WO2017150166A1 - 複層フィルム及び製造方法 - Google Patents
複層フィルム及び製造方法 Download PDFInfo
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- WO2017150166A1 WO2017150166A1 PCT/JP2017/005196 JP2017005196W WO2017150166A1 WO 2017150166 A1 WO2017150166 A1 WO 2017150166A1 JP 2017005196 W JP2017005196 W JP 2017005196W WO 2017150166 A1 WO2017150166 A1 WO 2017150166A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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Definitions
- the present invention relates to a multilayer film and a method for producing the same.
- an alkoxysilyl group-modified product in which an alkoxysilyl group is introduced into a hydride obtained by hydrogenating a block copolymer of an aromatic vinyl compound and a chain conjugated diene compound (hereinafter, this polymer is simply referred to as an “alkoxysilyl group”).
- modified products Sometimes referred to as “modified products”.
- a resin containing such an alkoxysilyl group-modified product is excellent in transparency, heat resistance, weather resistance, and adhesion to inorganic materials such as glass and metal. Therefore, such resin can be used for various applications such as optical applications.
- an optical device having an organic light emitting layer such as an organic electroluminescence display device and an organic electroluminescence light emitting device
- it is formed using such a resin as a material for sealing a light emitting element including the organic light emitting layer.
- Film can be used.
- An example of a method for producing a resin film containing an alkoxysilyl group-modified product is a method including an extrusion process. Specifically, using a screw extruder and a melt extrusion molding machine including a die, the resin is pumped from the screw extruder to the die, thereby extruding the resin in the form of a film from the die, thereby efficiently forming a film. Can be manufactured.
- an object of the present invention is to provide a film excellent in ease of manufacture, optical performance, and mechanical properties, and a method of manufacturing a film that can easily manufacture such a film. is there.
- the present inventors have found that the occurrence of foreign matters generated inside the extruder in the screw extruder can be a particular problem when extruding the alkoxysilyl group-modified product. It was.
- the present inventors have further found that the occurrence of foreign matters in such a screw extruder can be reduced by adding a specific compound as a plasticizer to the resin.
- the inventor has further found that undesired phenomena such as bleeding out of such a compound in the production process can be reduced by making the film a specific multilayer film.
- the present invention has been completed based on these findings. That is, the present invention is as follows.
- the resin [I] includes an alkoxysilyl-modified product [3] of a block copolymer hydride and an ester compound [4],
- the alkoxysilyl-modified product [3] is a hydride obtained by hydrogenating 90% or more of the carbon-carbon unsaturated bond of the main chain and the side chain of the block copolymer [1] and the carbon-carbon unsaturated bond of the aromatic ring.
- the block copolymer [1] comprises an aromatic vinyl compound unit as a main component, the block copolymer [1] two or more polymer blocks [A] per molecule, and a chain conjugated diene compound unit.
- the block copolymer [1] having at least one polymer block [B] per molecule, The weight fraction wA of the polymer block [A] in the entire block copolymer [1], and the weight fraction wB of the polymer block [B] in the entire block copolymer [1].
- the resin [II] includes a polymer selected from the group consisting of a cyclic olefin polymer, the hydride [2], the alkoxysilyl-modified product [3], and a mixture thereof.
- the resin [II] does not contain the ester compound [4], or the content of the ester compound [4] in the resin [II] is less than 0.1% by weight.
- a production method comprising a coextrusion molding step of coextruding the molten resin [I] and the resin [II].
- the co-extrusion molding step is performed using a melt extruder including a screw extruder and a die.
- the co-extrusion molding step is a manufacturing method according to [4], including feeding the resin [I] from a screw extruder to the die.
- the multilayer film of the present invention can be a film having excellent ease of production, optical performance, and mechanical properties. Moreover, according to the manufacturing method of the multilayer film of this invention, such a multilayer film of this invention can be manufactured easily.
- FIG. 1 is a cross-sectional view schematically showing an example of the multilayer film of the present invention.
- FIG. 2 is a side view schematically showing an example of a melt extrusion molding machine for carrying out the method for producing a multilayer film of the present invention and an example of the production method of the present invention using the same.
- the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the following embodiments and exemplifications, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.
- the “polarizing plate” includes not only a rigid member but also a flexible member such as a resin film, unless otherwise specified.
- FIG. 1 is a cross-sectional view schematically showing an example of the multilayer film of the present invention.
- the multilayer film 100 includes a first resin layer 110 and a second resin layer 120 provided on one surface 110 ⁇ / b> U of the first resin layer 110.
- the other surface 110 ⁇ / b> D of the first resin layer 110 is exposed on the outer surface of the multilayer film 100.
- the first resin layer is a layer made of resin [I].
- the resin [I] contains a specific alkoxysilyl modified product [3] and an ester compound [4].
- the alkoxysilyl modified product [3] is an alkoxysilyl group modified product of a hydride [2] obtained by hydrogenating an unsaturated bond of a specific block copolymer [1].
- the block copolymer [I] comprises two or more polymer blocks [A] per molecule of the block copolymer [1] and one or more polymer blocks [B] per molecule of the block copolymer [1]. ] Is a block copolymer.
- the polymer block [A] is a polymer block mainly composed of an aromatic vinyl compound unit.
- the aromatic vinyl compound unit refers to a structural unit having a structure formed by polymerizing an aromatic vinyl compound.
- Examples of the aromatic vinyl compound corresponding to the aromatic vinyl compound unit contained in the polymer block [A] include styrene; ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4 Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene; 4-chloro Styrenes having a halogen atom as a substituent, such as styrene, dichlorostyrene, 4-monofluorostyrene; Styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent, such as 4-methoxystyrene; 4-phenylstyrene Styrenes having an aryl group as a substituent, such
- aromatic vinyl compounds that do not contain a polar group, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferable, because they are easily available industrially. Styrene is particularly preferred.
- the content of the aromatic vinyl compound unit in the polymer block [A] is preferably 90% by weight or more, more preferably 95% by weight or more, and particularly preferably 99% by weight or more.
- the heat resistance of the first resin layer can be increased by increasing the amount of the aromatic vinyl compound unit in the polymer block [A] as described above.
- the polymer block [A] may contain an arbitrary structural unit in addition to the aromatic vinyl compound unit.
- the polymer block [A] may contain any structural unit alone or in combination of two or more at any ratio.
- Examples of an arbitrary structural unit that can be contained in the polymer block [A] include a chain conjugated diene compound unit.
- the chain conjugated diene compound unit refers to a structural unit having a structure formed by polymerizing a chain conjugated diene compound.
- Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit include, for example, the same examples as those exemplified as the chain conjugated diene compound corresponding to the chain conjugated diene compound unit included in the polymer block [B]. Is mentioned.
- the polymer block [A] can contain, for example, a structural unit having a structure formed by polymerizing an arbitrary unsaturated compound other than an aromatic vinyl compound and a chain conjugated diene compound is used.
- a structural unit having a structure formed by polymerizing an arbitrary unsaturated compound other than an aromatic vinyl compound and a chain conjugated diene compound is used.
- the optional unsaturated compound include vinyl compounds such as chain vinyl compounds and cyclic vinyl compounds; unsaturated cyclic acid anhydrides; unsaturated imide compounds; These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group.
- a vinyl compound having no polar group is preferred, a chain olefin having 2 to 20 carbon atoms per molecule is more preferred, and ethylene and propylene are particularly preferred.
- the content of an arbitrary structural unit in the polymer block [A] is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less.
- Block copolymer [1] The number of polymer blocks [A] in one molecule is preferably 2 or more, preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.
- the plurality of polymer blocks [A] in one molecule may be the same as or different from each other.
- the weight average molecular weight of the polymer block having the maximum weight average molecular weight in the polymer block [A] is expressed as Mw. (A1)
- the weight average molecular weight of the polymer block having the smallest weight average molecular weight is Mw (A2).
- the ratio “Mw (A1) / Mw (A2)” between Mw (A1) and Mw (A2) is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. It is. Thereby, the dispersion
- the lower limit of Mw (A1) / Mw (A2) can be 1.0 or more.
- the polymer block [B] is a polymer block mainly composed of a chain conjugated diene compound unit.
- the chain conjugated diene compound unit refers to a structural unit having a structure formed by polymerizing a chain conjugated diene compound.
- Examples of the chain conjugated diene compound corresponding to the chain conjugated diene compound unit included in the polymer block [B] include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1, Examples include 3-pentadiene. One of these may be used alone, or two or more of these may be used in combination at any ratio. Among these, in terms of hygroscopicity, a chain conjugated diene compound containing no polar group is preferable, and 1,3-butadiene and isoprene are particularly preferable.
- the content of the chain conjugated diene compound unit in the polymer block [B] is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
- the polymer block [B] may contain an arbitrary structural unit in addition to the chain conjugated diene compound unit.
- the polymer block [B] may contain any structural unit alone or in combination of two or more at any ratio.
- an arbitrary structural unit that can be contained in the polymer block [B] is formed by polymerizing an aromatic vinyl compound unit and any unsaturated compound other than the aromatic vinyl compound and the chain conjugated diene compound.
- Examples include structural units having a structure.
- Examples of the structural unit having a structure formed by polymerizing these aromatic vinyl compound units and any unsaturated compound include those exemplified as those which may be contained in the polymer block [A]. The same example is given.
- the content of any structural unit in the polymer block [B] is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 10% by weight or less.
- the flexibility of the first resin layer can be improved by reducing the content of any structural unit in the polymer block [B].
- Block copolymer [1] The number of polymer blocks [B] in one molecule is usually 1 or more, but may be 2 or more. When the number of polymer blocks [B] in the block copolymer [1] is 2 or more, the polymer blocks [B] may be the same as or different from each other.
- the weight average molecular weight of the polymer block having the maximum weight average molecular weight in the polymer block [B] is expressed as Mw. (B1)
- the weight average molecular weight of the polymer block having the smallest weight average molecular weight is Mw (B2).
- the ratio “Mw (B1) / Mw (B2)” between Mw (B1) and Mw (B2) is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. It is. Thereby, the dispersion
- the lower limit of Mw (B1) / Mw (B2) can be 1.0 or more.
- the form of the block of the block copolymer [1] may be a chain block or a radial block.
- a chain type block is preferable because of its excellent mechanical strength.
- the block copolymer [1] has a chain-type block form, it is desired that both ends of the molecular chain of the block copolymer [1] are polymer blocks [A], so that the resin [I] is not sticky. Is preferable because it can be suppressed to a low value.
