WO2015005292A1 - Film étiré et son procédé de fabrication - Google Patents

Film étiré et son procédé de fabrication Download PDF

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Publication number
WO2015005292A1
WO2015005292A1 PCT/JP2014/068088 JP2014068088W WO2015005292A1 WO 2015005292 A1 WO2015005292 A1 WO 2015005292A1 JP 2014068088 W JP2014068088 W JP 2014068088W WO 2015005292 A1 WO2015005292 A1 WO 2015005292A1
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Prior art keywords
block copolymer
film
molecular weight
polymer
stretched film
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PCT/JP2014/068088
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English (en)
Japanese (ja)
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淳 石黒
大輔 齋藤
小原　禎二
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日本ゼオン株式会社
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Priority to JP2015526329A priority Critical patent/JP6398975B2/ja
Publication of WO2015005292A1 publication Critical patent/WO2015005292A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/045—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique in a direction which is not parallel or transverse to the direction of feed, e.g. oblique
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3083—Birefringent or phase retarding elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to an obliquely stretched film made of a hydride of a block copolymer, which has small thickness unevenness and excellent phase difference and orientation axis angle accuracy, and a method for producing the same.
  • Liquid crystal displays have features such as high image quality, thinness, light weight, and low power consumption, and are widely used as flat panel displays for televisions and personal computers.
  • a super-twisted nematic (STN) liquid crystal with a simple matrix system and a simple structure is used for the color liquid crystal display, but the problem is that the hue of the liquid crystal display is green or yellow-red due to the elliptically polarized light based on the STN liquid crystal.
  • a countermeasure is used in which a retardation film is used, the retardation is compensated by birefringence of the STN liquid crystal, and the elliptically polarized light is returned to linearly polarized light.
  • a method for producing a retardation film for example, a predetermined tilt angle with respect to the side of the stretched film is obtained so as to have a desired orientation axis from a film uniaxially stretched in the length direction or width direction of the unstretched film.
  • a method of cutting the stretched film is known.
  • this method has a problem that even if the cutting is performed so as to obtain the maximum area, a cutting loss always occurs and the product yield is poor.
  • Patent Document 1 a plastic film such as polycarbonate or polyester is uniaxially stretched in the lateral or longitudinal direction, and the left and right sides of the stretching direction are stretched at different speeds in the longitudinal or lateral direction different from the stretching direction.
  • a technique for inclining the orientation axis with respect to the uniaxial stretching direction has been proposed. According to this method, the inclination angle of the orientation axis can be easily changed by controlling the stretching ratio in the longitudinal and transverse directions, and an obliquely oriented film in which the orientation axis is inclined at various angles with respect to the end side can be obtained efficiently. be able to.
  • the stretched film obtained by this method generates wrinkles or uneven thickness, and it is difficult to obtain a film with excellent accuracy.
  • the locus L1 of the holding means from the substantial holding start point of one end of a polymer film such as a polyvinyl alcohol film to the substantial holding release point, and the substantial holding of the other end of the polymer film are disclosed.
  • the trajectory L2 of the holding means from the start point to the substantial holding release point and the distance W to the two substantial holding release points satisfy the relationship of Expression (1):
  • the film obtained by this method also has a problem that optical characteristics change when used for a long period of time.
  • Patent Document 3 an unstretched film made of a polymer resin having an alicyclic structure such as a norbornene-based polymer or a vinyl alicyclic hydrocarbon polymer, and obtained by melt extrusion molding, A long stretched film obtained by continuously obliquely stretching in the direction of 1 to 50 ° is disclosed.
  • the obtained obliquely stretched film is used as, for example, a retardation plate and bonded to a long quarter-wave plate, (elliptical) circularly polarizing plates can be continuously produced. It is also disclosed that high productivity can be obtained.
  • norbornene-based polymers have a small industrial supply amount, an obliquely oriented film using a resin having higher industrial versatility is desired.
  • the obliquely stretched film of the vinyl alicyclic hydrocarbon polymer does not always exhibit sufficient retardation as desired for the retardation film, and the film thickness uniformity of the obliquely stretched film is not always sufficient. There was a problem such as.
  • Patent Document 4 a film obtained by melt extrusion molding a vinyl aromatic / butadiene block copolymer hydride in which both a vinyl aromatic block and a butadiene block are substantially completely hydrogenated is stretched. A retardation film obtained in this manner is disclosed.
  • this document does not describe the continuous stretching in the oblique direction, and the molecular weight and molecular weight of the block copolymer hydride desirable for controlling the retardation and retardation of the obliquely stretched film. There is no disclosure about the distribution.
  • the present invention has been made in view of the above-described prior art, and has an unevenly stretched film made of a hydride of a block copolymer having a small thickness unevenness and excellent accuracy in retardation and orientation axis angle, and a method for producing the same.
  • the purpose is to provide.
  • the inventors of the present invention formed a film by melt extrusion molding a block copolymer hydride [2] having a specific copolymer composition and a specific molecular weight and molecular weight distribution.
  • a block copolymer hydride [2] having a specific copolymer composition and a specific molecular weight and molecular weight distribution.
