WO2015178370A1 - 光学用フィルムの製造方法 - Google Patents
光学用フィルムの製造方法 Download PDFInfo
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- WO2015178370A1 WO2015178370A1 PCT/JP2015/064310 JP2015064310W WO2015178370A1 WO 2015178370 A1 WO2015178370 A1 WO 2015178370A1 JP 2015064310 W JP2015064310 W JP 2015064310W WO 2015178370 A1 WO2015178370 A1 WO 2015178370A1
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- film
- block copolymer
- optical film
- resin
- copolymer hydride
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/04—Prisms
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to a method for producing an optical film comprising a hydride of a block copolymer, and more specifically, a polarizing plate protective film, a retardation film, and a transparent adhesive film having excellent surface properties with few defects such as scratches on the surface.
- the present invention relates to a method for producing an optical film suitable for a base material film for use.
- an aromatic vinyl compound polymer hydride obtained by hydrogenating an aromatic ring of an aromatic vinyl compound polymer, a polymer block mainly composed of a repeating unit derived from an aromatic vinyl compound, and a chain conjugated diene compound A film obtained by extruding a block copolymer hydride obtained by hydrogenating an aromatic ring and a diene-derived double bond of a block copolymer comprising a polymer block containing a repeating unit of: a polarizing film or a retardation film It is known to be useful as an optical film such as (Patent Documents 1 to 4).
- Patent Document 2 when a block copolymer hydride is formed to produce a film, a masking film may be overlapped and wound for the purpose of preventing blocking between the films. It is described. However, there is no description regarding the physical properties and characteristics of the masking film for expressing the function of preventing the film surface from being scratched differently from blocking.
- JP 2002-105151 A (US2003 / 0207983 A1) JP 2003-114329 A WO2009 / 067290 pamphlet WO2009 / 137278 pamphlet
- the elastic modulus is higher when the content of the repeating unit derived from the aromatic vinyl compound is increased, and the birefringence is less likely to occur in the film formed from the same. Therefore, it is considered preferable.
- a block copolymer hydride having a high content of repeating units derived from an aromatic vinyl compound is molded in comparison with a block copolymer hydride having a low content of repeating units derived from an aromatic vinyl compound. There was a problem that the film surface was easily damaged by rubbing the film itself.
- the present invention has been made in view of such circumstances, and is applicable to a polarizing plate protective film, a retardation film, a base film for a transparent adhesive film, and the like having excellent surface properties with few defects such as scratches on the surface.
- An object of the present invention is to provide a method for producing an optical film comprising a specific hydride of a block copolymer.
- the present inventors have found that the surface is made of an optical film made of a specific block copolymer hydride and a resin having a bending elastic modulus and adhesiveness of a specific value or less.
- the present invention is completed by discovering that the surface of the optical film made of a specific block copolymer hydride can be effectively suppressed when the formed protective film is stacked and stored in a roll shape. It came to.
- block copolymer hydrogen obtained by hydrogenating 90% or more of all unsaturated bonds of block copolymer [C] having a ratio of wA to wB (wA: wB) of 60:40 to 90:10
- a method for producing an optical film comprising a compound [D]
- the optical film obtained by extruding the block copolymer hydride [D] and at least one surface portion have a flexural modulus at 23 ° C. of 1500 MPa or less, and the block copolymer hydride [D].
- the protective film is a single layer film made of the resin [E], a multilayer film having a layer made of the resin [E] on the outermost surface, or a resin [E] having a flexural modulus exceeding 1500 MPa.
- the method for producing an optical film according to (1) which is a multilayer film in which layers made of a resin [E] are formed on both surfaces of a resin film.
- the resin [E] is at least one selected from the group consisting of polyethylene, polypropylene, ethylene / ⁇ -olefin copolymer, ethylene / vinyl acetate copolymer, polyurethane, and polyester elastomer. (1) Or the manufacturing method of the optical film as described in (2).
- a method for producing an optical film comprising a hydride of a block copolymer, which has excellent surface properties with few defects such as scratches on the surface, a polarizing plate protective film, a retardation film, and a transparent adhesive film
- a method for producing an optical film suitable for a base material film or the like is provided.
- the method for producing an optical film of the present invention comprises at least two polymer blocks [A] having a repeating unit derived from an aromatic vinyl compound as a main component and a repeating unit derived from a chain conjugated diene compound as a main component.
- At least one polymer block [B] the weight fraction of the entire polymer block [A] in the entire block copolymer is wA, and the entire block copolymer of the entire polymer block [B] When the weight fraction occupied is wB, 90% or more of the total unsaturated bonds of the block copolymer [C] in which the ratio of wA to wB (wA: wB) is 60:40 to 90:10
- a method for producing an optical film comprising a hydrogenated block copolymer hydride [D], The optical film obtained by extruding the block copolymer hydride [D] and at least one surface portion have a flexural modulus at 23 ° C.
- Block copolymer hydride [D] used in the present invention is a polymer obtained by hydrogenating 90% or more of the total unsaturated bonds of the block copolymer [C] as a precursor.
- the block copolymer [C] is a polymer containing 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.
- the heat resistance of the optical film according to the present invention may be lowered.
- the polymer block [A] may contain components other than the structural unit derived from the aromatic vinyl compound.
- the component other than the structural unit derived from the aromatic vinyl compound include a structural unit derived from a chain conjugated diene and / or a structural unit derived from another vinyl compound.
- 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] contained in the block copolymer hydride [D] 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 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more.
- flexibility is imparted to the optical film according to the present invention.
- polymer block [B] may contain components other than the structural unit derived from a chain conjugated diene compound.
- the component other than the structural unit derived from the chain conjugated diene compound include a structural unit derived from an aromatic vinyl compound and / or a structural unit derived from another vinyl compound.
- the content thereof is usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less based on the polymer block [B]. If the content of the structural unit derived from the aromatic vinyl compound in the polymer block [B] is excessively large, the birefringence developability of the optical film according to the present invention is lowered, but the flexibility may be lowered.
- the block copolymer hydride [D] has a plurality of polymer blocks [B]
- the polymer blocks [B] may be the same as or different from each other.
- aromatic vinyl compound examples include styrene; ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-t-butylstyrene, Styrenes having a C 1-6 alkyl group as a substituent, such as 5-t-butyl-2-methylstyrene; halogen atoms as a substituent, such as 4-chlorostyrene, dichlorostyrene, 4-monofluorostyrene Styrenes having 1 to 6 carbon atoms as substituents such as 4-methoxystyrene; styrenes having aryl groups as substituents such as 4-phenylstyrene; 1-vinylnaphthalene, And vinyl naphthalenes such as 2-vinyl naphthalene; Among these, from
- chain-chain conjugated diene compounds examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like. Of these, a chain conjugated diene compound containing no polar group is preferred from the viewpoint of hygroscopicity, and 1,3-butadiene and isoprene are particularly preferred from the viewpoint of industrial availability.
- vinyl compounds examples 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.
- ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene Does not have a polar group such as a chain olefin having 2 to 20 carbon atoms such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene; a cyclic olefin having 5 to 20 carbon atoms such as vinylcyclohexane; Vinyl compounds are preferred, chain olefins having 2 to 20 carbon atoms are more preferred, and ethylene and propylene are particularly preferred.
- the block copolymer [C] is a precursor of the block copolymer hydride [D], and contains at least two polymer blocks [A] and at least one polymer block [B] in the molecule. It is a polymer.