- a particularly preferred block form of the block copolymer [1] is that the polymer block [A] is bonded to both ends of the polymer block [B] as represented by [A]-[B]-[A]. As shown by [A]-[B]-[A]-[B]-[A], the polymer block [B] is bonded to both ends of the polymer block [A]. And a pentablock copolymer in which the polymer block [A] is bonded to the other end of each of the polymer blocks [B].
- a triblock copolymer of [A]-[B]-[A] is particularly preferable because it can be easily produced and the physical properties can be easily within a desired range.
- the ratio (wA / wB) to the weight fraction wB falls within a specific range. Specifically, the ratio (wA / wB) is usually 20/80 or more, preferably 25/75 or more, more preferably 30/70 or more, particularly preferably 40/60 or more, and usually 60/40. Hereinafter, it is preferably 55/45 or less.
- the weight fraction wA of the polymer block [A] indicates the weight fraction of the whole polymer block [A]
- the weight fraction wB of the polymer block [B] is the whole polymer block [B]. The weight fraction is shown.
- the weight average molecular weight (Mw) of the block copolymer [1] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, preferably 200,000 or less. More preferably, it is 150,000 or less, Most preferably, it is 100,000 or less.
- the molecular weight distribution (Mw / Mn) of the block copolymer [1] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more.
- Mn represents a number average molecular weight.
- the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the block copolymer [1] were determined as polystyrene-converted values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. It can be measured.
- a monomer mixture (a) containing an aromatic vinyl compound as a main component and a chain conjugated diene compound as a main component are contained by a method such as living anion polymerization.
- a method of coupling ends of the polymer block [B] with a coupling agent for example, a monomer mixture (a) containing an aromatic vinyl compound as a main component and a chain conjugated diene compound as a main component are contained by a method such as living anion polymerization.
- the content of the aromatic vinyl compound in the monomer mixture (a) is usually 90% by weight or more, preferably 95% by weight or more, more preferably 99% by weight or more.
- the monomer mixture (a) may contain any monomer component other than the aromatic vinyl compound.
- the optional monomer component include a chain conjugated diene compound and an arbitrary unsaturated compound.
- the amount of the optional monomer component is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the monomer mixture (a).
- the content of the chain conjugated diene compound in the monomer mixture (b) is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more.
- the monomer mixture (b) may contain any monomer component other than the chain conjugated diene compound.
- Optional monomer components include aromatic vinyl compounds and arbitrary unsaturated compounds.
- the amount of the optional monomer component is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, based on the monomer mixture (b).
- radical polymerization, anion polymerization, cation polymerization, coordination anion polymerization, coordination cation polymerization and the like can be used.
- radical polymerization, anion polymerization, cation polymerization and the like are performed by living polymerization
- a method in which living polymerization is performed by living anion polymerization is particularly preferable.
- Polymerization can be performed in the presence of a polymerization initiator.
- a polymerization initiator monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium; dilithiomethane, 1,4-dilithiobutane, 1,4-dilithio A polyfunctional organolithium compound such as -2-ethylcyclohexane; 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 preferably 0 ° C. or higher, more preferably 10 ° C. or higher, particularly preferably 20 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower, particularly preferably 70 ° C. or lower.
- solution polymerization and slurry polymerization can be used as the form of the polymerization reaction.
- reaction heat can be easily removed.
- an inert solvent in which the polymer obtained in each step can be dissolved can be used as the solvent.
- the inert solvent examples include aliphatic hydrocarbon solvents such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, decalin, bicyclo And alicyclic hydrocarbon solvents such as [4.3.0] nonane and tricyclo [4.3.0.1 2,5 ] decane; aromatic hydrocarbon solvents such as benzene and toluene; One of these may be used alone, or two or more of these may be used in combination at any ratio.
- aliphatic hydrocarbon solvents such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane
- an alicyclic hydrocarbon solvent as the solvent because it can be used as it is as an inert solvent for the hydrogenation reaction and the solubility of the block copolymer [1] is good.
- the amount of the solvent used is preferably 200 to 2000 parts by weight with respect to 100 parts by weight of all the monomers used.
- a randomizer can be used to prevent only one component chain from becoming long.
- a Lewis base compound examples 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; and tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, and the like.
- Tertiary amine compounds such as potassium-t-amyl oxide and potassium-t-butyl oxide; phosphine compounds such as triphenylphosphine; and the like.
- alkali metal alkoxide compounds such as potassium-t-amyl oxide and potassium-t-butyl oxide
- phosphine compounds such as triphenylphosphine; and the like.
- One of these may be used alone, or two or more of these may be used in combination at any ratio.
- the hydride [2] is a polymer obtained by hydrogenating an amount of a specific amount or more of the unsaturated bond of the block copolymer [1].
- the unsaturated bond of the block copolymer [1] to be hydrogenated includes aromatic and non-aromatic carbon-carbon unsaturation of the main chain and side chain of the block copolymer [1]. Includes any bond.
- the hydrogenation rate of the hydride [2] is a value higher than a specific value.
- the hydrogenation rate of the hydride [2] is the carbon-carbon unsaturated bond of the main chain and side chain and the carbon-carbon unsaturated bond of the aromatic ring unless otherwise specified.
- the hydrogenation rate of the element [2] is 90% or more, preferably 97% or more, more preferably 99% or more.
- the higher the hydrogenation rate the better the transparency, heat resistance and weather resistance of the first resin layer, and the easier it is to reduce the birefringence of the first resin layer.
- the hydrogenation rate of the hydride [2] can be determined by measurement by 1 H-NMR.
- the upper limit of the hydrogenation rate of the hydride [2] can be 100% or less.
- the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond is preferably 95% or more, more preferably 99% or more.
- the light resistance and oxidation resistance of the first resin layer can be further increased.
- the hydrogenation rate of the aromatic carbon-carbon unsaturated bond is preferably 90% or more, more preferably 93% or more, and particularly preferably 95% or more.
- the glass transition temperature of the polymer block obtained by hydrogenating the polymer block [A] is increased, so that the heat resistance of the first resin layer is improved. Can be effectively increased.
- the photoelastic coefficient of the first resin layer can be lowered.
- the weight average molecular weight (Mw) of the hydride [2] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, preferably 200,000 or less, more preferably 150. 1,000 or less, particularly preferably 100,000 or less.
- the molecular weight distribution (Mw / Mn) of the hydride [2] is preferably 3 or less, more preferably 2 or less, particularly preferably 1.5 or less, and preferably 1.0 or more.
- the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the hydride [2] can be measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
- the hydride [2] described above can be produced by hydrogenating the block copolymer [1].
- a hydrogenation method that can increase the hydrogenation rate and causes little chain-breaking reaction of the block copolymer [1] is preferable. Examples of such a hydrogenation method include the methods described in International Publication No. 2011/096389 and International Publication No. 2012/043708.
- Examples of specific hydrogenation methods include, for example, hydrogenation using a hydrogenation catalyst containing at least one metal selected from the group consisting of nickel, cobalt, iron, rhodium, palladium, platinum, ruthenium, and rhenium.
- a hydrogenation catalyst may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the hydrogenation catalyst either a heterogeneous catalyst or a homogeneous catalyst can be used.
- the hydrogenation reaction is preferably performed in an organic solvent.
- the heterogeneous catalyst may be used as it is, for example, as a metal or a metal compound, or may be used by being supported on a suitable carrier.
- suitable carrier include activated carbon, silica, alumina, calcium carbonate, titania, magnesia, zirconia, diatomaceous earth, silicon carbide, calcium fluoride, and the like.
- the supported amount of the catalyst is preferably 0.1% by weight or more, more preferably 1% by weight or more, preferably 60% by weight or less, more preferably 50% by weight or less based on the total amount of the catalyst and the carrier. is there.
- the specific surface area of the supported catalyst is preferably 100 m 2 / g to 500 m 2 / g.
- the average pore diameter of the supported catalyst is preferably 100 mm or more, more preferably 200 mm or more, preferably 1000 mm or less, more preferably 500 mm or less.
- the specific surface area can be obtained by measuring the nitrogen adsorption amount and using the BET equation.
- the average pore diameter can be measured by a mercury intrusion method.
- homogeneous catalysts include catalysts in which nickel, cobalt, or iron compounds and organometallic compounds (eg, organoaluminum compounds, organolithium compounds) are combined; organometallics including rhodium, palladium, platinum, ruthenium, rhenium, etc. Complex catalysts; and the like can be used.
- organometallic compounds eg, organoaluminum compounds, organolithium compounds
- organometallics including rhodium, palladium, platinum, ruthenium, rhenium, etc.
- Complex catalysts and the like can be used.
- Examples of the nickel, cobalt, or iron compound include acetylacetonate compounds, carboxylates, cyclopentadienyl compounds, and the like of various metals.
- Examples of the organoaluminum compound include alkylaluminums such as triethylaluminum and triisobutylaluminum; aluminum halides such as diethylaluminum chloride and ethylaluminum dichloride; alkylaluminum hydrides such as diisobutylaluminum hydride; and the like.
- organometallic complex catalysts include transition metal complexes such as dihydrido-tetrakis (triphenylphosphine) ruthenium, dihydrido-tetrakis (triphenylphosphine) iron, bis (cyclooctadiene) nickel, and bis (cyclopentadienyl) nickel. Is mentioned.
- the amount of the hydrogenation catalyst used is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, particularly preferably 0.1 parts by weight or more with respect to 100 parts by weight of the block copolymer [1]. Preferably, it is 100 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less.
- the temperature of the hydrogenation reaction is preferably 10 ° C or higher, more preferably 50 ° C or higher, particularly preferably 80 ° C or higher, preferably 250 ° C or lower, more preferably 200 ° C or lower, particularly preferably 180 ° C or lower. .
- the hydrogenation rate can be increased, and the molecular cleavage of the block copolymer [1] can be reduced.
- the hydrogen pressure during the hydrogenation reaction is preferably 0.1 MPa or more, more preferably 1 MPa or more, particularly preferably 2 MPa or more, preferably 30 MPa or less, more preferably 20 MPa or less, and particularly preferably 10 MPa or less.
- the hydride [2] obtained by the above-described method is usually obtained as a reaction liquid containing a hydride [2], a hydrogenation catalyst, and a polymerization catalyst. Therefore, the hydride [2] may be recovered from the reaction solution after removing the hydrogenation catalyst and the polymerization catalyst from the reaction solution by a method such as filtration and centrifugation.