  • At least two polymer blocks [A] mainly comprising a repeating unit derived from an aromatic vinyl compound and a repeating unit derived from a chain conjugated diene compound as a main component, It is composed of at least one polymer block [B], and the weight fraction of the whole polymer block [A] in the whole block copolymer is wA, and the whole polymer block [B] is in the whole block copolymer.
  • the weight fraction is wB, 90% or more of all unsaturated bonds of the block copolymer [1] in which the ratio of wA to wB (wA: wB) is 50:50 to 75:25 is hydrogen.
  • a melt-extruded film comprising a block copolymer hydride [2] having a weight average molecular weight (Mw) of 45,000 to 150,000 and a molecular weight distribution (Mw / Mn) of 1.5 or less.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Stretched film in the direction of 5 ⁇ 80 ° obtained by continuous oblique stretching is provided for in the width direction.
  • the aromatic vinyl compound is preferably styrene
  • the chain conjugated diene compound is preferably butadiene and / or isoprene.
  • a method for producing a stretched film according to the present invention wherein the block copolymer hydride [2] pellets are melted by an extruder and attached to the extruder.
  • the film is extruded in the width direction by using a tenter type stretching machine that can apply feeding force, pulling force or pulling force at independent speeds in the lateral and longitudinal directions.
  • the hydride of the block copolymer [2] kept at a temperature of 50 to 120 ° C for 2 hours or more
  • a method for producing a stretched film characterized by using pellets.
  • an obliquely stretched film made of a hydride of a block copolymer which is free from wrinkles and thickness unevenness and is excellent in retardation accuracy and orientation axis angle accuracy, and a method for producing the same.
  • the stretched film of the present invention is useful as an optical film such as a polarizing plate protective film or a retardation film.
  • the unstretched film used in the examples and comparative examples can be stretched obliquely by moving the left and right tenter clips at a predetermined speed and bending the film feed path while stretching the film in the width direction. It is a conceptual diagram of a tenter stretching machine.
  • the stretched film obtained by oblique stretching of the present invention has at least two polymer blocks [A] having repeating units derived from an aromatic vinyl compound as main components and repeating units derived from a chain conjugated diene compound as main components.
  • the stretched film of the present invention may be a strip or a long one, but a long one is preferred from the viewpoint of handleability and productivity.
  • the “long” means one having a length of at least about 5 times or more with respect to the width direction of the film, preferably having a length of 10 times or more, specifically a roll shape. It has a length that is wound around and stored or transported.
  • Block copolymer [1] The block copolymer hydride [2] used in the present invention is obtained by hydrogenating 90% or more of the total unsaturated bonds of the block copolymer [1] as a precursor.
  • the block copolymer [1] is composed of at least two polymer blocks [A] and at least one polymer block [B].
  • the polymer block [A] has a structural unit derived from an aromatic vinyl compound as a main component.
  • the content of the structural unit derived from the aromatic vinyl compound in the polymer block [A] is usually 90% by weight or more, preferably 95% by weight or more, more preferably 99% by weight or more.
  • polymer block [A] may contain components other than the structural unit derived from an aromatic vinyl compound. Examples of such components include structural units derived from chain conjugated dienes and / or structural units derived from other vinyl compounds.
  • the content thereof is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the polymer block [A].
  • the plurality of polymer blocks [A] may be the same as or different from each other as long as the above range is satisfied.
  • the polymer block [B] has a structural unit derived from a chain conjugated diene compound as a main component.
  • the content of the structural unit derived from the chain conjugated diene compound in the polymer block [B] is usually 90% by weight or more, preferably 95% by weight or more, more preferably 99% by weight or more.
  • the structural unit derived from the chain conjugated diene compound is in the above range, the birefringence developability when the optical film of the present invention is stretched is good, and the flexibility of the film is also imparted.
  • polymer block [B] may contain components other than the structural unit derived from a chain conjugated diene compound. Such components include structural units derived from aromatic vinyl compounds and / or structural units derived from other vinyl compounds.
  • the content thereof is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less based on the polymer block [B].
  • the content of the structural unit derived from the aromatic vinyl compound in the polymer block [B] increases, the birefringence developability of the film may decrease.
  • the polymer blocks [B] may be the same as or different from each other as long as the above range is satisfied.
  • aromatic vinyl compound examples include styrene; ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, and 4-t-butylstyrene.
  • Alkyl group-substituted styrene having 1 to 6 carbon atoms such as 5-tert-butyl-2-methylstyrene; halogen-substituted styrene such as 4-chlorostyrene, dichlorostyrene, 4-fluorostyrene; 4-methoxystyrene, 3 1-C6 alkoxy group-substituted styrene such as 1,5-dimethoxystyrene; aryl group-substituted styrene such as 4-phenylstyrene; Among these, in terms of hygroscopicity, styrene and alkyl group-substituted styrene having 1 to 6 carbon atoms that do not contain a polar group are preferable, and styrene is particularly preferable from the viewpoint of industrial availability.
  • chain conjugated diene compound examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like.
  • those containing no polar group are preferable in terms of hygroscopicity, and 1,3-butadiene and isoprene are particularly preferable from the viewpoint of industrial availability.