- the number of the polymer blocks [A] in the cocoon block copolymer [C] 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 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, the Mw ( The ratio between A1) and Mw (A2) (Mw (A1) / Mw (A2)) and the ratio between Mw (B1) and Mw (B2) (Mw (B1) / Mw (B2)) are 4. It is 0 or less, preferably 3.0 or less, more preferably 2.0 or less.
- the block form of the eaves block copolymer [C] may be a chain block or a radial block, but a chain block is preferred because of its excellent mechanical strength.
- the most preferred form of the block copolymer [C] is a triblock copolymer ([A]-[B]-[A]) in which the polymer block [A] is bonded to both ends of the polymer block [B].
- 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]. [A]-[B]-[A]-[B]).
- the weight fraction of the whole polymer block [A] in the entire block copolymer is wA
- the weight fraction in which the whole polymer block [B] is in the whole block copolymer is wB
- the ratio of wA to wB is 60:40 to 90:10, preferably 65:35 to 85:15, more preferably 70:30 to 80:20 .
- the molecular weight of the block copolymer [C] is a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is usually 40,000 to 200. , Preferably 50,000 to 150,000, more preferably 60,000 to 100,000. Further, the molecular weight distribution (Mw / Mn) of the block copolymer [C] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less.
- the block copolymer [C] is prepared by, for example, a monomer mixture (a) containing an aromatic vinyl compound as a main component and a monomer mixture containing a chain conjugated diene compound (as a main component) by a method such as living anion polymerization. a method of alternately polymerizing b): a monomer mixture (a) containing an aromatic vinyl compound as a main component and a monomer mixture (b) containing a chain conjugated diene compound as a main component in order, It can be produced by a method of coupling the ends of the combined block [B] with a coupling agent;
- 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 components other than the aromatic vinyl compound. Examples of other components include chain conjugated diene compounds and 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 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 components other than the chain conjugated diene compound. Examples of other components include aromatic vinyl compounds and other vinyl compounds. The content thereof 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).
- the block copolymer hydride [D] is obtained by hydrogenating the carbon-carbon unsaturated bond of the main chain and the side chain of the block copolymer [C] and the carbon-carbon unsaturated bond of the aromatic ring. is there.
- 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, heat resistance and low birefringence of the molded body.
- the hydrogenation rate of the block copolymer hydride [D] 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.
- Examples of such hydrogenation methods include the methods described in WO2011 / 096389 pamphlet, WO2012 / 043708 pamphlet and the like.
- the block copolymer hydride [D] can be recovered from the resulting solution.
- the form of the recovered block copolymer hydride [D] is not limited, it can usually be formed into a pellet shape and subjected to subsequent film forming.
- the molecular weight of the block copolymer hydride [D] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 40,000 to 200,000, preferably 50,000 to 150. , 000, more preferably 60,000 to 100,000.
- the molecular weight distribution (Mw / Mn) of the block copolymer hydride [D] is preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. When Mw and Mw / Mn are within the above ranges, the molded optical film has good heat resistance and low birefringence.
- the block copolymer hydride [D] used in the present invention may contain other compounding agents.
- the compounding agent is not particularly limited, but is a stabilizer such as an antioxidant, a heat stabilizer, a light stabilizer, a weathering stabilizer, an ultraviolet absorber, a near infrared absorber, and the like; a resin modifier such as a lubricant and a plasticizer. 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.
- the compounding quantity of a compounding agent is suitably selected in the range which does not impair the objective of this invention.
- melt-extrusion of the block copolymer hydride [D] is formed 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.
- an antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
- Antioxidants can be used alone or in combination of two or more.
- phenolic antioxidants particularly alkyl-substituted phenolic antioxidants are preferred.
- 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-butyl
- tricyclic phenolic antioxidants tetracyclic [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] tetracyclic phenolic antioxidants such as methane; and the like.
- the blending amount of the antioxidant is appropriately selected within a range not impairing the object of the present invention.
- the amount is preferably 0.02 to 0.5 parts by weight, more preferably 0.05 to 0.3 parts by weight.
- the method for producing an optical film of the present invention comprises an optical film obtained by extruding the block copolymer hydride [D] and at least one surface portion bent at 23 ° C.
- the surface of the protective film made of resin [E] and the optical film are overlapped and wound so as to face each other.
- optical film of the present invention The optical film produced by the production method of the present invention (hereinafter sometimes referred to as “optical film of the present invention”) is composed of a block copolymer hydride [D].
- “consisting of block copolymer hydride [D]” means that “the optical film to be obtained consists essentially of block copolymer hydride [D]. As long as it is not impaired, it may contain other compounding agents.
- the content of the block copolymer hydride [D] in the optical film of the present invention is usually 95% by weight or more, preferably 97% by weight or more, more preferably 98% by weight or more, and further preferably 99% by weight or more. It is.
- the optical film of the present invention comprises a block copolymer hydride [D] pellet melted by an extruder and extruded from a die attached to the extruder into a sheet, and the extruded block copolymer block weight
- the combined hydride [D] can be produced by bringing it into close contact with at least one cooling drum and molding it.
- the surface roughness Ra has an average value of the surface roughness Ra of the die slip of 0.05 ⁇ m or less, and the distribution range of the surface roughness Ra over the entire width of the die slip is ⁇ 0.025 ⁇ m or less of the average value.
- the block copolymer hydride [D] pellet before the block copolymer hydride [D] pellet is melt-extruded by an extruder, it is usually at a temperature of 50 to 120 ° C. for 2 hours or more, preferably at a temperature of 60 to 115 ° C. for 3 hours or more. Preferably, those kept at a temperature of 70 to 110 ° C. for 4 hours or more are used.
- the amount of dissolved air in the pellets is reduced, thereby suppressing the generation of die lines, and the above-mentioned die having a small surface roughness Ra.
- an optical film having a small surface roughness Ra can be formed.
- the temperature and time of the heat treatment are below the above range, the amount of dissolved air removed is small, and the generation of die lines cannot be sufficiently suppressed, and it may be difficult to obtain an optical film having a small surface roughness Ra. .
- the melting temperature of the block copolymer hydride [D] in the extruder is usually 70 to 160 ° C. higher than the glass transition temperature of the block copolymer hydride [D], and 90 to 90 ° C. higher than the glass transition temperature. More preferably, the temperature is 140 ° C. higher.
- the glass transition temperature of the block copolymer hydride [D] can be determined as the peak top value of tan ⁇ in the viscoelastic spectrum. If the melting temperature in the extruder is excessively low, the fluidity of the resin may be insufficient. Conversely, if the melting temperature is excessively high, the resin may be decomposed and the molecular weight may be decreased.
- the block copolymer hydride [D] extruded from the opening of the dies is brought into close contact with the cast roll and cooled to form a film.
- the degree of adhesion of the extruded film-like block copolymer hydride [D] to the cast roll varies depending on the temperature of the cast roll. When the temperature of the cast roll is raised, the adhesion is improved. However, when the temperature is raised too much, the film-like block copolymer hydride [D] is not peeled off from the cast roll, and there is a possibility that a problem of winding around the roll may occur. Therefore, the temperature of the cast roll is usually (Tg + 10) ° C. or less, preferably (Tg-80) ° C.
- Tg-5 glass transition temperature of the block copolymer hydride [D] is Tg (° C.). ° C, more preferably (Tg-60) ° C to (Tg-10) ° C.