- a method for recovering the hydride [2] from the reaction solution for example, a steam coagulation method in which the solvent is removed from the reaction solution containing the hydride [2] by steam stripping; direct solvent removal to remove the solvent under reduced pressure heating And a solidification method in which the reaction solution is poured into a poor solvent of hydride [2] to precipitate or solidify.
- the recovered hydride [2] is preferably in the form of a pellet so that it can be easily subjected to a subsequent silylation modification reaction (reaction for introducing an alkoxysilyl group).
- a subsequent silylation modification reaction reaction for introducing an alkoxysilyl group
- the molten hydride [2] may be extruded from a die into strands, cooled, and then cut into pellets by a pelletizer, and used for various moldings.
- the obtained solidified product may be dried and then extruded in a molten state by an extruder and may be formed into pellets in the same manner as described above and used for various moldings.
- the alkoxysilyl group-modified product [3] is a polymer obtained by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1] described above.
- the alkoxysilyl group may be directly bonded to the hydride [2] described above, and may be indirectly bonded, for example, via a divalent organic group such as an alkylene group.
- the alkoxysilyl group-modified product [3] is particularly excellent in adhesion to inorganic materials such as glass and metal. Therefore, the first resin layer is usually excellent in adhesiveness with the inorganic material. Therefore, the first resin layer can maintain a high adhesive force to the inorganic material even after being exposed to a high temperature and high humidity environment for a long time.
- the introduction amount of the alkoxysilyl group in the modified alkoxysilyl group [3] is preferably 0.1 parts by weight or more, more preferably 0.1 parts by weight or more with respect to 100 parts by weight of the hydride [2] before introduction of the alkoxysilyl group. 2 parts by weight or more, particularly preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less.
- the amount of alkoxysilyl group introduced can be measured by 1 H-NMR spectrum. In addition, when the introduction amount of the alkoxysilyl group is measured, if the introduction amount is small, the number of integrations can be increased.
- the weight average molecular weight (Mw) of the alkoxysilyl group-modified product [3] is small in the amount of alkoxysilyl groups introduced, usually the weight average molecular weight (2) of the hydride [2] before introducing the alkoxysilyl group ( Mw) does not change significantly.
- the hydride [2] is modified in the presence of a peroxide, so that the hydride [2] undergoes a crosslinking reaction and a cleavage reaction, and the molecular weight distribution changes greatly. Tend to.
- the weight average molecular weight (Mw) of the alkoxysilyl group-modified product [3] is preferably 40,000 or more, more preferably 50,000 or more, particularly preferably 60,000 or more, and preferably 200,000 or less. Preferably it is 150,000 or less, Most preferably, it is 100,000 or less.
- the molecular weight distribution (Mw / Mn) of the modified alkoxysilyl group [3] is preferably 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less, preferably 1.0. That's it.
- weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the alkoxysilyl group-modified product [3] are within this range, good mechanical strength and tensile elongation of the first resin layer can be maintained.
- the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the alkoxysilyl group-modified product [3] can be measured as values in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. .
- the alkoxysilyl group-modified product [3] can be produced by introducing an alkoxysilyl group into the hydride [2] of the block copolymer [1] described above.
- Examples of the method for introducing an alkoxysilyl group into the hydride [2] include a method in which the hydride [2] and an ethylenically unsaturated silane compound are reacted in the presence of a peroxide.
- ethylenically unsaturated silane compound those capable of graft polymerization with hydride [2] and capable of introducing an alkoxysilyl group into hydride [2] can be used.
- ethylenically unsaturated silane compounds include: vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane and other alkoxy silanes; allyltrimethoxysilane, allyltriethoxysilane Alkoxysilanes having an allyl group such as p-styryltrimethoxysilane, p-styryltriethoxysilane and the like alkoxysilanes having a p-styryl group; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane Alkoxysilanes having a 3-meth
- vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, allyltrimethoxysilane, allyltriethoxysilane, p-styryltrimethoxy Silane is preferred.
- an ethylenically unsaturated silane compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the amount of the ethylenically unsaturated silane compound is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, particularly 100 parts by weight of the hydride [2] before introducing the alkoxysilyl group.
- the amount is preferably 0.3 parts by weight or more, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less.
- the peroxide one that functions as a radical reaction initiator can be used.
- an organic peroxide is usually used.
- the organic peroxide include dibenzoyl peroxide, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, t-butylcumyl peroxide, Dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxyhexane), di-t-butyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane-3, t-butylhydroperoxide, t-butylperoxyisobutyrate, lauroyl peroxide, dipropionyl peroxide, p-menthane hydroperoxide and the like.
- t-butylcumyl peroxide examples include t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl -2,5-di (t-butylperoxyhexane), di-t-butylperoxide and the like are preferable.
- a peroxide may be used individually by 1 type and may be used in combination of 2 or more type.
- the amount of the peroxide is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and particularly preferably 0 parts by weight based on 100 parts by weight of the hydride [2] before introducing the alkoxysilyl group. .2 parts by weight or more, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less.
- the method of reacting the hydride [2] of the block copolymer [1] with the ethylenically unsaturated silane compound in the presence of a peroxide can be performed using, for example, a heating kneader and a reactor.
- a heating kneader and a reactor As a specific example, a mixture of a hydride [2], an ethylenically unsaturated silane compound and a peroxide is heated and melted at a temperature equal to or higher than the melting temperature of the hydride [2] in a biaxial kneader to obtain a desired value. By kneading for this time, the alkoxysilyl group-modified product [3] can be obtained.
- the specific temperature during kneading is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, particularly preferably 200 ° C. or higher, preferably 240 ° C. or lower, more preferably 230 ° C. or lower, particularly preferably 220 ° C. or lower. It is.
- the kneading time is preferably 0.1 minutes or more, more preferably 0.2 minutes or more, particularly preferably 0.3 minutes or more, preferably 15 minutes or less, more preferably 10 minutes or less, particularly preferably. 5 minutes or less.
- kneading and extrusion can be performed continuously with the residence time being in the above range.
- the amount of the alkoxysilyl group-modified product [3] in the resin [I] is preferably 90% by weight or more, more preferably 93% by weight or more, still more preferably 95% by weight or more, and particularly preferably 97% by weight or more.
- the upper limit of the amount of the alkoxysilyl group-modified product [3] in the resin [I] can be 99.9% by weight or less.
- Ester compound] Resin [I] contains ester compound [4] in addition to alkoxysilyl-modified product [3].
- ester compound [4] By including the ester compound [4] in the resin [I], desired properties such as a small number of foreign matters and high peel strength can be imparted to the first resin layer.
- ester compounds include phosphate ester compounds, carboxylic acid ester compounds, phthalic acid ester compounds, and adipic acid ester compounds.
- an ester compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- carboxylic acid ester compounds are preferable from the viewpoint of satisfactorily expressing desired characteristics such as a small number of foreign substances and high peel strength.
- Examples of the phosphoric acid ester compound include triphenyl phosphate, tricresyl phosphate, phenyl diphenyl phosphate, and the like.
- carboxylic acid ester compounds include aromatic carboxylic acid esters and aliphatic carboxylic acid esters.
- the aromatic carboxylic acid ester is an ester of an aromatic carboxylic acid and an alcohol.
- aromatic carboxylic acid for example, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and the like can be used.
- Aromatic carboxylic acid may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the alcohol for example, a linear or branched alkyl alcohol can be used.
- a monohydric alcohol having one hydroxyl group per molecule may be used, and a polyhydric alcohol having two or more hydroxyl groups per molecule may be used.
- the monohydric alcohol examples include n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, tert-pentanol, n-hexanol, isohexanol, n- Examples include heptanol, isoheptanol, n-octanol, isooctanol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol, isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like.
- polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1, Examples include 5-hexanediol, 1,6-hexanediol, neopentyl glycol, pentaerythritol and the like.
- One kind of alcohol may be used alone, or two or more kinds of alcohols may be used in combination at any ratio.
- the aliphatic carboxylic acid ester is an ester of an aliphatic carboxylic acid and an alcohol.
- the aliphatic carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, stearic acid, and the like.
- Aliphatic carboxylic acid may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- alcohol the same example as the thing illustrated as alcohol which can be used for aromatic carboxylic acid ester is mentioned, for example.
- alcohol may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- the number of ester bonds per molecule of ester compound may be one, or two or more. Therefore, for example, a polyester compound may be used as the ester compound.
- the polyester compound can be produced by reacting a dihydric or higher acid with a polyhydric alcohol by using a monovalent acid or a monovalent alcohol as a stopper as required.
- ester compounds described above those containing an aromatic ring in the molecule are preferred, and those having an ester bond bonded to this aromatic ring are particularly preferred. Thereby, desired characteristics, such as a small number of foreign substances and high peel strength, can be expressed well. Therefore, among the ester compounds described above, aromatic carboxylic acid esters such as benzoic acid ester, phthalic acid ester, isophthalic acid ester, terephthalic acid ester, trimellitic acid ester, and pyromellitic acid ester are preferable, and benzoic acid ester is particularly preferable. . Among the benzoic acid esters, diethylene glycol dibenzoate and pentaerythritol tetrabenzoate are particularly preferable.
- the ester compound can function as a plasticizer in the resin [I]. Since the ester compound functions as a plasticizer, even in efficient production using a melt extrusion molding machine including a screw extruder, production with less foreign matter can be performed, and as a result, high quality and easy production can be achieved. A multilayer film can be obtained.
- the molecular weight of the ester compound is preferably 300 or more, more preferably 400 or more, particularly preferably 500 or more, preferably 2200 or less, more preferably 1800 or less, and particularly preferably 1400 or less. Bleed out can be suppressed by setting the molecular weight of the ester compound to be equal to or higher than the lower limit of the above range. Moreover, an ester compound can be easily functioned as a plasticizer by making it below an upper limit.
- the melting point of the ester compound is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, particularly preferably 50 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower, particularly preferably 120 ° C. or lower. is there. Bleed out can be suppressed by setting the melting point of the ester compound to be equal to or higher than the lower limit of the above range. Moreover, an ester compound can be easily functioned as a plasticizer by making it below an upper limit.
- the ratio of the ester compound in the resin [I] is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 2% by weight or more, and usually 10% by weight or less, preferably 9% by weight or less, more Preferably it is 8 weight% or less.
- Resin [I] can contain arbitrary components in addition to the alkoxysilyl group-modified product [3] and ester compound [4].
