4 μm. 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.
(10-1.ペレットブレンド物の製造)
製造例1で得たペレット状の樹脂[G1]と製造例3で得たペレット状の樹脂[G3]とを、ペレット状のまま[G1]:[G3]=7.5:2.5(重量比)の比率で混合した。これにより、ペレットブレンド物を得た。 Example 10
(10-1. Production of pellet blend)
The pellet-shaped resin [G1] obtained in Production Example 1 and the pellet-shaped resin [G3] obtained in Production Example 3 are kept in the form of pellets [G1]: [G3] = 7.5: 2.5 ( (Weight ratio). Thereby, a pellet blend was obtained.
下記の変更点以外は、実施例5と同じ操作により、積層フィルムを製造し評価した。
・熱可塑性樹脂Aとして、製造例1で得たペレット状の樹脂[G1]に代えて、(10-1)で得たペレットブレンド物を用いた。
・熱可塑性樹脂Bとして、樹脂B1に代えて、脂環式構造含有重合体を含む樹脂B2(日本ゼオン社製、熱軟化温度128℃)を用いた。
・樹脂A及び樹脂Bの押出の条件を変更した。但し、その後の延伸等の操作は変更せず、実施例5と同じ操作とした。その結果、積層フィルムのB層/A層/B’層の各層厚み5.1μm/30.6μm/5.1μmとした。積層フィルムの面内方向のレターデーションRe(total)は0.9nmであった。B層及びB’層の面配向係数P[B]は1.4×10-4であった。各層の密着性は良好であり、剥離強度は、3.2N/15mmであり、従ってBと判定された。 (10-2. Production and evaluation of laminated film)
A laminated film was produced and evaluated in the same manner as in Example 5 except for the following changes.
As the 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.
-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, the thickness of each layer of layer B / layer A / layer B ′ of the laminated film was set to 5.1 μm / 30.6 μm / 5.1 μm. 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.
目開き3μmのリーフディスク形状のポリマーフィルターを備える、ダブルフライト型単軸押出機(スクリューの直径D=50mm、スクリューの長さLとスクリューの直径Dとの比L/D=28)を用意した。この単軸押出機に、熱可塑性樹脂Aとして、製造例1で得たペレット状の樹脂[G1]を導入し、溶融させて、単層ダイに供給した。単軸押出機への樹脂Aの導入は、単軸押出機に装填されたホッパーを介して行った。また、前記の単層ダイのダイスリップの表面粗さ(算術平均粗さRa)は、0.1μmであった。さらに、樹脂Aの押出機出口温度は、260℃であった。 [Comparative Example 1]
A double flight type single screw extruder (screw diameter D = 50 mm, screw length L to screw diameter D ratio L / D = 28) equipped with a leaf disk-shaped polymer filter with a mesh opening of 3 μm was prepared. . Into this single-screw extruder, 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. The introduction of the resin A into the single screw extruder was performed through a hopper loaded in the single screw extruder. Moreover, the surface roughness (arithmetic mean roughness Ra) of the die slip of the single-layer die was 0.1 μm. Furthermore, the extruder A exit temperature of the resin A was 260 ° C.
得られた単層フィルムは、樹脂AからなるA層のみからなる1層のフィルムであった。この積層フィルムの厚みは、27.0μmであった。積層フィルムの面内方向のレターデーションRe(total)は0.9nmであった。剥離強度は0.16N/15mmであり、従ってCと判定された。 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 μm. 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.
下記の変更点以外は、比較例1と同じ操作により、積層フィルムを製造し評価した。
・製造例1で得たペレット状の樹脂[G1]に代えて、製造例2で得たペレット状の樹脂[G2]を用いた。 [Comparative Example 2]
A laminated film was produced and evaluated in the same manner as in Comparative 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.
下記の変更点以外は、実施例7と同じ操作(比較例3)又は実施例8と同じ操作(比較例4)により、積層フィルムを製造し評価した。
・熱可塑性樹脂Bとして、樹脂B1に代えて、脂環式構造含有重合体を含む樹脂B3(日本ゼオン社製、熱軟化温度128℃)を用いた。 [Comparative Examples 3 to 4]
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.
-As thermoplastic resin B, it replaced with resin B1, and used resin B3 (The Nippon Zeon company make, heat softening temperature 128 degreeC) containing an alicyclic structure containing polymer.
環式wD:水素化ブロック共重合体[G]における、単位[I]の割合(%)。
鎖状wE:水素化ブロック共重合体[G]における、単位[II]の割合(%)。
G1:製造例1で製造した、水素化ブロック共重合体[G1]。
G2:製造例2で製造した、水素化ブロック共重合体[G2]。
G3:製造例3で製造した、水素化ブロック共重合体[G3]。
B1:脂環式構造含有重合体を含む樹脂、熱軟化温度136℃、日本ゼオン社製「ZEONOR」の製品群の一つ。
B2:脂環式構造含有重合体を含む樹脂、熱軟化温度128℃、日本ゼオン社製「ZEONOR」の製品群の一つ。
B3:脂環式構造含有重合体を含む樹脂、熱軟化温度160℃、日本ゼオン社製「ZEONOR」の製品群の一つ。 The meanings of the abbreviations in the table are as follows.