  • vinyl compounds include chain vinyl compounds, cyclic vinyl compounds, unsaturated cyclic acid anhydrides, unsaturated imide compounds, and the like. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen group.
  • a chain olefin such as pentene and 4,6-dimethyl-1-heptene; a cyclic olefin such as vinylcyclohexane; and the like that does not contain a polar group are preferred in terms of hygroscopicity, a chain olefin is more preferred, ethylene, Propylene is particularly preferred.
  • the number of polymer blocks [A] in the block copolymer [1] is usually 5 or less, preferably 4 or less, more preferably 3 or less.
  • the weight average molecular weight of the polymer block having the maximum and minimum weight average molecular weight in the polymer block [A] is expressed as Mw (A1 ) And Mw (A2), and Mw (A1) when the weight average molecular weight of the polymer block having the largest and smallest weight average molecular weight in the polymer block [B] is Mw (B1) and Mw (B2), respectively.
  • Mw (A2) Mw (A1) / Mw (A2)
  • Mw (B1) and Mw (B2) Mw (B1) / Mw (B2)
  • Mw (B1) / Mw (B2) are 2 respectively. 0.0 or less, preferably 1.5 or less, more preferably 1.2 or less.
  • the form of the block of the block copolymer [1] may be a chain type block or a radial type block, but a chain type block is preferred because of excellent mechanical strength.
  • the most preferred form of the block copolymer [1] is a triblock copolymer ([A]-[B]-[A]) in which the polymer block [A] is bonded to both ends of the polymer block [B].
  • a pentablock copolymer in which the polymer block [B] is bonded to both ends of the polymer block [A], and the polymer block [A] is bonded to the other end of the both polymer blocks [B].
  • the weight fraction of the entire polymer block [A] in the entire block copolymer is wA
  • the weight fraction of the entire polymer block [B] in the entire block copolymer is wA.
  • the ratio of wA to wB is 50:50 to 75:25, preferably 55:45 to 70:30, and more preferably 60:40 to 65:35.
  • wA is too high
  • the heat resistance of the block copolymer hydride [2] used in the present invention is high, but the flexibility is low, the optical film is easily broken on the cutting surface, and wA is too low. Is not preferable because the heat resistance is lowered, and even if the film is stretched, the film shrinks over time and the retardation cannot be maintained.
  • the molecular weight of the block copolymer [1] is a polystyrene-reduced weight average molecular weight (Mw) measured by GPC using tetrahydrofuran (THF) as a solvent, and is usually from 45,000 to 150,000, preferably from 50,000 to 120,000, more preferably 55,000 to 100,000. Further, the molecular weight distribution (Mw / Mn) of the block copolymer [1] is preferably 1.5 or less, more preferably 1.3 or less, and particularly preferably 1.2 or less.
  • 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.
  • Block copolymer hydride [2] The block copolymer hydride [2] according to the present invention is obtained by hydrogenating 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. Is obtained.
  • the hydrogenation rate is usually 90% or more, preferably 97% or more, more preferably 99% or more. The higher the hydrogenation rate, the better the weather resistance and heat resistance of the molded body.
  • the hydrogenation rate of the block copolymer hydride [2] can be determined by measurement by 1 H-NMR.
  • the hydrogenation method and reaction mode of the unsaturated bond are not particularly limited, and may be carried out according to a known method, but a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction is preferable.
  • a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction is preferable. Examples of such a hydrogenation method include the methods described in International Publication WO2011 / 096389, International Publication WO2012 / 043708, and the like.
  • the block copolymer hydride [2] obtained by the above method is recovered from the reaction solution after removing the hydrogenation catalyst and / or the polymerization catalyst from the reaction solution containing the block copolymer hydride [2].
  • the form of the recovered block copolymer hydride [2] is not particularly limited. Usually, it can be made into a pellet shape and can be used for the subsequent molding of the film.
  • the molecular weight of the block copolymer hydride [2] is a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is usually 45,000. To 150,000, preferably 50,000 to 120,000, more preferably 55,000 to 100,000.
  • Mw / Mn The molecular weight distribution (Mw / Mn) of the block copolymer hydride [2] is preferably 1.5 or less, more preferably 1.3 or less, and particularly preferably 1.2 or less. When Mw and Mw / Mn are within the above ranges, the mechanical strength and heat resistance of the formed film are improved.
  • the compounding agent is not particularly limited, but is a layered crystal compound; inorganic fine particles; antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, ultraviolet absorbers, near infrared absorbers and other stabilizers; lubricants, plastics Resin modifiers such as agents; Colorants such as dyes and pigments; Antistatic agents and the like.
  • These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not impairing the object of the present invention.
  • the block copolymer hydride [2] When the block copolymer hydride [2] is melt-extruded to form a film, it is effective to add an antioxidant in order to suppress adhesion of a resin oxidation degradation product to the lip portion of the die.
  • the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Among these, phenolic antioxidants, particularly alkyl-substituted phenolic antioxidants are preferable.
  • Phenol antioxidants include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxy).
  • Phenyl) propionate methane and the like.
  • phosphorus antioxidants include triphenyl phosphite and diphenylisodecyl phosphite.
  • sulfur-based antioxidant include dilauryl thiodipropionate and dimyristyl thiodipropionate.