- Arbitrary components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- optional components include additional plasticizers other than the ester compound [4]. Since the glass transition temperature and elastic modulus of the resin [I] can be adjusted by using an additional plasticizer in addition to the ester compound [4], the heat resistance and mechanical strength of the resin [I] are adjusted. It is possible.
- the additional plasticizer is preferably one that can be easily mixed with the alkoxysilyl group-modified product [3] and does not impair the transparency of the first resin layer by mixing with the plasticizer.
- plasticizers examples include polyisobutene, hydrogenated polyisobutene, hydrogenated polyisoprene, hydrogenated 1,3-pentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, hydrogenated styrene / indene petroleum resin, and the like. Can be mentioned. Moreover, an additional plasticizer may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- the amount in the case of adding an additional plasticizer is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and particularly preferably 5 parts by weight or more with respect to 100 parts by weight of the alkoxysilyl group-modified product [3]. Preferably, it is 30 parts by weight or less, more preferably 20 parts by weight or less, and particularly preferably 15 parts by weight or less.
- antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
- antioxidant may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- phenolic antioxidants particularly alkyl-substituted phenolic antioxidants are preferable.
- alkyl-substituted phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, and 2,6-dicyclohexyl-4- Methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6- Dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t- Hexylphenol, 2-cyclohexyl-4-n-
- tricyclic phenolic antioxidants tetracyclic [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] tetracyclic phenolic antioxidants such as methane; and the like.
- the amount of the antioxidant is preferably 0.01 parts by weight or more, more preferably 0.02 parts by weight or more, particularly preferably 0.05 parts by weight or more with respect to 100 parts by weight of the alkoxysilyl group-modified product [3]. It is preferably 1.0 part by weight or less, more preferably 0.5 part by weight or less, and particularly preferably 0.3 part by weight or less.
- optional components include: heat stabilizers, light stabilizers, weathering stabilizers, ultraviolet absorbers, near infrared absorbers and other stabilizers; resin modifiers such as lubricants; colorants such as dyes and pigments; An inhibitor etc. are mentioned. These amounts can be appropriately selected within a range not impairing the object of the present invention.
- the resin [I] can be prepared by mixing the alkoxysilyl group-modified product [3], the ester compound [4], and optional components if necessary.
- Resin [I] is also prepared by mixing a precursor (modified hydride [2], etc.) of alkoxysilyl group-modified product [3], ester compound [4], and optional components if necessary, and then precursor.
- a hydride [2] is an ester compound [4 And the like, and those obtained by mixing the alkoxysilyl group-modified product [3] into pellets, and melt-kneading to uniformly disperse them. Addition of an arbitrary component can also be performed by a method according to any of these methods.
- the resin [I] is preferably transparent.
- the first resin layer made of such a transparent resin [I] can be suitably used for optical applications.
- the transparent resin refers to a resin having a total light transmittance of 70% or more, preferably 80% or more, more preferably 90% or more, measured using the resin as a test piece having a thickness of 1 mm.
- the total light transmittance can be measured in a wavelength range of 400 nm to 700 nm using an ultraviolet / visible spectrometer.
- the glass transition temperature Tg I of the resin [I] is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, particularly preferably 70 ° C. or higher, preferably 140 ° C. or lower, more preferably 120 ° C. or lower, particularly preferably. It is 100 degrees C or less.
- the highest glass transition temperature of the resin is preferably within the above range.
- the deflection temperature under load of the resin [I] is preferably 40 ° C or higher, more preferably 45 ° C or higher, preferably 60 ° C or lower, more preferably 55 ° C or lower.
- the load deflection temperature of the resin [I] can be measured under the conditions of B method and load of 0.45 MPa in accordance with JIS K7191-2 by preparing a test piece by injection molding.
- the second resin layer is a layer made of resin [II].
- Resin [II] can be any resin suitable for use as a general optical film material.
- the resin [II] may include the polymer [II].
- examples of the polymer [II] include a polymer selected from the group consisting of a cyclic olefin polymer, a hydride [2], an alkoxysilyl modified product [3], and a mixture thereof.
- the cyclic olefin polymer is a polymer in which the structural unit of the polymer has an alicyclic structure.
- a resin containing such a cyclic olefin polymer is usually excellent in performance such as transparency, dimensional stability, retardation development, and stretchability at low temperatures.
- the cyclic olefin polymer includes a polymer having an alicyclic structure in a main chain, a polymer having an alicyclic structure in a side chain, a polymer having an alicyclic structure in a main chain and a side chain, and these 2 A mixture of any of the above ratios can be obtained.
- a polymer having an alicyclic structure in the main chain is preferable.
- alicyclic structure examples include a saturated alicyclic hydrocarbon (cycloalkane) structure and an unsaturated alicyclic hydrocarbon (cycloalkene, cycloalkyne) structure.
- cycloalkane saturated alicyclic hydrocarbon
- cycloalkene unsaturated alicyclic hydrocarbon
- cycloalkyne unsaturated alicyclic hydrocarbon
- a cycloalkane structure and a cycloalkene structure are preferable, and a cycloalkane structure is particularly preferable.
- the number of carbon atoms constituting the alicyclic structure is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, particularly preferably per alicyclic structure. Is 15 or less. When the number of carbon atoms constituting the alicyclic structure is within this range, the mechanical strength, heat resistance and moldability of the cyclic olefin resin are highly balanced.
- the proportion of the structural unit having an alicyclic structure can be selected according to the purpose of use of the multilayer film of the present invention.
- the proportion of the structural unit having an alicyclic structure in the cyclic olefin polymer is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
- the proportion of the structural unit having an alicyclic structure in the cyclic olefin polymer is within this range, the transparency and heat resistance of the cyclic olefin resin are improved.
- a cycloolefin polymer is a polymer having a structure obtained by polymerizing a cycloolefin monomer.
- the cycloolefin monomer is a compound having a ring structure formed of carbon atoms and having a polymerizable carbon-carbon double bond in the ring structure.
- Examples of the polymerizable carbon-carbon double bond include a carbon-carbon double bond capable of polymerization such as ring-opening polymerization.
- Examples of the ring structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and polycycles obtained by combining these.
- a polycyclic cycloolefin monomer is preferable from the viewpoint of highly balancing the dielectric properties and heat resistance of the resulting polymer.
- norbornene polymers preferred are norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, hydrides thereof, and the like.
- norbornene-based polymers are particularly suitable because of good moldability.
- Examples of the norbornene polymer include a ring-opening polymer of a monomer having a norbornene structure and a hydride thereof; an addition polymer of a monomer having a norbornene structure and a hydride thereof.
- Examples of a ring-opening polymer of a monomer having a norbornene structure include a ring-opening homopolymer of one kind of monomer having a norbornene structure and a ring-opening of two or more kinds of monomers having a norbornene structure. Examples thereof include a copolymer and a ring-opening copolymer with a monomer having a norbornene structure and another monomer that can be copolymerized therewith.
- examples of the addition polymer of a monomer having a norbornene structure include an addition homopolymer of one kind of monomer having a norbornene structure and an addition copolymer of two or more kinds of monomers having a norbornene structure. And addition copolymers with monomers having a norbornene structure and other monomers copolymerizable therewith.
- a hydride of a ring-opening polymer of a monomer having a norbornene structure is particularly suitable from the viewpoints of moldability, heat resistance, low moisture absorption, dimensional stability, lightness, and the like.
- Examples of monomers having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 2,5 ] deca-3,7. -Diene (common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.0.1 2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4. 0.1 2,5 . 1 7,10 ] dodec-3-ene (common name: tetracyclododecene) and derivatives of these compounds (for example, those having a substituent in the ring).
- examples of the substituent include an alkyl group, an alkylene group, and a polar group. Moreover, these substituents may be the same or different, and a plurality thereof may be bonded to the ring.
- One type of monomer having a norbornene structure may be used alone, or two or more types may be used in combination at any ratio.
- Examples of polar groups include heteroatoms and atomic groups having heteroatoms.
- Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom.
- Specific examples of polar groups include carboxyl groups, carbonyloxycarbonyl groups, epoxy groups, hydroxyl groups, oxy groups, ester groups, silanol groups, silyl groups, amino groups, amide groups, imide groups, nitrile groups, and sulfonic acid groups. Is mentioned.
- the polymer constituting the resin [II] those containing such a polar group and those not containing a polar group can be preferably used.
- Examples of the monomer capable of ring-opening copolymerization with a monomer having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; And derivatives thereof.
- monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof
- cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene
- the monomer having a norbornene structure and a monomer capable of ring-opening copolymerization one type may be used alone, or two or more types may be used in combination at any ratio.
- a ring-opening polymer of a monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing a monomer in the presence of a ring-opening polymerization catalyst.
- Examples of monomers that can be copolymerized with a monomer having a norbornene structure include ⁇ -olefins having 2 to 20 carbon atoms such as ethylene, propylene, and 1-butene, and derivatives thereof; cyclobutene, cyclopentene, and cyclohexene. And non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and the like.
- ⁇ -olefin is preferable, and ethylene is more preferable.
- the monomer which can carry out addition copolymerization with the monomer which has a norbornene structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- An addition polymer of a monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing a monomer in the presence of an addition polymerization catalyst.
- the hydrogenated product of the above-described ring-opening polymer and addition polymer is, for example, carbon in the presence of a hydrogenation catalyst containing a transition metal such as nickel or palladium in a solution of these ring-opening polymer or addition polymer.
- a hydrogenation catalyst containing a transition metal such as nickel or palladium in a solution of these ring-opening polymer or addition polymer.
- -Carbon unsaturated bonds can be prepared by hydrogenation, preferably more than 90%.
- X bicyclo [3.3.0] octane-2,4-diyl-ethylene structure and Y: tricyclo [4.3.0.1 2,5 ] decane- Having a 7,9-diyl-ethylene structure, and the amount of these structural units is 90% by weight or more based on the total structural units of the norbornene polymer, and the ratio of X to Y The ratio is preferably 100: 0 to 40:60 by weight ratio of X: Y.
- Examples of monocyclic olefin polymers include addition polymers of cyclic olefin monomers having a single ring such as cyclohexene, cycloheptene, and cyclooctene.
- cyclic conjugated diene polymers include polymers obtained by cyclization of addition polymers of conjugated diene monomers such as 1,3-butadiene, isoprene and chloroprene; cyclic conjugates such as cyclopentadiene and cyclohexadiene. Mention may be made of 1,2- or 1,4-addition polymers of diene monomers; and their hydrides.