- an optical film obtained by extruding the block copolymer hydride [D] and at least one surface portion has a flexural modulus at 23 ° C. of 1500 MPa or less.
- the surface portion made of the resin [E] and the optical film are overlapped and wound so as to face each other.
- At least one surface portion has a flexural modulus at 23 ° C. of 1500 MPa or less, and the adhesiveness to the optical film made of the block copolymer hydride [D] is peeled off at 23 ° C. It is a film made of resin [E] having a strength of 0.1 N / cm or less.
- Resin [E] has a flexural modulus at 23 ° C. of 1500 MPa or less, and has an adhesive strength to an optical film composed of a block copolymer hydride [D] of 0.1 N / cm or less as a peel strength at 23 ° C. It is a certain polymer.
- the protective film [E] having the above specific physical properties is opposed to the optical film made of the block copolymer hydride [D], and the surface portion made of the resin [E] of the protective film and the optical film are opposed to each other.
- the optical film made of the block copolymer hydride [D] can be effectively reduced in the occurrence of scratches on the film surface and the protective film is peeled off.
- the resin [E] include at least one selected from the group consisting of polyethylene, polypropylene, ethylene / ⁇ -olefin copolymer, ethylene / vinyl acetate copolymer, polyurethane, and polyester elastomer.
- the protective film used in the present invention is not limited as long as at least one surface portion is made of the resin [E], but the single layer film made of the resin [E] and the layer made of the resin [E] Or a multilayer film in which a layer made of a resin [E] is formed on both surfaces of a film made of a resin other than a resin [E] having a flexural modulus exceeding 1500 MPa. preferable.
- the layer which consists of resin [E] on both surfaces of the multilayer film which has a layer which consists of resin [E] on the outermost surface, or a film which consists of resin other than resin [E] whose bending elastic modulus exceeds 1500 Mpa.
- the thickness of the layer made of the resin [E] is usually 0.01 to 100 ⁇ m, preferably 0.1 to 50 ⁇ m.
- the thickness of the wrinkle protection film is usually 15 to 100 ⁇ m, preferably 20 to 80 ⁇ m, more preferably 30 to 60 ⁇ m.
- the thickness is less than 15 ⁇ m, the handling property is inferior, and when the thickness is more than 100 ⁇ m, the weight of the optical film wound in a roll shape becomes heavy, the workability is inferior, and the economy is inferior.
- an optical film composed of a block copolymer hydride [D] peeled off from a cast roll of an extrusion molding machine, and at least one surface portion From a resin [E] having a flexural modulus at 23 ° C. of 1500 MPa or less and an adhesiveness to an optical film made of a block copolymer hydride [D] of 0.1 N / cm or less as a peel strength at 23 ° C. And a step of superposing and winding the protective film such that the surface portion of the protective film made of the resin [E] and the optical film face each other.
- the optical film of the present invention obtained as described above is a film having a thickness of usually 15 to 200 ⁇ m, preferably 20 to 150 ⁇ m.
- the thickness variation of the optical film of the present invention is preferably within 3%, more preferably within 2.5%.
- the thickness variation of the film is a value calculated from [(maximum or minimum thickness of film ⁇ average thickness of film) / average thickness of film] ⁇ 100].
- the optical film of the present invention is excellent in surface smoothness.
- the surface roughness of both surfaces is 0.2 ⁇ m or less, preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less in terms of average roughness Ra.
- the average roughness Ra is the same as the “arithmetic average height Ra” defined by JIS B 0601: 2001.
- a color 3D laser microscope product name “VK-9500”, manufactured by Keyence Corporation)
- the films of the block copolymer hydride [D] are in contact with each other. In this case, the slipperiness is inferior and the surface is easily scratched.
- the optical film of the present invention is a member used in a display device such as a liquid crystal display device, 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, It can also be used for prism sheets and the like.
- a polarizing plate protective film the in-plane retardation Re is preferably 10 nm or less, and more preferably 3 nm or less.
- the phase difference is 10 nm or less, color unevenness when incorporated in a liquid crystal display unit can be suppressed. In particular, color unevenness tends to be conspicuous in a large-screen liquid crystal display device, which is also suitable for such a large-screen display device.
- the block copolymer hydride [D] was press-molded to produce a test piece having a length of 50 mm, a width of 10 mm, and a thickness of 1 mm.
- a loss elastic modulus measuring device product name “DMS6100”, manufactured by Seiko Instruments Inc.
- a viscoelasticity measuring device product name “ARES”, TEA).
- the glass transition temperature was determined from the peak top temperature on the high temperature side of the loss coefficient tan ⁇ .
- Flexural modulus Resin [E] used for the protective film was injection molded to prepare a test piece having a length of 100 mm, a width of 10 mm, and a thickness of 4 mm. Using this test piece, a bending test was performed according to JIS K 7171 using a strograph (product name “V10-B”, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the flexural modulus at 23 ° C. was measured. (5) Tackiness A film made of a block copolymer hydride [D] was stacked, and a plate having a thickness of 1.1 to 1.2 mm was produced using a vacuum laminator.
- a test piece for a peel test having a length of 125 mm and a width of 50 mm was cut out from this plate.
- a protective film having a length of 200 mm, a width of 24 mm, and a thickness of 50 ⁇ m is superimposed on a test piece made of a block copolymer hydride [D], and is pressure-bonded at a temperature of 50 ° C. using a roller having a weight of 2 kg.
- Test specimens were prepared. Using an autograph (product name “AGS-10NX”, manufactured by Shimadzu Corporation), a 180 ° peel test was performed from a non-adhesive portion of the film at a peel rate of 100 mm / min in accordance with JIS Z 0237 at 23 ° C. The peel strength was measured.
- a test piece of an optical film composed of a block copolymer hydride [D] (in the case where there is a protective film, the protective film is peeled off and removed) is sandwiched between polarizing plates having a polarization degree of 99.5% by crossed Nicols, Illuminate with a backlight with an illuminance of 10,000 lux, visually observe the light leakage, ⁇ (good) when no light leakage is observed, ⁇ (bad) when light leakage is observed As evaluated.
- Block copolymer hydride [D1] A reactor equipped with a stirrer and sufficiently purged with nitrogen inside was charged with 550 parts of dehydrated cyclohexane, 50.0 parts of dehydrated styrene, and 0.475 part of di-n-butyl ether. While stirring the whole volume at 60 ° C., 0.62 part of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization, and the whole volume was further stirred at 60 ° C. for 60 minutes. When the reaction solution was measured by gas chromatography, the polymerization conversion rate at this point was 99.5%.
- the polymer solution was transferred to a pressure-resistant reactor equipped with a stirrer, and a diatomaceous earth supported nickel catalyst (product name “product name“ E22U ”, nickel supported amount 60%, JGC Catalysts & Chemicals Co., Ltd.) as a hydrogenation catalyst. 7.0 parts) and 100 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was performed at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours.
- the weight average molecular weight (Mw) of the block copolymer hydride [D1] contained in the reaction solution after the hydrogenation reaction was 72,900, and the molecular weight distribution (Mw / Mn) was 1.05.
- reaction solution was filtered to remove the hydrogenation catalyst, and the filtrate was then subjected to pentaerythrityl tetrakis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate] (product name “Songnox 1010”, manufactured by Koyo Chemical Laboratory 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.