  • the blending amount of the antioxidant is appropriately selected within the range not impairing the object of the present invention, but is usually 0.005 to 1 part by weight, preferably 100 parts by weight, based on 100 parts by weight of the block copolymer hydride [2]. 0.01 to 0.5 part by weight.
  • the melt-extruded film of the block copolymer hydride [2] is usually prepared by melting the block copolymer hydride [2] with an extruder and from a die attached to the extruder. It is formed by a method of extruding into a sheet shape, forming the extruded sheet in close contact with at least one cooling drum, and taking it out.
  • a method for forming an optical film there are a melt extrusion method and a solution casting method.
  • the molding conditions in the melt extrusion molding are appropriately selected according to the composition, molecular weight, etc. of the block copolymer hydride to be used [2], but the cylinder temperature of the extruder is usually 190 to 280 ° C., more preferably It is set in the range of 200 to 260 ° C.
  • the temperature of the cooling drum of the film take-up machine is usually set in the range of 50 to 200 ° C, preferably 70 to 180 ° C.
  • the thickness of the melt-extruded film can be appropriately determined according to the purpose of use of the obliquely stretched film to be formed thereafter.
  • the thickness of the melt-extruded film is usually 50 to 200 ⁇ m, preferably 80 to 150 ⁇ m, from the viewpoint of obtaining a homogeneous stretched film by a stable stretching process.
  • the melt-extruded film can be rolled and used for the next stretching step, or can be subjected to a stretching step continuous with the melt-extrusion step.
  • the melt-extruded film formed here may be stretched in the extrusion direction.
  • the draw ratio is usually 2 times or less, preferably 1.5 times or less, more preferably 1.2 times or less.
  • a block copolymer hydride [2] pellet which is kept at a predetermined heating temperature for a predetermined time before being melt-extruded by an extruder. Specifically, the one kept at a temperature of usually 50 to 120 ° C., preferably 60 to 115 ° C., more preferably 70 to 110 ° C. for 2 hours or more, preferably 48 hours or less is used.
  • the temperature and time of the heat treatment are below the above range, the amount of dissolved air removed is small, the film thickness unevenness and the generation of die lines cannot be sufficiently suppressed, and if the temperature of the heat treatment exceeds the above range Further, the block copolymer hydride [2] pellets are likely to be blocked, and may not be subjected to extrusion molding. If the heat treatment time exceeds the above range, the color tone may be deteriorated. .
  • the amount of dissolved air removed by the heat treatment is usually 100 ppm or more, preferably 150 ppm or more.
  • the amount of dissolved air released by heating the pellet can be measured from the weight loss of the pellet before and after the heat treatment.
  • the amount of dissolved air released from the pellet can also be measured using a tepler pump.
  • Stretched film The melt-extruded film obtained as described above is continuously stretched obliquely in the direction of an arbitrary angle ⁇ 1 (5 ° ⁇ ⁇ ⁇ 80 °) with respect to the width direction thereof, whereby the width of the film A stretched film having an orientation axis at an angle ⁇ S (where ⁇ S ⁇ ⁇ 1 ) with respect to the direction can be obtained.
  • the refractive index nx in the in-plane slow axis direction, the refractive index ny in the direction perpendicular to the in-plane slow axis, and the thickness direction can be set to a desired value.
  • the oblique stretching method is not particularly limited as long as it is continuously stretched in a direction of 5 to 80 ° with respect to the width direction, and the orientation axis of the polymer is inclined to a desired angle. Can be adopted.
  • the stretching machine used for the oblique stretching is not particularly limited, and a conventionally known tenter type stretching machine that can add a feed force, a pulling force, or a pulling force at independent speeds in the horizontal or vertical direction is used. Can do.
  • the tenter type stretching machine includes a horizontal uniaxial stretching machine, a simultaneous biaxial stretching machine, and the like, but is not particularly limited as long as a long film can be continuously obliquely stretched. These types of stretching machines can be used.
  • FIG. 1 An example of oblique tenter stretching that can be used in the present invention is shown in FIG.
  • the tenter stretching machine shown in FIG. 1 moves the left and right tenter clips at a predetermined speed (5L, 5R) along a rail (3) along which a tenter grip clip (not shown) travels, and melt-extruded film (1 ) Is stretched in the width direction through the preheating zone (6), the stretching zone (7), and the fixing zone (8), and the feeding path (4) of the stretched film (2) is fed in the feeding direction of the melt extruded film (1).
  • a tenter stretching machine was so performed to oblique stretching by the bend in the angle theta 1 direction relative.
  • This tenter stretching machine can obtain an obliquely stretched film having an orientation axis (B) at an angle ⁇ S (5 ° ⁇ ⁇ S ⁇ 80 °) with respect to the width direction (A) of the film.
  • the oblique stretching method that can be used in the present invention is not limited to that shown in FIG.
  • JP-A-50-83482, JP-A-2-113920, JP-A-3-182701, JP-A-2000-9912, JP-A-2002-86554, JP-A-2002-22944 Etc. can be used.