- the weight average molecular weight (Mw) of the cyclic olefin polymer can be appropriately selected according to the purpose of use of the multilayer film, and is preferably 10,000 or more, more preferably 15,000 or more, and particularly preferably 20,000 or more. , Preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 50,000 or less. When the weight average molecular weight is in such a range, the mechanical strength and moldability of the multilayer film are highly balanced.
- the weight average molecular weight is calculated by polyisoprene or polystyrene measured by gel permeation chromatography using cyclohexane as a solvent (however, toluene may be used when the sample does not dissolve in cyclohexane).
- the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the cyclic olefin polymer is preferably 1.2 or more, more preferably 1.5 or more, particularly preferably 1.8 or more, preferably Is 3.5 or less, more preferably 3.0 or less, and particularly preferably 2.7 or less.
- productivity of a polymer can be improved and manufacturing cost can be suppressed.
- the quantity of a low molecular component becomes small by making it into an upper limit or less, relaxation at the time of high temperature exposure can be suppressed and the stability of a multilayer film can be improved.
- resins can be used as the cyclic olefin polymer and the resin containing it.
- examples of commercially available resins include Zeonoa (manufactured by Nippon Zeon Co., Ltd.), Arton (manufactured by JSR Corporation), TOPAS (manufactured by Polyplastics Co., Ltd.) and Appel (manufactured by Mitsui Chemicals, Inc.).
- Resin [II] can contain arbitrary components in addition to polymer [II].
- the resin [II] may also contain an ester compound [4].
- the proportion of the ester compound [4] in the resin [II] is preferably less than 0.1% by weight, more preferably less than 0.05% by weight, and even more preferably less than 0.01% by weight. .
- Resin [II] can also include materials similar to those listed as optional components that resin [I] can contain. Resin [II] may also contain ester compound [4]. However, from the viewpoint of preventing bleed-out, it is preferable that these components are not included or the content ratio is small even if included. Specifically, the ratio of the polymer [II] in the resin [II] is preferably 98% by weight or more, more preferably 99% by weight or more, and even more preferably 99.5% by weight or more.
- the multilayer film of the present invention can be a two-type two-layer film composed of one first resin layer and one second resin layer.
- the multilayer film of this invention is not restricted to this, For example, you may have a 1st resin layer of 1 layer and a 2nd resin layer of 2 layers provided in the surface of the both sides.
- the multilayer film of the present invention may also have any layer other than the first resin layer and the second resin layer.
- the multilayer film of the present invention can be a film with less foreign matter contained in the resin. That is, in the multilayer film of the present invention, the number of non-translucent particles observed with the naked eye and a microscope is small. In particular, the number of foreign matters having a size of 100 ⁇ m or more in the first resin layer may be small.
- the foreign matter of “100 ⁇ m size or more” is a foreign matter having a major axis dimension of 100 ⁇ m or more when the film is observed.
- the number of foreign matters having a size of 100 ⁇ m or more in the first resin layer per 100 mm 2 of the area of the film can be preferably 2 or less, more preferably 1 or less. Such a small number of foreign matters can be achieved when the resin [I] contains the ester compound [4].
- each of the first resin layer and the second resin layer is not particularly limited and may be a desired thickness according to the application.
- the thickness per layer of each of the first resin layer and the second resin layer is, for example, preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
- the ratio of the total thickness of the first resin layer to the total thickness of the second resin layer is about 1: 1, specifically 0.7: 1.3 to 1.3: 0. Is preferably in the range of .7.
- the transparency of the multilayer film of the present invention is not particularly limited. However, the transparency of the multilayer film of the present invention is preferably high from the viewpoint that the multilayer film can be usefully used as a member that is required to transmit light. In this case, the total light transmittance of the multilayer film is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more.
- the haze of the multilayer film of the present invention is not particularly limited. However, when the multilayer film of the present invention is used for an optical application not specifically intended to diffuse light, the haze is generally preferably low. In this case, the haze of the multilayer film of the present invention is preferably 3.0% or less, more preferably 1.0% or less. The haze can be measured using a film piece obtained by cutting the first resin layer into 50 mm ⁇ 50 mm in accordance with JIS K 7136.
- the multilayer film of the present invention preferably has a sufficiently high adhesiveness with an inorganic material.
- the peel strength required to peel the multilayer film from the glass plate is preferably 15 N / cm or more, more preferably 20 N / cm or more. It is. Although there is no restriction
- the multilayer film of the present invention preferably has a low moisture permeability.
- a low moisture permeability By having a low moisture permeability, it can be preferably used as a material for sealing a light emitting element including an organic light emitting layer in an optical device including the organic light emitting layer.
- the moisture permeability of the multilayer film of the present invention is preferably 4 g / m 2 ⁇ 24 h or less, more preferably 2 g / m 2 ⁇ 24 h or less, and ideally 0 g / m 2 in an atmosphere of 40 ° C. and 90% RH. m 2 ⁇ 24h.
- the second resin layer preferably contains a cyclic olefin polymer as the polymer [II].
- the multilayer film of the present invention can be produced by any production method.
- it can be produced by a melt molding method or a solution casting method.
- the melt molding method can be classified into an extrusion molding method, a press molding method, an inflation molding method, an injection molding method, a blow molding method, a stretch molding method, and the like.
- an extrusion molding method, an inflation molding method, and a press molding method are preferable.
- a viewpoint that the first resin layer can be produced efficiently and easily. Therefore, the extrusion molding method is particularly preferable.
- the multilayer film of the present invention is particularly preferably produced by a production method including a coextrusion molding step described below. Below, this manufacturing method is demonstrated as a manufacturing method of the multilayer film of this invention.
- the method for producing a multilayer film of the present invention includes a coextrusion molding step in which the molten resin [I] and the resin [II] are coextruded.
- the coextrusion molding process uses a melt extrusion molding machine including a screw extruder and a die, and the coextrusion molding process includes pumping the resin [I] from the screw extruder to the die.
- FIG. 2 is a side view schematically showing an example of a melt extrusion molding machine for carrying out the method for producing a multilayer film of the present invention and an example of the production method of the present invention using the same.
- the melt extrusion molding machine 200 includes the multilayer film 100 shown in FIG. 1, that is, one first resin layer 110 made of resin [I] and one second resin layer made of resin [II]. This is an apparatus for producing a double film having two layers of 120.
- the melt extrusion molding machine 200 includes a screw extruder 210 and a T die 220.
- the melt extrusion molding machine 200 further includes a cooling roll 230 provided downstream of the T die, a hopper 240 provided at the upstream end of the screw extruder, and an introduction pipe 250 connected to the T die as optional components.
- the screw extruder 210 includes a cylinder 211, a shaft 213 provided inside the cylinder 211, and a screw 212 provided around the shaft 213.
- the screw 212 is provided in such a manner that the shaft 212 can be rotated when the shaft 213 is rotated about its axis, and has a size adapted to the inner diameter of the cylinder 211.
- the cylinder 211, the T die 220, the hopper 240, and the introduction pipe 250 are shown by their longitudinal sections.
- the resin [I] molded into a shape such as a pellet is put into the hopper 240 and supplied to the screw extruder 210. If necessary, the supply amount can be adjusted by a feeder (not shown) provided between the hopper 240 and the screw extruder 210. The temperature in the screw extruder can be adjusted by a device such as a heater (not shown) provided in the screw extruder. Thereby, resin [I] can be melted. By rotating the shaft 213 and thereby rotating the screw 212, the molten resin [I] can be pressed out in the direction of the arrow A1 and fed to the die 220.
- the temperature of the resin [I] in the screw extruder is preferably Tg I + 50 ° C. or higher, more preferably Tg I + 70 ° C. or higher, preferably Tg I + 160 ° C. or lower, more preferably Tg I + 140 ° C. or lower.
- Tg I represents the glass transition temperature of the resin [I].
- An efficient multilayer film can be produced by performing pumping using such a screw extruder.
- the structure inside the screw extruder is slightly cut, and minute foreign matters may be mixed in the resin.
- the mixing of such foreign substances can be a problem particularly when the alkoxysilyl modified product [3] of the block copolymer hydride is used.
- the ester compound [4] in addition to the alkoxysilyl modified product [3] of the combined hydride, it becomes possible to reduce the number of such foreign substances and efficiently produce a high-quality multilayer film.
- the resin [II] can be pumped through the introduction pipe 250 to the die 220 in the direction of arrow A2.
- the resin [II] can be pumped by connecting a screw extruder similar to that for the resin [I] to the introduction pipe 250 and operating it.
- the resin [I] and the resin [II] fed to the T die 220 are discharged from the T die 220 in the form of a two-layer / two-layer film.
- the temperature of the resin [I] and the resin [II] in the T die can be appropriately adjusted by a device such as a heater (not shown) provided in the T die so that both of the molten states are maintained. .
- the discharged molten film 300 is supplied onto the peripheral surface of the cooling roll 230.
- the molten film 300 is supplied to the cooling roll 230 such that the surface 310D on the resin [I] side is opposite to the surface in contact with the cooling roll 230.
- the temperature of the cooling roll can be appropriately adjusted within a range in which problems such as slipping and scratching can be suppressed.
- the film 300 in the molten state is cooled by cooling with the cooling roll 230, and becomes a two-layer / two-layer multilayer film 100.
- the obtained multilayer film 100 is carried out of the apparatus and can be further processed as necessary to obtain a product.
- the multilayer film 100 is efficiently manufactured as a long film.
- the long film means a film having a length of usually 5 times or more with respect to the width of the film, preferably a length of 10 times or more, and specifically wound in a roll shape. It refers to a film having a length that can be stored or transported.
- the upper limit of the ratio of the length to the film width is not particularly limited, but may be, for example, 100,000 times or less.
- the multilayer film of the present invention can be used for various applications such as optical applications.
- it can be used as an optical film such as a polarizing plate protective film, a retardation film, a brightness enhancement film, a transparent conductive film, a touch panel substrate, a liquid crystal substrate, a light diffusion sheet, a prism sheet, and a sealing film.
- an optical device including an organic light emitting layer such as an organic electroluminescence display device and an organic electroluminescence light emitting device, it can be preferably used as a film for sealing a light emitting element including the organic light emitting layer.
- Example 1 (1-1. Synthesis of block copolymer [1]) A block copolymer was produced by the following procedure using styrene as the aromatic vinyl compound and isoprene as the chain conjugated diene compound. In the following description, the polymerization conversion rate was measured by gas chromatography unless otherwise specified.