- the obtained block-like block copolymer hydride [D1] had a weight average molecular weight (Mw) of 72,200, a molecular weight distribution (Mw / Mn) of 1.10, and a hydrogenation rate of almost 100%.
- the molded product of the cocoon block copolymer hydride [D1] was colorless and transparent, had a glass transition temperature on the high temperature side of 133 ° C. and a flexural modulus of 1400 MPa, and was useful as a resin for optical films.
- the reaction solution was filtered to remove the hydrogenation catalyst, an antioxidant was added to the filtrate, and then concentrated to dryness to obtain a block copolymer hydride [D2 ] 96 parts of a pellet was obtained.
- the pelletized block copolymer hydride [D2] had a weight average molecular weight (Mw) of 73,900, a molecular weight distribution (Mw / Mn) of 1.11 and a hydrogenation rate of almost 100%.
- the molded product of cocoon block copolymer hydride [D2] was colorless and transparent, had a glass transition temperature of 121 ° C. and a flexural modulus of 1980 MPa, and was useful as a resin for optical films.
- Block copolymer hydride Styrene and isoprene were divided into 3 portions, the polymerization reaction was carried out in the same manner as in Reference Example 1 except that 15.0 parts of styrene, 70.0 parts of isoprene and 15.0 parts of styrene were added in this order, and the reaction was stopped to give a polymer. A solution was obtained.
- the polymer solution was hydrogenated in the same manner as in Reference Example 1.
- the weight average molecular weight (Mw) of the block copolymer hydride [D3] after the hydrogenation reaction was 68,900, and the molecular weight distribution (Mw / Mn) was 1.05.
- the reaction solution was filtered to remove the hydrogenation catalyst, an antioxidant was added to the filtrate, and then concentrated to dryness to obtain a block copolymer hydride [ 96 parts of D3 pellets were obtained.
- the obtained block-like block copolymer hydride [D3] had a weight average molecular weight (Mw) of 68,200, a molecular weight distribution (Mw / Mn) of 1.10, and a hydrogenation rate of almost 100%.
- the molded body of the cocoon block copolymer hydride [D3] was colorless and transparent, had a glass transition temperature on the high temperature side of 116 ° C. and a flexural modulus of 110 MPa, and was a soft resin.
- T-die film melt extrusion molding machine (T-die width 600 mm) having an extruder equipped with a 40 mm ⁇ screw, an extrusion laminating machine equipped with a cast roll and two kinds of laminating film supply devices Then, without supplying the laminating film, the film was extruded onto the cast roll surface, and a single layer film [F1] (thickness 40 ⁇ m) of low density polyethylene was extruded.
- the obtained protective film [F1] was cut off at the ear with a slitter, wound to a width of 450 mm, and collected.
- the adhesive strength of the protective film [F1] to the test pieces of the block copolymer hydride [D1] and the block copolymer hydride [D2] prepared in Reference Example 1 and Reference Example 2 was 0.02 N in terms of peel strength. / Cm and 0.01 N / cm.
- Table 1 shows the constitution of the protective film [F1] and the adhesiveness to the block copolymer hydrides [D1] and [D2].
- a film of high-density polyethylene (resin [E2]) previously molded from a film supply device is bonded to the surface of the ethylene / vinyl acetate copolymer film that is not in contact with the cast roll, and the two layers of two types Protective film [F2] (high-density polyethylene [E2] (thickness 30 ⁇ m) / ethylene-vinyl acetate copolymer [E3] (thickness 10 ⁇ m); width 450 mm).
- the adhesiveness of the protective film [F2] to the test pieces of the block copolymer hydride [D1] and the block copolymer hydride [D2] prepared in Reference Example 1 and Reference Example 2 is high-density polyethylene [E2] side.
- the peel strength was 0.02 N / cm and 0.01 N / cm, respectively, and the ethylene / vinyl acetate copolymer [E3] side had a peel strength of 0.05 N / cm and 0.04 N / cm, respectively.
- Table 1 shows the constitution of the protective film [F2] and the adhesiveness to the block copolymer hydrides [D1] and [D2].
- two-layer protective film [F3] polypropylene (thickness 30 ⁇ m) / ethylene-vinyl acetate copolymer [E3] (thick 10 ⁇ m); width 450 mm).
- the adhesiveness of the protective film [F3] to the test pieces of the block copolymer hydride [D1] and the block copolymer hydride [D2] prepared in Reference Example 1 and Reference Example 2 is the peel strength on the polypropylene side. Were 0.01 N / cm or less and 0.01 N / cm or less, respectively, and the ethylene / vinyl acetate copolymer [E3] side had a peel strength of 0.05 N / cm and 0.04 N / cm, respectively.
- Table 1 shows the constitution of the protective film [F3] and the adhesiveness to the block copolymer hydrides [D1] and [D2].
- the adhesiveness of the protective film [F4] to the test piece of the block copolymer hydride [D1] and the block copolymer hydride [D2] prepared in Reference Example 1 and Reference Example 2 is peeled off on the polyethylene terephthalate side.
- the strength was 0.01 N / cm or less and 0.01 N / cm or less, respectively, and the ethylene / vinyl acetate copolymer [E3] side had a peel strength of 0.05 N / cm and 0.04 N / cm, respectively.
- Table 1 shows the constitution of the protective film [F4] and the adhesiveness to the block copolymer hydrides [D1] and [D2].
- Protective film [F5] (ethylene / vinyl acetate copolymer [E3] (thickness 10 ⁇ m) / polyethylene terephthalate (thickness 30 ⁇ m) / ethylene / vinyl acetate copolymer [E3] (thickness 10 ⁇ m); width 450 mm) Produced.
- the adhesiveness of the protective film [F5] to the test pieces of the block copolymer hydride [D1] and the block copolymer hydride [D2] prepared in Reference Example 1 and Reference Example 2 is the same for both sides of ethylene / vinyl acetate.
- the peel strength on the polymer [E3] side was 0.05 N / cm and 0.04 N / cm, respectively.
- Table 1 shows the constitution of the protective film [F5] and the adhesiveness to the block copolymer hydrides [D1] and [D2].
- the adhesiveness of the protective film [F6] to the test piece of the block copolymer hydride [D1] and the block copolymer hydride [D2] prepared in Reference Example 1 and Reference Example 2 is low-density polyethylene [E1] side.
- the peel strength was 0.02 N / cm and 0.01 N / cm, respectively, and the block copolymer hydride [D3] side had a peel strength of 0.23 N / cm and 0.20 N / cm, respectively.
- Table 1 shows the constitution of the protective film [F6] and the adhesiveness to the block copolymer hydrides [D1] and [D2].
- the “layer constituent resin” is as follows. (1) Low density polyethylene Product name “Novatec (registered trademark) LF443”, manufactured by Nippon Polyethylene (2) High density polyethylene Product name “Novatech (registered trademark) HY430”, manufactured by Nippon Polyethylene (3) Ethylene / vinyl acetate Polymer Product name “Novatec (registered trademark) LV430”, vinyl acetate content 15% by weight, manufactured by Nippon Polyethylene (4) Polypropylene Product name “Novatech (registered trademark) FB3HAT”, manufactured by Nippon Polyethylene (5) Polyethylene terephthalate Name “TRN-8550FF”, manufactured by Teijin Limited
- the film wound up in the shape of a cocoon roll was pulled out from the film end and discarded, and then a 100 cm long film was collected as a test piece.