  • the temperature at which the melt-extruded film is obliquely stretched is preferably between (Tg ⁇ 40 ° C.) and (Tg + 20 ° C.), more preferably (Tg + 20 ° C.), where Tg is the glass transition temperature of the block copolymer hydride [2]. Tg-30 ° C) to (Tg + 10 ° C).
  • the draw ratio is usually 1.2 to 10 times, preferably 1.3 to 5 times, more preferably 1.5 to 3 times.
  • the obliquely stretched film of the present invention obtained as described above has an orientation axis of 5 ° to 80 ° with respect to the width direction. Further, it has no wrinkles or thickness unevenness, has a uniform retardation with little unevenness due to the part, and is excellent in stability of optical characteristics, and thus is useful as a polarizing film or a retardation film.
  • the obliquely stretched film of the present invention obtained as described above has an orientation axis of 5 ° to 80 ° with respect to the width direction. In addition, there is no wrinkle or thickness unevenness, and there is a uniform retardation with small unevenness depending on the part, and the stability of optical characteristics is excellent. It is useful as a phase difference plate, a ⁇ / 4 phase difference plate with an orientation axis angle of 75 °, and the like.
  • a block copolymer hydride is press-molded to prepare a test piece having a length of 20 mm, a width of 4 mm, and a thickness of 1 mm, and a loss elastic modulus measuring device based on the JIS K 7244-4 method ( Using a product name “DMS6100” (manufactured by Seiko Instruments Inc.), measure the viscoelasticity spectrum in the range of ⁇ 100 ° C. to + 150 ° C. with a vibration frequency of 10 Hz and a heating rate of 5 ° C./min. The glass transition temperature was determined from the peak top temperature.
  • the accuracy (%) was defined as the larger difference between the maximum value and the minimum value of the phase difference and the average value. It can be determined that the phase difference accuracy is 2% or less.
  • (6) Angle and accuracy of orientation axis In-plane with a polarizing microscope (product name “ECLIPSE (registered trademark) E600 POL”, manufactured by Nikon Corporation) in the width direction of the stretched film at an interval of 5 cm over the center part of 1340 mm. The angle of the slow axis of the direction with respect to the width direction of the stretched film was measured. The average value ⁇ S of the angles was obtained, and the accuracy of the orientation axis angle was defined as the difference between the maximum value and the minimum value of the orientation axis angle. It can be judged that the accuracy of the angle of the orientation axis is good if it is 1 ° or less.
  • Block copolymer hydride [2] -1 (Synthesis of block copolymer [1] -1)
  • a reactor equipped with a stirrer in which the inside was sufficiently purged with nitrogen 550 parts of dehydrated cyclohexane, 30.0 parts of dehydrated styrene and 0.475 part of n-dibutyl ether were placed, and while stirring at 60 ° C.
  • Polymerization was initiated by adding 0.61 part of lithium (15% cyclohexane solution). The mixture was reacted at 60 ° C. for 60 minutes with stirring. At this point in time as measured by gas chromatography, the polymerization conversion was 99.5%.
  • the reaction solution was filtered to remove the hydrogenation catalyst, and then the phenolic antioxidant pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate] (product name “Songnox 1010”, manufactured by Koyo Chemical Research Co., Ltd.) 1.0 part of xylene solution in which 0.1 part was dissolved was added and dissolved.
  • the above solution was filtered with a metal fiber filter (pore size 0.4 ⁇ m, manufactured by Nichidai) to remove minute solids, and then a cylindrical concentration dryer (product name “Contro”, manufactured by Hitachi, Ltd.) ), The solvent cyclohexane, xylene and other volatile components were removed from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less.
  • the molten polymer is continuously filtered at a temperature of 260 ° C.
  • pellets of block copolymer hydride [2] -1 were prepared by a pelletizer.
  • the pelletized block copolymer hydride [2] -1 had a weight average molecular weight (Mw) of 80,200 and a molecular weight distribution (Mw / Mn) of 1.04.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Block copolymer hydride [2] -2 (Synthesis of block copolymer [1] -2) Styrene and isoprene were divided into 5 portions, and 20.0 parts of styrene, 20.0 parts of isoprene, 20.0 parts of styrene, 20.0 parts of isoprene, and 20.0 parts of styrene were added in this order, as in Production Example 1. Polymerization and reaction termination were performed.
  • the pelletized block copolymer hydride [2] -2 had a weight average molecular weight (Mw) of 78,900 and a molecular weight distribution (Mw / Mn) of 1.06.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Example 1 The block copolymer hydride [2] -1 pellets obtained in Production Example 1 were heat-treated at 85 ° C. for 4 hours using a hot air dryer in which air was circulated. The pellets after the heat treatment are supplied to an extruder equipped with a T-type die having a die slip with an average value of the surface roughness Ra of 0.03 ⁇ m in the entire surface width of the die slip made of a polymer filter and tungsten carbide within one hour. Then, it was extruded into a sheet shape on a casting drum maintained at 80 ° C. at a cylinder temperature of 230 ° C., and cooled without being stretched to obtain a long melt extruded film [2] -1A1 having a thickness of 150 ⁇ m. The melt-extruded film [2] -1A1 was wound up on a roll.
  • the amount of air released into the test tube was measured with a Tepler pump at 25 ° C. and normal pressure.
  • the measured air volume was 0.787 ml.