- the reaction solution containing the hydride was filtered to remove the hydrogenation catalyst. Thereafter, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (IRGANOX1010, manufactured by BASF Japan), which is a phenolic antioxidant, was added to the filtered reaction solution. .1 part xylene solution 1.0 part was added and dissolved.
- the reaction solution was filtered with a metal fiber filter (pore size 0.4 ⁇ m, manufactured by Nichidai Co., Ltd.) to remove minute solids. Thereafter, from the filtered reaction solution, using a cylindrical concentrating dryer (“Contro” manufactured by Hitachi, Ltd.), the temperature is 260 ° C. and the pressure is 0.001 MPa or less, and the solvents cyclohexane and xylene, and other volatile components are used. Was removed. Then, from the die directly connected to the concentration dryer, the solid content of the reaction solution is extruded in the form of a strand in a molten state, cooled, and cut with a pelletizer to obtain 90 parts of hydride [2] pellets. It was. The obtained hydride [2] had a weight average molecular weight (Mw) of 64,600 and a molecular weight distribution (Mw / Mn) of 1.11. The hydrogenation rate was almost 100%.
- Mw weight average molecular weight
- ester compound [4] As the ester compound [4], pentaerythritol distearate (“Unistar H476D” manufactured by NOF Corporation, pentaerythritol distearate (C (CH 2 OCOC 17 H 35 ) 2 (CH 2 OH) 2 ), molecular weight 657, melting point 53 ° C.). 90 parts of pellets of hydride [2] obtained in (1-2) and 8 parts of ester compound [4] were mixed at a resin temperature of 200 ° C. using a twin screw extruder (“TEM35B” manufactured by Toshiba Machine Co., Ltd.). To obtain a resin containing a hydride [2] and an ester compound [4]. The resin was extruded in a strand form from a twin screw extruder, cooled with water, and then cut with a pelletizer to obtain pellets.
- a twin screw extruder a twin screw extruder
- the kneaded resin is extruded into a strand shape, air-cooled, and then cut with a pelletizer, and the resin containing the alkoxysilyl group-modified product [3] in which an alkoxysilyl group is introduced into the hydride [2] and the ester compound [4] 97 parts of [I] pellets were obtained. It was 48 degreeC when the deflection temperature under load of obtained resin [I] was measured. When the obtained resin [I] was analyzed by 1 H-NMR spectrum (in deuterated chloroform), an absorption band based on protons of methoxy group was observed at 3.6 ppm. From the peak area ratio, the hydride [2] It was confirmed that 1.7 parts of vinyltrimethoxysilane was bonded to 100 parts.
- the resin [I] obtained in (1-4) and the resin [II] obtained in (1-5) are filled in each of two screw extruders and melted from the screw extruder to the T die.
- the film was co-extruded using a film melt extrusion molding machine, cooled with a cooling roll, and formed into a film of two types and two layers. Molding conditions are: die lip opening 0.8 mm, die lip width 120 mm, T die temperature 200 ° C., cooling roll temperature 50 ° C., and contact with the cooling roll so that the surface on the resin [II] side is in contact with the cooling roll during cooling. went.
- a two-kind, two-layer film including a first resin layer made of resin [I] and a second resin layer made of resin [II] was obtained.
- the thickness of the multilayer film was 20 ⁇ m, and the ratio of (first resin layer thickness) :( second resin layer thickness) was 1: 1.
- the obtained multilayer film was evaluated for total light transmittance, peel strength from glass, and moisture permeability.
- the resin [I] obtained in (1-4) is filled in a screw extruder in a melted state, pumped from the screw extruder to a T die, extruded using a film melt extrusion molding machine, and cooled roll And cooled to a single layer film.
- the molding conditions were a die lip opening of 0.8 mm, a die lip width of 120 mm, a T die temperature of 200 ° C., and a cooling roll temperature of 50 ° C.
- the thickness of the single layer film was 20 ⁇ m.
- the number of foreign matters was evaluated for the obtained single layer film.
- Example 2 In mixing the ester compound [4] of (1-3), the amount of hydride [2] pellets was changed from 90 parts to 93 parts, and the amount of ester compounds [4] was changed from 8 parts to 5 parts. Others were evaluated in the same manner as Example 1 by obtaining a multilayer film and a single layer film.
- Example 3 In the introduction of the alkoxysilyl group of (1-4), the addition amount of vinyltrimethoxysilane is changed from 1.8 parts to 7.2 parts, and the addition amount of di-t-butyl peroxide is changed from 0.2 parts to 0.2 parts. A multilayer film and a single layer film were obtained and evaluated in the same manner as in Example 1 except that the amount was changed to 8 parts. However, in the production of the resin [II] of (1-5), the amount of vinyltrimethoxysilane added was not changed and was as in (1-4) of Example 1. When the obtained resin [I] was analyzed by 1 H-NMR spectrum (in deuterated chloroform), an absorption band based on protons of methoxy group was observed at 3.6 ppm. From the peak area ratio, the hydride [2] It was confirmed that 7.0 parts of vinyltrimethoxysilane was bonded to 100 parts.
- Example 4 In mixing the ester compound [4] of (1-3), the amount of the hydride [2] pellets was changed from 90 parts to 97.7 parts, and the amount of the ester compound [4] was changed from 8 parts to 0.3 parts. A multilayer film and a single-layer film were obtained and evaluated in the same manner as in Example 1 except for changing to parts.
- Example 5 In the production of the multilayer film of (1-6), instead of the resin [II] obtained in (1-5), a cyclic olefin polymer resin (trade name “ZEONOR1215”, manufactured by Nippon Zeon Co., Ltd., A multilayer film and a single layer film were obtained and evaluated in the same manner as in Example 1 except that the T die temperature was changed from 200 ° C to 240 ° C.
- a cyclic olefin polymer resin trade name “ZEONOR1215”, manufactured by Nippon Zeon Co., Ltd.
- Non-ester plasticizer The weight (parts) of the plasticizer of the non-ester compound in the resin [I] constituting the first resin layer.