- the surface roughness Ra and appearance of the optical film [G1] were evaluated.
- Ra was 0.07 ⁇ m, and in the appearance evaluation, a light leakage portion was recognized and evaluated as x.
- surface defects such as scratches and rolls of the film wound up in a roll shape were observed. The results are shown in Table 2.
- Example 1 A block copolymer hydride [D1] pellet was used and melt extrusion molded in the same manner as in Comparative Example 1 to form an optical film [G2].
- the obtained optical film [G2] was cut into a roll by overlapping the protective film [F1] produced in Reference Example 4 by cutting off the ears with a slitter to a width of 450 mm.
- the film wound up in the shape of a cocoon roll was pulled out from the film end and discarded, and then a 100 cm long film was collected as a test piece.
- the protective film [F1] was peeled off from the test piece, and the surface roughness Ra of the optical film [G2] was measured and the appearance was evaluated.
- Ra was 0.04 ⁇ m, and no part of light leakage was observed in the appearance evaluation, and scratches or the like that were optically defective were not observed, and were evaluated as “ ⁇ ”. The results are shown in Table 2.
- Example 2 Using the block copolymer hydride [D1] pellets, the optical film [G3] was formed in the same manner as in Example 1, and the protective film [F2] prepared in Reference Example 5 was layered and wound into a roll. I took it. A test piece was collected from the roll-wound film in the same manner as in Example 1, and the surface roughness Ra of the optical film [G3] was measured and the appearance was evaluated. The evaluation results are shown in Table 2.
- Example 3 Using the block copolymer hydride [D1] pellets, the optical film [G6] was formed in the same manner as in Example 1, and the protective film [F5] produced in Reference Example 8 was stacked and wound into a roll. I took it. A test piece was collected from the film wound up in a roll shape in the same manner as in Example 1, and the surface roughness Ra of the optical film [G6] was measured and the appearance was evaluated. The evaluation results are shown in Table 2.
- An optical film [G8] is formed in the same manner as in Comparative Example 1 except that the block copolymer hydride [D2] prepared in Reference Example 2 is used instead of the block copolymer hydride [D1] pellets. And it rolled up in roll shape, without using a protective film. Test pieces were collected from the film wound up in a roll shape in the same manner as in Comparative Example 1, and the surface roughness Ra and appearance of the optical film [G8] were evaluated. The evaluation results are shown in Table 2.
- Example 4 An optical film [G9] is formed in the same manner as in Example 1 except that the block copolymer hydride [D2] prepared in Reference Example 2 is used in place of the block copolymer hydride [D1] pellets. Then, the protective film [F1] produced in Reference Example 4 was layered and wound into a roll. A test piece was collected from the film wound up in a roll shape in the same manner as in Example 1, and the surface roughness Ra of the optical film [G9] was measured and the appearance was evaluated. The evaluation results are shown in Table 2.
- Example 5 An optical film [G10] is formed in the same manner as in Example 1 except that the block copolymer hydride [D2] prepared in Reference Example 2 is used instead of the block copolymer hydride [D1] pellets. Then, the protective film [F2] produced in Reference Example 5 was stacked and wound into a roll. A test piece was collected from the film wound up in a roll shape in the same manner as in Example 1, and the surface roughness Ra of the optical film [G10] was measured and the appearance was evaluated. The evaluation results are shown in Table 2.
- An optical film [G11] is formed in the same manner as in Example 1 except that the block copolymer hydride [D2] prepared in Reference Example 2 is used instead of the block copolymer hydride [D1] pellets. Then, the protective film [F3] produced in Reference Example 6 was stacked and wound into a roll. A test piece was collected from the film wound up in a roll shape in the same manner as in Example 1, and the surface roughness Ra of the optical film [G11] was measured and the appearance was evaluated. The evaluation results are shown in Table 2.
- An optical film [G12] is formed in the same manner as in Example 1 except that the block copolymer hydride [D2] prepared in Reference Example 2 is used instead of the block copolymer hydride [D1] pellets. Then, the protective film [F4] produced in Reference Example 7 was stacked and wound into a roll. A test piece was collected from the film wound up in a roll shape in the same manner as in Example 1, and the surface roughness Ra of the optical film [G12] was measured and the appearance was evaluated. The evaluation results are shown in Table 2.
- Example 6 An optical film [G13] is formed in the same manner as in Example 1 except that the block copolymer hydride [D2] prepared in Reference Example 2 is used instead of the block copolymer hydride [D1] pellets. Then, the protective film [F5] produced in Reference Example 8 was stacked and wound into a roll. A test piece was collected from the film wound up in a roll shape in the same manner as in Example 1, and the surface roughness Ra of the optical film [G13] was measured and the appearance was evaluated. The evaluation results are shown in Table 2.
- An optical film [G14] is formed in the same manner as in Example 1 except that the block copolymer hydride [D2] prepared in Reference Example 2 is used in place of the block copolymer hydride [D1] pellets. Then, the protective film [F6] produced in Reference Example 9 was stacked and wound into a roll. A test piece was collected from the film wound up in a roll shape in the same manner as in Example 1, and the surface roughness Ra of the optical film [G14] was measured and the appearance was evaluated. The evaluation results are shown in Table 2.
- the optical film made of the block copolymer hydride [D] has a flexural modulus equal to or lower than a specific value, and is wound in a roll shape by contacting a protective film having a surface made of a resin having low adhesiveness. If this occurs, the generation of scratches can be suppressed (Examples 1 to 6).
- the optical film molded from the block copolymer hydride [D] is wound up alone in a roll shape, scratches are generated (Comparative Example 1 and Comparative Example 5).
- One surface is made of a resin having a sufficiently low flexural modulus, but has one or more specific values and the other surface has a specific value or less.
- the optical film of the block copolymer hydride [D] may cause scratches even when it is wound into a roll shape in contact with a protective film made of a resin having a lower flexural modulus (comparison).
- Example 6 Flexural modulus: “D2”> polypropylene).
- the method for producing an optical film of the present invention makes it possible to produce an optical film composed of a block copolymer hydride having excellent surface properties with few defects such as scratches and peeling marks on the surface, and industrially. Useful.
- the optical film obtained by the production method of the present invention includes a polarizing plate protective film, a retardation film, a base film for a transparent adhesive film, a brightness enhancement film, a transparent conductive film, a touch panel substrate, a liquid crystal substrate, a light diffusion sheet, Suitable as a prism sheet or the like.