  • the amount of remaining air in the test tube was 0.01 ml or less, which was negligible.
  • the amount of released air was 10.12 ⁇ 10 ⁇ 4 g, which was 202 ppm with respect to the weight of the block copolymer hydride [2] -1 pellet. It was.
  • the melt-extruded film [2] -1A1 is pulled out from the roll and continuously supplied to a tenter stretching machine as shown in FIG. 1, and the traveling speed of the gripping means of the tenter stretching machine is almost equal at both ends of the film.
  • both ends of the stretched film obtained were left trimmed in the width direction at 1340 mm, wound on a roll, and an obliquely stretched film [F1] having a width of 1340 mm was obtained.
  • the thickness, the in-plane retardation (Re), and the orientation axis angle ( ⁇ S ) were measured. The results are shown in Table 1.
  • Example 2 The length of 150 ⁇ m in thickness was the same as in Example 1 except that the block copolymer hydride [2] -2 pellets obtained in Production Example 2 were used and the pellet heat treatment temperature was 80 ° C. A long melt extruded film [2] -2A2 was formed and wound on a roll.
  • melt-extruded film [2] -2A2 was used, and the stretching was performed in the same manner as in Example 1 except that the stretching zone temperature was 110 ° C.
  • the both ends were trimmed and the diagonally stretched film [F2] having a width of 1340 mm Got.
  • the thickness, the in-plane retardation (Re), and the orientation axis angle ( ⁇ S ) were measured. The results are shown in Table 1.
  • Example 3 The same procedure as in Example 1 was performed except that pellets of the block copolymer hydride [2] -2 obtained in Production Example 2 were used, the pellet heat treatment temperature was 60 ° C., and the heat treatment time was 5 hours. A long melt-extruded film [2] -2A3 having a thickness of 150 ⁇ m was formed and wound on a roll.
  • Block copolymer hydride [2] -3 (Synthesis of block copolymer [1] -3) Polymerization and reaction termination were carried out in the same manner as in Production Example 1 except that the amount of n-butyllithium (15% cyclohexane solution) as a polymerization initiator was changed to 1.10 parts.
  • the pelletized block copolymer hydride [2] -3 had a weight average molecular weight (Mw) of 43,900 and a molecular weight distribution (Mw / Mn) of 1.03.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Block copolymer hydride [2] -4 (Synthesis of block copolymer [1] -4) Polymerization and reaction termination were carried out in the same manner as in Production Example 1 except that the amount of n-butyllithium (15% cyclohexane solution) as a polymerization initiator was 0.40 part.
  • a block copolymer hydride [2] -4 pellet was produced in the same manner as in Production Example 1 except that an antioxidant was added in the same manner as in Production Example 1, followed by concentration and drying at 280 ° C. 87 parts were produced.
  • the pelletized block copolymer hydride [2] -4 had a weight average molecular weight (Mw) of 98,000 and a molecular weight distribution (Mw / Mn) of 1.53.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Block copolymer hydride [2] -5 (Synthesis of block copolymer [1] -5) After introducing 600 parts of dehydrated cyclohexane into the reactor, 0.12 part of n-butyllithium (15% cyclohexane solution) was added and stirred for 30 minutes to carry out pretreatment to sufficiently remove moisture. Thereafter, polymerization and reaction termination were carried out in the same manner as in Production Example 1 except that n-butyllithium (15% cyclohexane solution) as a polymerization initiator was changed to 0.28 part.
  • the block copolymer hydride [2] -5 was prepared in the same manner as in Production Example 1 except that an antioxidant was added in the same manner as in Production Example 1 and then concentrated and dried at a temperature of 280 ° C. 91 parts of pellets were made.
  • the obtained block-like block copolymer hydride [2] -5 had a weight average molecular weight (Mw) of 166,000 and a molecular weight distribution (Mw / Mn) of 1.10.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • Example 2 Stretched was performed in the same manner as in Example 1 except that the melt-extruded film [2] -3A4 was used and the stretching zone temperature was set to 131 ° C., but the film was easily broken when stretched 3 times or more. The developability of retardation due to stretching was low, and a good film having a retardation of 150 nm as an obliquely stretched film was not obtained.
  • melt-extruded film [2] -4A5 was used and stretched in the same manner as in Example 1 except that the stretching zone temperature was set to 119 ° C., and both ends were trimmed and the diagonally stretched film [F5] having a width of 1340 mm Got.
  • the thickness, the in-plane retardation (Re), and the orientation axis angle ( ⁇ S ) were measured. The results are shown in Table 1.
  • an obliquely stretched film [F6] having a width of 1340 mm was obtained in the same manner as in Example 1 except that the melt-extruded film [2] -5A6 was used and the stretching zone temperature was 153 ° C.
  • the thickness, the in-plane retardation (Re), and the orientation axis angle ( ⁇ S ) were measured. The results are shown in Table 1.
  • the resulting block-like block copolymer hydride [2] -6 had a weight average molecular weight (Mw) of 48,200, a molecular weight distribution (Mw / Mn) of 1.06, a hydrogenation rate of almost 100%, and glass.
  • the transition temperature was 129 ° C.