- Deflection temperature under load Deflection temperature under load of resin [I] constituting the first resin layer.
- Resin [II] Type of resin [II] constituting the second resin layer.
- HSIS + Silane modification Alkoxysilyl group modification product of block copolymer hydride [3].
- COP Cyclic olefin polymer resin.
- PET Polyethylene terephthalate.
- the multilayer film satisfying the requirements of the present invention can have a small number of foreign substances, a high total light transmittance, a high peel strength from glass, and a low moisture permeability. .
- Multi-layer film 110 First resin layer 110D: The other surface of the first resin layer 110U: One surface of the first resin layer 120: Second resin layer 200: Melt extrusion molding machine 210: Screw extruder 211: Cylinder 212: Screw 213: Shaft 220: T die 230: Cooling roll 240: Hopper 250: Introduction pipe
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Abstract
Description
すなわち、本発明は下記の通りである。
前記樹脂[I]は、ブロック共重合体水素化物のアルコキシシリル変性物[3]及びエステル化合物[4]を含み、
前記アルコキシシリル変性物[3]は、ブロック共重合体[1]の主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の90%以上を水素化した水素化物[2]のアルコキシシリル基変性物であり、
前記ブロック共重合体[1]は、芳香族ビニル化合物単位を主成分とする、前記ブロック共重合体[1]1分子あたり2個以上の重合体ブロック[A]と、鎖状共役ジエン化合物単位を主成分とする、前記ブロック共重合体[1]1分子あたり1個以上の重合体ブロック[B]とを有し、
前記ブロック共重合体[1]の全体に占める前記重合体ブロック[A]の重量分率wAと、前記ブロック共重合体[1]の全体に占める前記重合体ブロック[B]の重量分率wBとの比(wA/wB)が、20/80~60/40であり、
前記樹脂[I]における前記エステル化合物[4]の割合が0.1重量%~10重量%である、複層フィルム。
〔2〕 前記樹脂[II]が、環状オレフィン重合体、前記水素化物[2]、前記アルコキシシリル変性物[3]、及びこれらの混合物からなる群より選択される重合体を含む、〔1〕に記載の複層フィルム。
〔3〕 前記樹脂[II]は前記エステル化合物[4]を含まないか、又は前記樹脂[II]における前記エステル化合物[4]の含有割合が0.1重量%未満である、
〔1〕又は〔2〕に記載の複層フィルム。
〔4〕 〔1〕~〔3〕のいずれか1項に記載の複層フィルムの製造方法であって、
溶融された前記樹脂[I]及び前記樹脂[II]を共押出しする、共押出成形工程を含む、製造方法。
〔5〕 前記共押出成形工程を、スクリュー押出機及びダイを含む溶融押出成形機を用い、
前記共押出成形工程は、前記樹脂[I]を、スクリュー押出機から前記ダイに圧送することを含む、〔4〕に記載の製造方法。
以下の説明において、「偏光板」とは、別に断らない限り、剛直な部材だけでなく、例えば樹脂製のフィルムのように可撓性を有する部材も含む。
本発明の複層フィルムは、特定の樹脂[I]からなる第一樹脂層と、第一樹脂層の少なくとも片面に設けられた、樹脂[II]からなる第二樹脂層とを備える。
図1は、本発明の複層フィルムの一例を模式的に示す断面図である。図1において、複層フィルム100は、第一樹脂層110と、第一樹脂層110の一方の面110Uに設けられた第二樹脂層120とを備える。この例では、第一樹脂層110の他方の面110Dは、複層フィルム100の外表面に露出した状態となっている。
第一樹脂層は、樹脂[I]からなる層である。樹脂[I]は、特定のアルコキシシリル変性物[3]及びエステル化合物[4]を含む。アルコキシシリル変性物[3]は、特定のブロック共重合体[1]の不飽和結合を水素化した水素化物[2]のアルコキシシリル基変性物である。
ブロック共重合体[I]は、ブロック共重合体[1]1分子あたり2個以上の重合体ブロック[A]と、ブロック共重合体[1]1分子あたり1個以上の重合体ブロック[B]とを有するブロック共重合体である。
また、ブロック共重合体[1]の分子量分布(Mw/Mn)は、好ましくは3以下、より好ましくは2以下、特に好ましくは1.5以下であり、好ましくは1.0以上である。ここで、Mnは、数平均分子量を表す。
前記ブロック共重合体[1]の重量平均分子量(Mw)及び分子量分布(Mw/Mn)は、テトラヒドロフラン(THF)を溶媒とするゲル・パーミエーション・クロマトグラフィー(GPC)によって、ポリスチレン換算の値として測定しうる。
溶液重合を行う場合、溶媒としては、各工程で得られる重合体が溶解しうる不活性溶媒を用いうる。不活性溶媒としては、例えば、n-ブタン、n-ペンタン、イソペンタン、n-ヘキサン、n-ヘプタン、イソオクタン等の脂肪族炭化水素溶媒;シクロペンタン、シクロヘキサン、メチルシクロペンタン、メチルシクロヘキサン、デカリン、ビシクロ[4.3.0]ノナン、トリシクロ[4.3.0.12,5]デカン等の脂環式炭化水素溶媒;ベンゼン、トルエン等の芳香族炭化水素溶媒;などが挙げられる。これらは、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。中でも、溶媒として脂環式炭化水素溶媒を用いると、水素化反応にも不活性な溶媒としてそのまま使用でき、ブロック共重合体[1]の溶解性も良好であるため、好ましい。溶媒の使用量は、全使用モノマー100重量部に対して、好ましくは200重量部~2000重量部である。
水素化物[2]は、ブロック共重合体[1]の不飽和結合の特定量以上の量を水素化して得られる重合体である。ここで、水素化されるブロック共重合体[1]の不飽和結合には、ブロック共重合体[1]の主鎖及び側鎖の、芳香族性及び非芳香族性の炭素-炭素不飽和結合をいずれも含む。
水素化物[2]の分子量分布(Mw/Mn)は、好ましくは3以下、より好ましくは2以下、特に好ましくは1.5以下であり、好ましくは1.0以上である。水素化物[2]の分子量分布(Mw/Mn)を前記の範囲に収めることにより、第一樹脂層の機械強度及び耐熱性を向上させることができ、更には第一樹脂層の複屈折を小さくし易い。
水素化物[2]の重量平均分子量(Mw)及び分子量分布(Mw/Mn)は、テトラヒドロフランを溶媒としたゲル・パーミエーション・クロマトグラフィー(GPC)により、ポリスチレン換算の値で測定しうる。
有機アルミニウム化合物としては、例えば、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;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;等が挙げられる。
アルコキシシリル基変性物[3]は、上述したブロック共重合体[1]の水素化物[2]に、アルコキシシリル基を導入して得られる重合体である。この際、アルコキシシリル基は、上述した水素化物[2]に直接結合していてもよく、例えばアルキレン基などの2価の有機基を介して間接的に結合していてもよい。アルコキシシリル基変性物[3]は、ガラス、金属等の無機材料との接着性に特に優れる。そのため、第一樹脂層は、通常、前記の無機材料との接着性に優れる。したがって、第一樹脂層は、高温高湿環境に長時間暴露された後も、無機材料に対する高い接着力を維持することができる。
アルコキシシリル基の導入量は、1H-NMRスペクトルにて計測しうる。また、アルコキシシリル基の導入量の計測の際、導入量が少ない場合は、積算回数を増やして計測しうる。
アルコキシシリル基変性物[3]の重量平均分子量(Mw)及び分子量分布(Mw/Mn)は、テトラヒドロフランを溶媒としたゲル・パーミエーション・クロマトグラフィー(GPC)によって、ポリスチレン換算の値として測定しうる。
樹脂[I]は、アルコキシシリル変性物[3]に加えて、エステル化合物[4]を含む。樹脂[I]がエステル化合物[4]を含むことにより、少ない異物数、高い剥離強度等の所望の特性を、第一樹脂層に付与することができる。
芳香族カルボン酸としては、例えば、安息香酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸などを用いうる。芳香族カルボン酸は、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。
アルコールとしては、例えば、直鎖又は分岐のアルキルアルコールを用いうる。また、アルコールとしては、水酸基を1分子当たり1個有する1価のアルコールを用いてもよく、水酸基を1分子当たり2個以上有する多価アルコールを用いてもよい。1価のアルコールの具体例としては、n-プロパノール、イソプロパノール、n-ブタノール、イソブタノール、tert-ブタノール、n-ペンタノール、イソペンタノール、tert-ペンタノール、n-ヘキサノール、イソヘキサノール、n-ヘプタノール、イソヘプタノール、n-オクタノール、イソオクタノール、2-エチルヘキサノール、n-ノナノール、イソノナノール、n-デカノール、イソデカノール、ラウリルアルコール、ミリスチルアルコール、パルミチルアルコール、ステアリルアルコール等が挙げられる。また、多価アルコールの具体例としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、1,2-プロピレングリコール、1,3-プロピレングリコール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ヘキサンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、ペンタエリスリトール等が挙げられる。アルコールは、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。
脂肪族カルボン酸としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバチン酸、ステアリン酸等が挙げられる。脂肪族カルボン酸は、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。
アルコールとしては、例えば、芳香族カルボン酸エステルに用いうるアルコールとして例示した物と同様の例が挙げられる。また、アルコールは、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。
樹脂[I]は、アルコキシシリル基変性物[3]及びエステル化合物[4]に加えて、任意の成分を含みうる。任意の成分は、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。
樹脂[I]は、アルコキシシリル基変性物[3]と、エステル化合物[4]と、必要であれば任意の成分とを混合することにより調製しうる。樹脂[I]はまた、アルコキシシリル基変性物[3]の前駆体(水素化物[2]等)と、エステル化合物[4]と、必要であれば任意の成分とを混合し、その後前駆体をアルコキシシリル基変性物[3]に変換することによっても調製しうる。
樹脂[I]は、透明であることが好ましい。このような透明の樹脂[I]からなる第一樹脂層は、光学用途に好適に用いうる。ここで、透明な樹脂とは、当該樹脂を厚み1mmの試験片として測定した全光線透過率が、通常70%以上、好ましくは80%以上、より好ましくは90%以上である樹脂を言う。全光線透過率は、紫外・可視分光計を用いて、波長400nm~700nmの範囲で測定しうる。
第二樹脂層は、樹脂[II]からなる層である。樹脂[II]は、一般的な光学フィルムの材料として用いるのに適した任意の樹脂としうる。好ましくは、樹脂[II]は、重合体[II]を含むものとしうる。かかる重合体[II]の例としては、環状オレフィン重合体、水素化物[2]、アルコキシシリル変性物[3]、及びこれらの混合物からなる群より選択される重合体が挙げられる。
環状オレフィン重合体は、その重合体の構造単位が脂環式構造を有する重合体である。このような環状オレフィン重合体を含む樹脂は、通常、透明性、寸法安定性、位相差発現性、及び低温での延伸性等の性能に優れる。
重合体[II]としての水素化物[2]及びアルコキシシリル変性物[3]としては、樹脂[I]を構成するアルコキシシリル変性物[3]及びその前駆体としての水素化物[2]として説明したものと同様のものを用いうる。
樹脂[II]は、重合体[II]に加えて、任意の成分を含みうる。例えば、樹脂[II]はまた、エステル化合物[4]を含んでいてもよい。但し、ブリードアウトを防ぐ観点から、樹脂[II]はエステル化合物[4]を含まないか、又は含んでいてもその含有割合が少ないことが好ましい。具体的には、樹脂[II]におけるエステル化合物[4]の割合は、好ましくは0.1重量%未満、より好ましくは0.05重量%未満、さらにより好ましくは0.01重量%未満としうる。