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Abstract
Description
しかし他方で、芳香族ビニル化合物由来の繰り返し単位の含有率の高いブロック共重合体水素化物は、芳香族ビニル化合物由来の繰り返し単位の含有率が低いブロック共重合体水素化物に比して、成形されたフィルム自身同士が擦れ合うことによるフィルム表面の傷が発生し易いという問題があった。
(1)芳香族ビニル化合物由来の繰り返し単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の繰り返し単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなり、全重合体ブロック[A]のブロック共重合体全体に占める重量分率をwAとし、全重合体ブロック[B]のブロック共重合体全体に占める重量分率をwBとしたときに、wAとwBとの比(wA:wB)が60:40~90:10であるブロック共重合体[C]の、全不飽和結合の90%以上を水素化したブロック共重合体水素化物[D]からなる光学用フィルムの製造方法であって、
前記ブロック共重合体水素化物[D]を押出し成形して得られる光学用フィルムと、少なくとも一方の表面部が、23℃における曲げ弾性率が1500MPa以下であり、ブロック共重合体水素化物[D]からなる光学用フィルムに対する粘着性が、23℃における剥離強度で0.1N/cm以下である樹脂[E]からなる保護フィルムとを、前記保護フィルムの樹脂[E]からなる表面部と前記光学用フィルムとが対向するように重ね合せて巻き取ることを特徴とする光学用フィルムの製造方法。
(2)前記保護フィルムが、前記樹脂[E]からなる単層フィルム、前記樹脂[E]からなる層を最表面に有する多層フィルム、又は、曲げ弾性率が1500MPaを超える樹脂[E]以外の樹脂からなるフィルムの両面に、樹脂[E]からなる層が形成されてなる多層フィルムである、(1)に記載の光学用フィルムの製造方法。
(3)前記樹脂[E]が、ポリエチレン、ポリプロピレン、エチレン・α-オレフィン共重合体、エチレン・酢酸ビニル共重合体、ポリウレタン、及びポリエステルエラストマーからなる群から選ばれる少なくとも一種である、(1)又は(2)に記載の光学用フィルムの製造方法。
本発明の光学用フィルムの製造方法は、芳香族ビニル化合物由来の繰り返し単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の繰り返し単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなり、全重合体ブロック[A]のブロック共重合体全体に占める重量分率をwAとし、全重合体ブロック[B]のブロック共重合体全体に占める重量分率をwBとしたときに、wAとwBとの比(wA:wB)が60:40~90:10であるブロック共重合体[C]の、全不飽和結合の90%以上を水素化したブロック共重合体水素化物[D]からなる光学用フィルムの製造方法であって、
前記ブロック共重合体水素化物[D]を押出し成形して得られる光学用フィルムと、少なくとも一方の表面部が、23℃における曲げ弾性率が1500MPa以下であり、ブロック共重合体水素化物[D]からなる光学用フィルムに対する粘着性が、23℃における剥離強度で0.1N/cm以下である樹脂[E]からなる保護フィルムとを、前記保護フィルムの樹脂[E]からなる表面部と前記光学用フィルムとが対向するように重ね合せて巻き取ることを特徴とする。
本発明に用いるブロック共重合体水素化物[D]は、その前駆体であるブロック共重合体[C]の全不飽和結合の90%以上を水素化して得られる高分子である。
ブロック共重合体[C]は、少なくとも2つの重合体ブロック[A]と、少なくとも1つの重合体ブロック[B]を含有する高分子である。
重合体ブロック[A]は、芳香族ビニル化合物由来の構造単位を主成分とするものである。
重合体ブロック[A]中の、芳香族ビニル化合物由来の構造単位の含有量は、通常90重量%以上、好ましくは95重量%以上、より好ましくは99重量%以上である。
重合体ブロック[A]中の芳香族ビニル化合物由来の構造単位が少な過ぎると、本発明に係る光学用フィルムの耐熱性が低下するおそれがある。
その含有量は、重合体ブロック[A]に対し、通常10重量%以下、好ましくは5重量%以下、より好ましくは1重量%以下である。
ブロック共重合体水素化物[D]に含まれる複数の重合体ブロック[A]同士は、上記の範囲を満足すれば互いに同じであっても、相異なっていても良い。
重合体ブロック[B]は、鎖状共役ジエン化合物由来の構造単位を主成分とするものである。
重合体ブロック[B]中の、鎖状共役ジエン化合物由来の構造単位の含有量は、通常70重量%以上、好ましくは80重量%以上、より好ましくは90重量%以上である。
重合体ブロック[B]中の、鎖状共役ジエン化合物由来の構造単位が上記範囲にあると、本発明に係る光学用フィルムに柔軟性が付与される。
その含有量は、重合体ブロック[B]に対し、通常30重量%以下、好ましくは20重量%以下、より好ましくは10重量%以下である。
重合体ブロック[B]中の、芳香族ビニル化合物由来の構造単位の含有量があまりに多くなると、本発明に係る光学用フィルムの複屈折発現性は低下するが、柔軟性が低下するおそれがある。
ブロック共重合体水素化物[D]が重合体ブロック[B]を複数有する場合、重合体ブロック[B]同士は、互いに同じであっても、相異なっていても良い。
ブロック共重合体[C]は、ブロック共重合体水素化物[D]の前駆体であり、分子内に、少なくとも2つの重合体ブロック[A]と、少なくとも1つの重合体ブロック[B]を含有する高分子である。
ブロック共重合体水素化物[D]は、上記のブロック共重合体[C]の主鎖及び側鎖の炭素-炭素不飽和結合、並びに芳香環の炭素-炭素不飽和結合を水素化したものである。その水素化率は、通常90%以上、好ましくは97%以上、より好ましくは99%以上である。水素化率が高いほど、成形体の耐候性、耐熱性及び低複屈折性が良好である。ブロック共重合体水素化物[D]の水素化率は、1H-NMRによる測定において求めることができる。
アルキル置換フェノール系酸化防止剤の具体例としては、2,6-ジ-t-ブチル-p-クレゾール、2,6-ジ-t-ブチル-4-エチルフェノール、2,6-ジシクロヘキシル-4-メチルフェノール、2,6-ジイソプロピル-4-エチルフェノール、2,6-ジ-t-アミル-4-メチルフェノール、2,6-ジ-t-オクチル-4-n-プロピルフェノール、2,6-ジシクロヘキシル-4-n-オクチルフェノール、2-イソプロピル-4-メチル-6-t-ブチルフェノール、2-t-ブチル-4-エチル-6-t-オクチルフェノール、2-イソブチル-4-エチル-6-t-ヘキシルフェノール、2-シクロヘキシル-4-n-ブチル-6-イソプロピルフェノール、ステアリルβ-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート等の単環のフェノール系酸化防止剤;2,2´-メチレンビス(4-メチル-6-t-ブチルフェノール)、4,4´-ブチリデンビス(3-メチル-6-t-ブチルフェノール)、4,4´-チオビス(3-メチル-6-t-ブチルフェノール)、2,2´-チオビス(4-メチル-6-t-ブチルフェノール)、4,4´-メチレンビス(2,6-ジ-t-ブチルフェノール)、2,2´-メチレンビス[6-(1-メチルシクロヘキシル)-p-クレゾール]、2,2´-エチリデンビス(4,6-ジ-t-ブチルフェノール)、2,2´-ブチリデンビス(2-t-ブチル-4-メチルフェノール)、3,6-ジオキサオクタメチレンビス[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート]、トリエチレングリコールビス[3-(3-t-ブチル-5-メチル-4-ヒドロキシフェニル)プロピオネート]、1,6-ヘキサンジオール ビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]、2,2´-チオジエチレンビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]等の2環のフェノール系酸化防止剤;1,1,3-トリス(2-メチル-4-ヒドロキシ-5-t-ブチルフェニル)ブタン、1,3,5-トリス(2,6-ジメチル-3-ヒドロキシ-4-t-ブチルベンジル)イソシアヌレート、1,3,5-トリス[(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシエチル]イソシアヌレート、トリス(4-t-ブチル-2,6-ジメチル-3-ヒドロキシベンジル)イソシアヌレート、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン等の3環のフェノール系酸化防止剤;テトラキス[メチレン-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]メタン等の4環のフェノール系酸化防止剤;等が挙げられる。
酸化防止剤の配合量は、本発明の目的を損なわない範囲で適宜選択されるが、ブロック共重合体水素化物[D]100重量部に対して、通常0.01~1.0重量部、好ましくは0.02~0.5重量部、より好ましくは0.05~0.3重量部である。
本発明の光学用フィルムの製造方法は、前記ブロック共重合体水素化物[D]を押出し成形して得られる光学用フィルムと、少なくとも一方の表面部が、23℃における曲げ弾性率が1500MPa以下であり、ブロック共重合体水素化物[D]からなる光学用フィルムに対する粘着性が、23℃における剥離強度で0.1N/cm以下である樹脂[E]からなる保護フィルムとを、前記保護フィルムの樹脂[E]からなる表面部と前記光学用フィルムとが対向するように重ね合せて巻き取ることを特徴とする。
本発明の製造方法により製造される光学用フィルム(以下、「本発明の光学用フィルム」ということがある。)は、ブロック共重合体水素化物[D]からなる。
ここで、「ブロック共重合体水素化物[D]からなる」とは、「得られる光学用フィルムが、実質的にブロック共重合体水素化物[D]からなるものであり、本発明の目的を損なわない限り、他の配合剤を含有していてもよい」という意味である。本発明の光学用フィルムにおけるブロック共重合体水素化物[D]の含有量は、通常、95重量%以上、好ましくは97重量%以上、より好ましくは98重量%以上、さらに好ましくは99重量%以上である。
この場合、例えば、ダイスリップの表面粗さRaの平均値が0.05μm以下で、かつダイスリップ全幅における表面粗さRaの分布の範囲が前記平均値の±0.025μm以下である面粗さの小さいダイスを使用することにより、前記の平均粗さRaを有する光学用フィルムの成形が可能となる。
本発明に用いる保護フィルムは、少なくとも一方の表面部が、23℃における曲げ弾性率が1500MPa以下であり、ブロック共重合体水素化物[D]からなる光学用フィルムに対する粘着性が、23℃における剥離強度で0.1N/cm以下である樹脂[E]からなるフィルムである。
ブロック共重合体水素化物[D]からなる光学用フィルムに、上記の特定の物性を有する保護フィルム[E]を、前記保護フィルムの樹脂[E]からなる表面部と前記光学用フィルムとが対向するように重ね合せて巻き取ることにより、ブロック共重合体水素化物[D]からなる光学用フィルム自身同士が擦れ合うことによるフィルム表面の傷の発生を効果的に低減でき、また、保護フィルムを剥離する際にブロック共重合体水素化物[D]からなる光学用フィルムの表面に剥離跡が残り難くなる。 樹脂[E]の曲げ弾性率が1500MPaを超える場合は、それと接触するブロック共重合体水素化物[D]からなる光学用フィルムの表面に傷が付き易くなる。また、樹脂[E]のブロック共重合体水素化物[D]からなる光学用フィルムに対する粘着性が、剥離強度で0.1N/cmを超える場合は、樹脂[E]により表面が形成された保護フィルムをブロック共重合体水素化物[D]からなる光学用フィルムから剥離する際に、ブロック共重合体水素化物[D]からなる光学用フィルムの表面に剥離跡が残り易くなる。
樹脂[E]の曲げ弾性率はJIS K 7171に準じて測定される値であり、剥離強度はJIS Z 0237に準じて測定される値である。
保護フィルムが、樹脂[E]からなる層を最表面に有する多層フィルム、又は、曲げ弾性率が1500MPaを超える樹脂[E]以外の樹脂からなるフィルムの両面に、樹脂[E]からなる層が形成されてなる多層のフィルムである場合、前記樹脂[E]からなる層の厚みは、通常、0.01~100μm、好ましくは0.1~50μmである。
(1)重量平均分子量(Mw)及び分子量分布(Mw/Mn)
ブロック共重合体[C]及びブロック共重合体水素化物[D]の分子量は、THF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)による標準ポリスチレン換算値として、38℃において測定した。測定装置として、東ソー社製、HLC8020GPCを用いた。
(2)水素化率
ブロック共重合体水素化物[D]の主鎖、側鎖及び芳香環の水素化率は、1H-NMRスペクトルを測定して算出した。
ブロック共重合体水素化物[D]をプレス成形して、長さ50mm、幅10mm、厚さ1mmの試験片を作製した。この試験片を用いて、JIS-K7244-4法に基づき、損失弾性率測定装置(製品名「DMS6100」、セイコーインスツル社製)を、粘弾性測定装置(製品名「ARES」、ティー・エイ・インスツルメント・ジャパン社製)をそれぞれ使用して、-100℃から+150℃の範囲で、昇温速度5℃/分で粘弾性スペクトルを測定した。損失係数tanδの高温側のピークトップ温度から、ガラス転移温度を求めた。
保護フィルムに使用する樹脂[E]を射出成型して、長さ100mm、幅10mm、厚さ4mmの試験片を作製した。この試験片を用いて、ストログラフ(製品名「V10-B」、東洋精機製作所社製)を用いて、JIS K 7171に準じて曲げ試験を行い、23℃における曲げ弾性率を測定した。
(5)粘着性
ブロック共重合体水素化物[D]からなるフィルムを重ねて、真空ラミネータを使用して厚さ1.1~1.2mmの板を作製した。この板から、長さ125mm、幅50mmの剥離試験用の試験片を切り出した。長さ200mm、幅24mm、厚さ50μmの保護フィルムをブロック共重合体水素化物[D]からなる試験片に重ねて、温度50℃にて重さ2kgのローラーを使用して圧着し、剥離試験用の試験片を作製した。オートグラフ(製品名「AGS-10NX」、島津製作所社製)を使用して、フィルムの非粘着部位から、剥離速度100mm/分で、JIS Z 0237に準じて180°剥離試験を行い、23℃における剥離強度を測定した。
ブロック共重合体水素化物[D]からなるフィルムを切り出して試験片とし、カラー3Dレーザ顕微鏡(製品名「VK-9500」、キーエンス社製)を用いて、JIS B 0601:2001に準じて測定した。
(7)光学用フィルムの外観
ブロック共重合体水素化物[D]からなる光学用フィルムを巻き取ったロールからフィルム(尚、保護フィルムが有る場合は保護フィルムと共に)を引出し、長さ100cmのフィルム試験片を切り出した。ブロック共重合体水素化物[D]からなる光学用フィルムの試験片(尚、保護フィルムが有る場合は保護フィルムを剥がして除去し)を偏光度99.5%の偏光板にクロスニコルで挟み、照度10,000ルクスのバックライトにより光を照射し、光の漏れ具合を目視観察し、光の漏れが認められない場合を○(良好)、光の漏れ箇所が認められる場合を×(不良)として評価した。