  • the polymer solution was hydrogenated in the same manner as in Production Example 1.
  • the weight average molecular weight (Mw) of the block copolymer hydride [2] -7 after the hydrogenation reaction was 70,700, and the molecular weight distribution (Mw / Mn) was 1.05.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • the polymer solution was hydrogenated in the same manner as in Production Example 1.
  • the weight average molecular weight (Mw) of the block copolymer hydride [2] -8 after the hydrogenation reaction was 143,000, and the molecular weight distribution (Mw / Mn) was 1.06.
  • Block copolymer hydride [2] -9 (Synthesis of block copolymer [1] -9) Styrene and isoprene were divided into 3 portions, 40.0 parts of styrene, 20.0 parts of isoprene and 40.0 parts of styrene were added in this order, and n-butyllithium (15% cyclohexane solution) was changed to 0.64 parts. Polymerization and reaction termination were carried out in the same manner as in Production Example 1.
  • the polymer solution was hydrogenated in the same manner as in Production Example 1.
  • the weight average molecular weight (Mw) of the block copolymer hydride [2] -9 after the hydrogenation reaction was 72,300, and the molecular weight distribution (Mw / Mn) was 1.06.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • the polymer solution was hydrogenated in the same manner as in Production Example 1.
  • the weight average molecular weight (Mw) of the block copolymer hydride [2] -10 after the hydrogenation reaction was 55,700, and the molecular weight distribution (Mw / Mn) was 1.04.
  • the resulting block-like block copolymer hydride [2] -10 has a weight average molecular weight (Mw) of 55,200, a molecular weight distribution (Mw / Mn) of 1.05, a hydrogenation rate of almost 100%, glass
  • the transition temperature was 120 ° C.
  • Example 4 Except that the block copolymer hydride [2] -1 pellet obtained in Production Example 1 was used, the pellet heat treatment temperature was 45 ° C., and the heat treatment time was 5 hours. A long melt extruded film [2] -1A7 having a thickness of 150 ⁇ m was formed and wound on a roll.
  • Example 5 Except that the block copolymer hydride [2] -1 pellets obtained in Production Example 1 were used, the pellet heat treatment temperature was 85 ° C., and the heat treatment time was 1 hour, the same as in Example 1. A long melt extruded film [2] -1A8 having a thickness of 150 ⁇ m was formed and wound on a roll.
  • Example 6 Except that the block copolymer hydride [2] -6 pellet obtained in Production Example 6 was used, the pellet heat treatment temperature was 60 ° C., and the heat treatment time was 5 hours, the same as in Example 1. A long melt extruded film [2] -6A9 having a thickness of 150 ⁇ m was formed and wound on a roll.
  • Example 7 A long melt extruded film [2] -7A10 having a thickness of 150 ⁇ m was formed in the same manner as in Example 1, except that the block copolymer hydride [2] -7 obtained in Production Example 7 was used. And wound up on a roll.
  • an obliquely stretched film [F10] having a width of 1340 mm was obtained in the same manner as in Example 1 using the melt-extruded film [2] -7A10.
  • the thickness, the in-plane retardation (Re), and the orientation axis angle ( ⁇ S ) were measured. The results are shown in Table 1.
  • Example 8 A long length of 150 ⁇ m in the same manner as in Example 1 except that the block copolymer hydride [2] -8 pellets obtained in Production Example 8 were used and the extrusion conditions were set at a cylinder temperature of 250 ° C. A melt-extruded film [2] -8A11 was formed and wound on a roll.
  • Example 4 A long length of 150 ⁇ m in the same manner as in Example 1 except that the pellet of the block copolymer hydride [2] -9 obtained in Production Example 9 was used and the extrusion conditions were set to a cylinder temperature of 260 ° C. A melt-extruded film [2] -9A12 was formed and wound on a roll.
  • melt-extruded film [2] -9A12 was used and stretched in the same manner as in Example 1. However, when stretched, the film was easily broken, and a good film having a retardation of 150 nm as an obliquely stretched film was obtained. There wasn't. The results are shown in Table 1.
  • the weight fraction wA of the block copolymer hydride [2] in the whole polymer block [A] in the whole block copolymer and the weight fraction wB in the whole polymer block [B] in the whole block copolymer When the ratio (wA: wB) is outside the range of the present invention and wA is large (Comparative Example 4), the mechanical strength is weak, the film is easily broken during oblique stretching, and a film having a desired retardation is obtained. In addition, when wA is small (Comparative Example 5), the heat resistance is not sufficient, and the retardation of the obliquely stretched film tends to decrease with time, and the desired retardation cannot be stably maintained.