本発明の複層フィルムは、1層の第一樹脂層及び1層の第二樹脂層からなる2種2層のフィルムとしうる。しかしながら本発明の複層フィルムはこれに限られず、例えば、1層の第一樹脂層と、その両側の面に設けられた2層の第二樹脂層を有するものであってもよい。本発明の複層フィルムはまた、第一樹脂層及び第二樹脂層以外の任意の層を有していてもよい。
本発明の複層フィルムは、任意の製造方法により製造しうる。例えば、溶融成形法、溶液流延法の成形方法により製造しうる。溶融成形法は、さらに詳細には、押出成形法、プレス成形法、インフレーション成形法、射出成形法、ブロー成形法、延伸成形法などに分類できる。これらの方法の中でも、機械強度及び表面精度に優れた第一樹脂層を得るために、押出成形法、インフレーション成形法及びプレス成形法が好ましく、中でも効率よく簡単に第一樹脂層を製造できる観点から、押出成形法が特に好ましい。本発明の複層フィルムは、以下に述べる共押出成形工程を含む製造方法で製造することが特に好ましい。以下においては、この製造方法を、本発明の複層フィルムの製造方法として説明する。
本発明の複層フィルムは、光学的用途等の様々な用途に用いうる。例えば、偏光板保護フィルム、位相差フィルム、輝度向上フィルム、透明導電フィルム、タッチパネル用基板、液晶基板、光拡散シート、プリズムシート、封止フィルム等の光学フィルムとして用いうる。特に、有機エレクトロルミネッセンス表示装置、有機エレクトロルミネッセンス発光装置等の、有機発光層を備える光学装置において、かかる有機発光層を含む発光素子を封止するためのフィルムとして好ましく用いうる。
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。
〔1.重量平均分子量(Mw)及び分子量分布(Mw/Mn)の測定方法〕
重合体の重量平均分子量(Mw)及び数平均分子量(Mn)は、テトラヒドロフランを溶離液とするゲル・パーミエーション・クロマトグラフィー(GPC)によって、標準ポリスチレン換算値として測定した。測定は、38℃において行った。また、測定装置としては、東ソー社製「HLC8020GPC」を用いた。
ブロック共重合体の水素化物の主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の水素化率は、1H-NMRスペクトルを測定して算出した。
実施例及び比較例で得られた複層フィルムを光学顕微鏡を用いて観察し、100μmサイズ以上の異物の数を計数し、100mm2当たりの数を求めた。
実施例及び比較例で得られた複層フィルムを試料として、JIS K 7361に従い測定した(単位:%)。
実施例及び比較例で得られた複層フィルムを切断し、100mm×100mmの矩形の形状とし、これを試料とした。試料の第一樹脂層側の表面と、ガラス(500mm×1000mm×1.1mmt)の表面とを重ね合せ、170℃5分間真空脱気を行い、10分間0.1MPaで加圧プレスをすることにより接着した。オートグラフ(島津製作所社製「AGS-10NX」)を使用して、JIS Z 0237に準じて、試料をガラス板から剥離させる180°剥離試験を行い、剥離強度を測定した(単位:N/10mm)。この際の測定条件は、剥離速度100mm/分、温度23℃とした。
実施例及び比較例で得られた複層フィルムの透湿度を、JIS Z 0208に準じて、40℃、90%RHの環境条件で測定した(単位:g/m2・24h)。
実施例及び比較例で得られた樹脂[I]を、射出成形して試験片を作製し、JIS K7191-2に準拠し、B法、荷重0.45MPaの条件で測定した。
(1-1.ブロック共重合体[1]の合成)
芳香族ビニル化合物としてスチレンを用い、鎖状共役ジエン化合物としてイソプレンを用いて、以下の手順によってブロック共重合体を製造した。以下の説明において、重合転化率は、別に断らない限り、ガスクロマトグラフィーによって測定した。
次に、ブロック共重合体[1]を含む前記の重合体溶液を、攪拌装置を備えた耐圧反応器に移送し、水素化触媒としてシリカ-アルミナ担持型ニッケル触媒(ズードケミー触媒社製「T-8400RL」)3.0部及び脱水シクロヘキサン100部を添加して混合した。反応器内部を水素ガスで置換し、更に溶液を攪拌しながら水素を供給し、温度170℃、圧力4.5MPaにて6時間水素化反応を行った。これにより、溶液中のブロック共重合体[1]が水素化されて、ブロック共重合体[1]の水素化物を含む反応溶液を得た。この水素化物の重量平均分子量(Mw)は65,300、分子量分布(Mw/Mn)は1.06であった。
エステル化合物[4]として、ペンタエリスリトールジステアレート(日油社製「ユニスターH476D」、ペンタエリスリトールジステアレート(C(CH2OCOC17H35)2(CH2OH)2)、分子量657、融点53℃)を用意した。
(1-2)で得た水素化物[2]のペレット90部と、エステル化合物[4]8部とを、二軸押出機(東芝機械社製「TEM35B」)を用いて、樹脂温度200℃で混練して、水素化物[2]及びエステル化合物[4]を含む樹脂を得た。この樹脂を、二軸押出機からストランド状に押出し、水冷した後、ペレタイザーによりカッティングして、ペレットを得た。
(1-3)で得たペレット98部に対して、ビニルトリメトキシシラン1.8部及びジ-t-ブチルパーオキサイド0.2部を添加した。この混合物を、二軸押出機(東芝機械社製「TEM37B」)を用いて、樹脂温度210℃、滞留時間80秒~90秒で混練した。その後、混練した樹脂をストランド状に押し出し、空冷した後、ペレタイザーによりカッティングして、水素化物[2]にアルコキシシリル基を導入したアルコキシシリル基変性物[3]及びエステル化合物[4]を含む樹脂[I]のペレット97部を得た。得られた樹脂[I]の荷重たわみ温度を測定したところ、48℃であった。得られた樹脂[I]を1H-NMRスペクトル(重クロロホルム中)により分析したところ、3.6ppmにメトキシ基のプロトンに基づく吸収帯が観察され、ピーク面積比から、水素化物[2]の100部に対して、ビニルトリメトキシシラン1.7部が結合したことが確認された。
(1-3)で得たペレットに代えて、(1-2)で得られた水素化物[2]のペレットそのままのものを98部用いた他は、(1-4)と同様にして、アルコキシシリル基変性物[3]を含む(但し及びエステル化合物[4]を含まない)樹脂[II]のペレットを得た。
フィルム溶融押出成形機(据置型、GSIクレオス社製)を用意した。このフィルム溶融押出成形機は、スクリュー径20mm、圧縮比3.1、L/D=30のスクリュー押出機を2台備え、且つ、共押出用2層のハンガーマニホールドタイプのTダイ(Tダイ幅150mm)を備えるものであった。
フィルム溶融押出成形機(据置型、GSIクレオス社製)を用意した。このフィルム溶融押出成形機は、スクリュー径20mm、圧縮比3.1、L/D=30のスクリュー押出機を1台備え、且つ、単層押出用Tダイ(Tダイ幅150mm)を備えるものであった。
(1-3)のエステル化合物[4]の混合において、水素化物[2]のペレットの量を90部から93部に変更し、エステル化合物[4]の量を8部から5部に変更した他は、実施例1と同様にして、複層フィルム及び単層フィルムを得て評価した。
(1-4)のアルコキシシリル基の導入において、ビニルトリメトキシシランの添加量を1.8部から7.2部に、ジ-t-ブチルパーオキサイドの添加量を0.2部から0.8部に変更した他は、実施例1と同様にして、複層フィルム及び単層フィルムを得て評価した。但し、(1-5)の樹脂[II]の製造においては、ビニルトリメトキシシランの添加量は変更せず実施例1の(1-4)の通りとした。得られた樹脂[I]を1H-NMRスペクトル(重クロロホルム中)により分析したところ、3.6ppmにメトキシ基のプロトンに基づく吸収帯が観察され、ピーク面積比から、水素化物[2]の100部に対して、ビニルトリメトキシシラン7.0部が結合したことが確認された。
(1-3)のエステル化合物[4]の混合において、水素化物[2]のペレットの量を90部から97.7部に変更し、エステル化合物[4]の量を8部から0.3部に変更した他は、実施例1と同様にして、複層フィルム及び単層フィルムを得て評価した。
(1-6)の複層フィルムの製造において、樹脂[II]として、(1-5)で得たものに代えて、環状オレフィン重合体樹脂(商品名「ZEONOR1215」、日本ゼオン株式会社製、Tg約123℃)を用い、Tダイ温度を200℃から240℃に変更した他は、実施例1と同様にして、複層フィルム及び単層フィルムを得て評価した。
(1-4)のアルコキシシリル基の導入において、(1-3)で得たペレットに代えて、(1-2)で得られた水素化物[2]のペレットそのままのものを98部用いた他は、実施例と同様にして、複層フィルム及び単層フィルムを得て評価した。即ち、(1-6)の複層フィルムの製造においては、樹脂[I]及び樹脂[II]の組み合わせに代えて、同一の樹脂[II]を用いて、1種2層の複層フィルムを形成した。
下記の点を変更した他は、実施例1と同様にして、複層フィルム及び単層フィルムを得て評価した。
・(1-3)のエステル化合物[4]の混合において、エステル化合物[4]としてのペンタエリスリトールジステアレート8部に代えて、非エステル化合物の可塑剤である流動パラフィン(和光特級、和光純薬工業(株)製、融点-24℃)8部を用いた。
・(1-6)の複層フィルムの製造において、樹脂[II]として、(1-5)で得たものに代えて、ポリエチレンテレフタレート(帝人社製「TRN-8550FF」)のペレットを用い、Tダイ温度を200℃から260℃に変更した。
(1-3)のエステル化合物[4]の混合において、エステル化合物[4]として、ペンタエリスリトールジステアレート8部に代えて、非エステル化合物の可塑剤である流動パラフィン(和光特級、和光純薬工業(株)製)8部を用いた他は、実施例1と同様にして、複層フィルム及び単層フィルムを得て評価した。
重合体割合:第一樹脂層を構成する樹脂[I]中の、ブロック共重合体水素化物のアルコキシシリル基変性物[3]のうちの、アルコキシシリル基の導入前の水素化物[2]に相当する分の重量(部)。
シラン変性:第一樹脂層を構成する樹脂[I]中の、ビニルトリメトキシシランに相当する分の重量(部)。
アルキキシリル基導入量:アルコキシシリル基変性物におけるアルコキシシリル基の導入量(重量部)。
エステル化合物:第一樹脂層を構成する樹脂[I]中の、エステル化合物の重量(部)。
非エステル可塑剤:第一樹脂層を構成する樹脂[I]中の、非エステル化合物の可塑剤の重量(部)。
荷重たわみ温度:第一樹脂層を構成する樹脂[I]の荷重たわみ温度。
樹脂[II]:第二樹脂層を構成する樹脂[II]の種類。HSIS+シラン変性:ブロック共重合体水素化物のアルコキシシリル基変性物[3]。COP:環状オレフィン重合体樹脂。PET:ポリエチレンテレフタレート。
110:第一樹脂層
110D:第一樹脂層の他方の面
110U:第一樹脂層の一方の面
120:第二樹脂層
200:溶融押出成形機
210:スクリュー押出機
211:シリンダー
212:スクリュー
213:シャフト
220:Tダイ
230:冷却ロール
240:ホッパー
250:導入管
Claims (5)
- 樹脂[I]からなる第一樹脂層と、前記第一樹脂層の少なくとも片面に設けられた、樹脂[II]からなる第二樹脂層とを備え、
前記樹脂[I]は、ブロック共重合体水素化物のアルコキシシリル変性物[3]及びエステル化合物[4]を含み、
前記アルコキシシリル変性物[3]は、ブロック共重合体[1]の主鎖及び側鎖の炭素-炭素不飽和結合及び芳香環の炭素-炭素不飽和結合の90%以上を水素化した水素化物[2]のアルコキシシリル基変性物であり、
前記ブロック共重合体[1]は、芳香族ビニル化合物単位を主成分とする、前記ブロック共重合体[1]1分子あたり2個以上の重合体ブロック[A]と、鎖状共役ジエン化合物単位を主成分とする、前記ブロック共重合体[1]1分子あたり1個以上の重合体ブロック[B]とを有し、
前記ブロック共重合体[1]の全体に占める前記重合体ブロック[A]の重量分率wAと、前記ブロック共重合体[1]の全体に占める前記重合体ブロック[B]の重量分率wBとの比(wA/wB)が、20/80~60/40であり、
前記樹脂[I]における前記エステル化合物[4]の割合が0.1重量%~10重量%である、複層フィルム。 - 前記樹脂[II]が、環状オレフィン重合体、前記水素化物[2]、前記アルコキシシリル変性物[3]、及びこれらの混合物からなる群より選択される重合体を含む、請求項1に記載の複層フィルム。
- 前記樹脂[II]は前記エステル化合物[4]を含まないか、又は前記樹脂[II]における前記エステル化合物[4]の含有割合が0.1重量%未満である、
請求項1又は2に記載の複層フィルム。 - 請求項1~3のいずれか1項に記載の複層フィルムの製造方法であって、
溶融された前記樹脂[I]及び前記樹脂[II]を共押出しする、共押出成形工程を含む、製造方法。 - 前記共押出成形工程を、スクリュー押出機及びダイを含む溶融押出成形機を用い、
前記共押出成形工程は、前記樹脂[I]を、スクリュー押出機から前記ダイに圧送することを含む、請求項4に記載の製造方法。
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CN112154160A (zh) * | 2018-05-31 | 2020-12-29 | 株式会社可乐丽 | 改性加氢物及其制造方法、树脂组合物、以及它们的各种用途 |
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CN114126865A (zh) * | 2019-07-31 | 2022-03-01 | 日本瑞翁株式会社 | 多层膜及其制造方法以及卷绕体 |
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