Cyclic wD: Ratio (%) of unit [I] in hydrogenated block copolymer [G].
Chain wE: Ratio (%) of unit [II] in hydrogenated block copolymer [G].
G1: Hydrogenated block copolymer [G1] produced in Production Example 1.
G2: Hydrogenated block copolymer [G2] produced in Production Example 2.
G3: Hydrogenated block copolymer [G3] produced in Production Example 3.
B1: A resin containing an alicyclic structure-containing polymer, a heat softening temperature of 136 ° C., one of the “ZEONOR” product group manufactured by Nippon Zeon.
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.
Claims (7)
- 熱可塑性樹脂AからなるA層、及び前記A層の少なくとも一方の面上に設けられた熱可塑性樹脂BからなるB層を備える積層フィルムであって、
前記熱可塑性樹脂Aは、
単位[I]を主成分とする、2つ以上の重合体ブロック[D]と、
単位[II]、又は前記単位[I]及び前記単位[II]の組み合わせを主成分とする1つ以上の重合体ブロック[E]
を含む水素化ブロック共重合体[G]を含み、
前記単位[I]は、環式炭化水素基含有化合物水素化物単位であり、
前記単位[II]は、鎖状炭化水素化合物水素化物単位であり、
前記熱可塑性樹脂Bは、前記熱可塑性樹脂Aとは異なる樹脂であり、
前記熱可塑性樹脂Aの熱軟化温度Ts[A]、前記熱可塑性樹脂Bの熱軟化温度Ts[B]、前記A層の厚みt[A]、前記B層の厚みt[B]、前記積層フィルムの面内方向のレターデーションRe(total)、及び前記B層の面配向係数P[B]が、下記式(1)~(6)を満たす、積層フィルム。
(1)130℃≦Ts[A]≦145℃
(2)120℃≦Ts[B]≦145℃
(3)0≦Re(total)≦5nm
(4)20μm≦t[A]≦50μm
(5)1μm≦t[B]≦15μm
(6)1.0×10-5≦|P[B]|≦2.0×10-3 A laminated film comprising 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 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]
A hydrogenated block copolymer [G] containing
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,
Thermal softening temperature Ts [A] of the thermoplastic resin A, thermal softening temperature Ts [B] of the thermoplastic resin B, thickness t [A] of the A layer, thickness t [B] of the B layer, the lamination A laminated film in which the in-plane retardation Re (total) of the 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.
(3) 0 ≦ Re (total) ≦ 5 nm
(4) 20 μm ≦ t [A] ≦ 50 μm
(5) 1 μm ≦ t [B] ≦ 15 μm
(6) 1.0 × 10 −5 ≦ | P [B] | ≦ 2.0 × 10 −3 - 前記環式炭化水素基含有化合物が芳香族ビニル化合物であり、前記鎖状炭化水素化合物が鎖状共役ジエン系化合物である、請求項1に記載の積層フィルム。 The laminated film according to claim 1, wherein the cyclic hydrocarbon group-containing compound is an aromatic vinyl compound, and the chain hydrocarbon compound is a chain conjugated diene compound.
- 前記熱可塑性樹脂Aは、2種類以上の熱可塑性樹脂のブレンド物である、請求項1又は2に記載の積層フィルム。 The laminated film according to claim 1 or 2, wherein the thermoplastic resin A is a blend of two or more kinds of thermoplastic resins.
- 前記熱可塑性樹脂Bは脂環式構造を含有する重合体を含む樹脂である請求項1~3のいずれか1項に記載の積層フィルム。 The laminated film according to any one of claims 1 to 3, wherein the thermoplastic resin B is a resin containing a polymer containing an alicyclic structure.
- 請求項1~4のいずれか1項に記載の積層フィルムの製造方法であって、
前記熱可塑性樹脂Aからなるa層、及び前記a層の少なくとも一方の面上に設けられた熱可塑性樹脂Bからなるb層を備える延伸前フィルムを調製する工程、及び
前記延伸前フィルムを、少なくとも1の方向に延伸する延伸工程を含む、製造方法。 A method for producing a laminated film according to any one of claims 1 to 4,
Preparing a pre-stretch film comprising a layer comprising the thermoplastic resin A, and a b layer comprising a thermoplastic resin B provided on at least one surface of the a layer; and at least the pre-stretch film, The manufacturing method including the extending | stretching process extended | stretched in 1 direction. - 請求項1~4のいずれか1項に記載の積層フィルムと偏光子とを備える偏光板。 A polarizing plate comprising the laminated film according to any one of claims 1 to 4 and a polarizer.
- 請求項1~4のいずれか1項に記載の積層フィルムを備える表示装置。 A display device comprising the laminated film according to any one of claims 1 to 4.
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