  • the obliquely stretched film made of the block copolymer hydride of the present invention has a small thickness unevenness and is excellent in retardation accuracy and orientation axis angle accuracy, such as polarizing plate protective film and retardation film. It is useful as an industrial film. Moreover, when the stretched film of this invention is a long thing, it can wind up and preserve

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Abstract

　Selon l'invention, un copolymère bloc (1) est constitué: d'au moins deux blocs polymères (A) ayant pour constituant principal une unité répétitive dérivée d'un composé vinyle aromatique; et d'au moins un bloc polymère (B) ayant pour constituant principal une unité répétitive dérivée d'un composé diène à chaîne ramifiée. Lorsque la fraction en poids pour tous les copolymères blocs des blocs polymères (A) est wA et la fraction en poids pour tous les copolymères blocs du bloc copolymère (B) est wB, alors le rapport wA:wB est compris entre 50:50 et 75:25. Au moins 90% de toutes les liaisons non saturées du bloc copolymère (1) sont hydrogénées. Ensuite, un film constitué d'un produit hydrogéné (2) de copolymères blocs dont la masse moléculaire moyenne en poids (Mw) est comprise entre 45000 et 150000, et la distribution de masse moléculaire (Mw/Mn) égale ou inférieure à 1,5 est obtenu par extrusion de matière fondue. Puis ce film est étiré en continu dans une direction de 5 à 80 ° par rapport à la direction de sa largeur, et un film étiré selon l'invention est obtenu.
PCT/JP2014/068088 2013-07-08 2014-07-07 Film étiré et son procédé de fabrication WO2015005292A1 (fr)

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WO2016158353A1 (fr) * 2015-03-31 2016-10-06 日本ゼオン株式会社 Procédé de fabrication de film étiré et film étiré
JP2019164222A (ja) * 2018-03-19 2019-09-26 日本ゼオン株式会社 位相差フィルムの製造方法、偏光板、有機エレクトロルミネッセンス表示装置、及び、液晶表示装置
WO2019181892A1 (fr) * 2018-03-19 2019-09-26 日本ゼオン株式会社 Film de retard et procédé de production de film de retard
WO2020080202A1 (fr) 2018-10-17 2020-04-23 日本ゼオン株式会社 Hydrure de copolymère, procédé de production d'hydrure de copolymère, composition contenant un hydrure de copolymère, film intermédiaire pour verre feuilleté, stratifié de film intermédiaire pour verre feuilleté, matériau d'encapsulation, film optique, corps moulé médical, procédé de fabrication d'un corps moulé médical, adhésif, ensemble et procédé de fabrication de l'ensemble
JP2020086402A (ja) * 2018-11-30 2020-06-04 日本ゼオン株式会社 位相差フィルム
CN111239862A (zh) * 2020-02-17 2020-06-05 中国科学技术大学 一种兼具1/4波片功能的保护膜、其制备方法及其应用
KR20200131833A (ko) 2018-03-19 2020-11-24 니폰 제온 가부시키가이샤 위상차 필름 및 위상차 필름의 제조 방법

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WO2016158353A1 (fr) * 2015-03-31 2016-10-06 日本ゼオン株式会社 Procédé de fabrication de film étiré et film étiré
CN107405822A (zh) * 2015-03-31 2017-11-28 日本瑞翁株式会社 拉伸膜的制造方法及拉伸膜
JPWO2016158353A1 (ja) * 2015-03-31 2018-01-25 日本ゼオン株式会社 延伸フィルムの製造方法、及び、延伸フィルム
KR20200131822A (ko) 2018-03-19 2020-11-24 니폰 제온 가부시키가이샤 위상차 필름 및 위상차 필름의 제조 방법
WO2019181892A1 (fr) * 2018-03-19 2019-09-26 日本ゼオン株式会社 Film de retard et procédé de production de film de retard
KR20200131833A (ko) 2018-03-19 2020-11-24 니폰 제온 가부시키가이샤 위상차 필름 및 위상차 필름의 제조 방법
JP2019164222A (ja) * 2018-03-19 2019-09-26 日本ゼオン株式会社 位相差フィルムの製造方法、偏光板、有機エレクトロルミネッセンス表示装置、及び、液晶表示装置
JP7059722B2 (ja) 2018-03-19 2022-04-26 日本ゼオン株式会社 位相差フィルムの製造方法、並びに、偏光板、有機エレクトロルミネッセンス表示装置、及び、液晶表示装置の、製造方法
US11970562B2 (en) 2018-03-19 2024-04-30 Zeon Corporation Retardation film and production method for retardation film
WO2020080202A1 (fr) 2018-10-17 2020-04-23 日本ゼオン株式会社 Hydrure de copolymère, procédé de production d'hydrure de copolymère, composition contenant un hydrure de copolymère, film intermédiaire pour verre feuilleté, stratifié de film intermédiaire pour verre feuilleté, matériau d'encapsulation, film optique, corps moulé médical, procédé de fabrication d'un corps moulé médical, adhésif, ensemble et procédé de fabrication de l'ensemble
US11773193B2 (en) 2018-10-17 2023-10-03 Zeon Corporation Hydrogenated copolymer and method of producing the same, hydrogenated copolymer-containing composition, interlayer film for laminated glass, interlayer film laminate for laminated glass, sealing material, optical film, medical shaped article and method of producing the same, adhesive, and assembly and method of producing the same
JP2020086402A (ja) * 2018-11-30 2020-06-04 日本ゼオン株式会社 位相差フィルム
JP7305949B2 (ja) 2018-11-30 2023-07-11 日本ゼオン株式会社 位相差フィルム
CN111239862A (zh) * 2020-02-17 2020-06-05 中国科学技术大学 一种兼具1/4波片功能的保护膜、其制备方法及其应用

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