攪拌装置を備え、内部が十分に窒素置換された反応器に、脱水シクロヘキサン550部、脱水スチレン50.0部、及び、ジ-n-ブチルエーテル0.475部を入れた。全容を60℃で攪拌しながら、n-ブチルリチウム(15%シクロヘキサン溶液)0.62部を加えて重合を開始させ、さらに60℃で60分間全容を攪拌した。反応液をガスクロマトグラフィーにより測定したところ、この時点での重合転化率は99.5%であった。
次に、反応液に脱水イソプレン30.0部を加え、そのまま30分間攪拌を続けた。この時点での重合転化率は99.5%であった。その後、更に、脱水スチレンを20.0部加え、60分間攪拌した。この時点での重合転化率はほぼ100%であった。
ここでイソプロピルアルコール0.5部を加えて反応を停止させて重合体溶液を得た。重合体溶液に含まれるブロック共重合体[C1]の重量平均分子量(Mw)は68,800、分子量分布(Mw/Mn)は1.04、wA:wB=70:30であった。
次いで、上記溶液を、金属ファイバー製フィルター(孔径0.4μm、ニチダイ社製)にてろ過して微小な固形分を除去した後、円筒型濃縮乾燥器(製品名「コントロ」、日立製作所社製)を用いて、温度260℃、圧力0.001MPa以下で、溶液から溶媒であるシクロヘキサン、キシレン及びその他の揮発成分を除去した。連続して溶融ポリマーを、濃縮乾燥器に連結した孔径5μmのステンレス製焼結フィルターを備えたポリマーフィルター(富士フィルター製)により、温度260℃でろ過した後、ダイから溶融ポリマーをストランド状に押出し、冷却後、ペレタイザーによりブロック共重合体水素化物[D1]のペレット95部を得た。得られたペレット状のブロック共重合体水素化物[D1]の重量平均分子量(Mw)は72,200、分子量分布(Mw/Mn)は1.10、水素化率はほぼ100%であった。
スチレンとイソプレンを5回に分け、スチレン40.0部、イソプレン10.0部、スチレン25.0部、イソプレン10.0部及びスチレン15.0部をこの順に加える以外は参考例1と同様に重合反応を行い、反応を停止させて重合体溶液を得た。重合体溶液に含まれるブロック共重合体[C2]の重量平均分子量(Mw)は70,400、分子量分布(Mw/Mn)は1.05、wA:wB=80:20であった。
スチレンとイソプレンを3回に分け、スチレン15.0部、イソプレン70.0部及びスチレン15.0部をこの順に加える以外は参考例1と同様に重合反応を行い、反応を停止させて重合体溶液を得た。重合体溶液に含まれるブロック共重合体[C3]の重量平均分子量(Mw)は65,100、分子量分布(Mw/Mn)は1.04、wA:wB=30:70であった。
低密度ポリエチレン(製品名「ノバテック(登録商標)LF443」、日本ポリエチレン社製;射出成形品の曲げ弾性率170MPa;樹脂[E1])のペレットを、空気を流通させた熱風乾燥機を用いて、50℃で4時間加熱処理した。このペレットを、40mmφのスクリューを備えた押出し機を有するTダイ式フィルム溶融押出し成形機(Tダイ幅600mm)、キャストロール及び二種の貼り合わせ用フィルム供給装置を備えた押出しラミネート成形機を使用して、貼り合わせ用フィルムは供給せずに、キャストロール面に押出し、低密度ポリエチレンの単層フィルム[F1](厚さ40μm)を押出し成形した。得られた保護フィルム[F1]は、スリッターで耳部を切除し、幅450mmにしてロール状に巻き取り回収した。
低密度ポリエチレンに代えて高密度ポリエチレン(製品名「ノバテック(登録商標)HY430」、日本ポリエチレン社製;射出成形品の曲げ弾性率1100MPa;樹脂[E2])のペレットを使用する以外は、参考例4と同様にして高密度ポリエチレンの単独フィルム(厚さ30μm、幅450mm)を成形し、ロール状に巻き取り回収した。
次に、同じ押出しラミネート成形機を使用し、40℃で、4時間熱風加熱処理を行ったエチレン・酢酸ビニル共重合体(製品名「ノバテック(登録商標)LV430」、酢酸ビニル含有率15重量%、日本ポリエチレン社製;射出成形品の曲げ弾性率45MPa;樹脂[E3])のペレットを、Tダイからキャストロール面上に、厚さ10μmとなるように押出した。エチレン・酢酸ビニル共重合体フィルムのキャストロールに接していない側の面に、フィルム供給装置から先に成形した高密度ポリエチレン(樹脂[E2])のフィルムを供給して貼り合わせ、二種2層の保護フィルム[F2](高密度ポリエチレン[E2](厚さ30μm)/エチレン・酢酸ビニル共重合体[E3](厚さ10μm);幅450mm)を作製した。
70℃で、4時間熱風加熱処理を行ったポリプロピレン(製品名「ノバテック(登録商標) FB3HAT」、日本ポリエチレン社製;射出成形品の曲げ弾性率1750MPa)のペレットを使用し、参考例5と同様にして、先にポリプロピレンの単独フィルム(厚さ30μm、幅450mm)を成形し、ロール状に巻き取り回収した。
次に、参考例5で使用したのと同じエチレン・酢酸ビニル共重合体(樹脂[E3])のペレットを使用し、参考例5と同様にして、Tダイからエチレン・酢酸ビニル共重合体を押出し、フィルム供給装置から先に成形したポリプロピレンのフィルムを供給して貼り合わせ、二種2層の保護フィルム[F3](ポリプロピレン(厚さ30μm)/エチレン・酢酸ビニル共重合体[E3](厚さ10μm);幅450mm)を作製した。
50℃で、4時間熱風加熱処理を行ったポリエチレンテレフタレート(製品名「「TRN-8550FF」、帝人社製;射出成形品の曲げ弾性率3200MPa)のペレットを使用し、参考例5と同様にして、先にポリエチレンテレフタレートの単独フィルム(厚さ30μm、幅450mm)を成形し、ロール状に巻き取り回収した。
次に、参考例5で使用したのと同じエチレン・酢酸ビニル共重合体(樹脂[E3])のペレットを使用し、参考例5と同様にして、Tダイからエチレン・酢酸ビニル共重合体を押出し、フィルム供給装置から先に成形したポリエチレンテレフタレートのフィルムを供給して貼り合わせ、二種2層の保護フィルム[F4](ポリエチレンテレフタレート(厚さ30μm)/エチレン・酢酸ビニル共重合体[E3](厚さ10μm);幅450mm)を作製した。
化物[D1]及び[D2]に対する粘着性を表1に示した。
参考例5で使用したのと同じエチレン・酢酸ビニル共重合体(樹脂[E3])のペレットを使用し、参考例5と同様にして、Tダイからエチレン・酢酸ビニル共重合体を押出し、フィルム供給装置から参考例7で成形したポリエチレンテレフタレート/エチレン・酢酸ビニル共重合体の二種2層のフィルムを供給して貼り合わせ、二種3層の保護フィルム[F5](エチレン・酢酸ビニル共重合体[E3](厚さ10μm)/ポリエチレンテレフタレート(厚さ30μm)/エチレン・酢酸ビニル共重合体[E3](厚さ10μm);幅450mm)を作製した。
参考例4で使用したのと同じ低密度ポリエチレン(樹脂[E1])のペレットを使用し、参考例5と同様にして、先に低密度ポリエチレンの単独フィルム(厚さ30μm、幅450mm)を成形し、ロール状に巻き取り回収した。
次に、参考例5で使用したエチレン・酢酸ビニル共重合体に代えて参考例3で作成したブロック共重合体水素化物[D3](射出成形品の曲げ弾性率110MPa)のペレットを使用し、参考例5と同様にして、Tダイからブロック共重合体水素化物[D3]を押出し、フィルム供給装置から先に成形した低密度ポリエチレンのフィルムを供給して貼り合わせ、二種2層の保護フィルム[F6](低密度ポリエチレン(厚さ30μm)/ブロック共重合体水素化物[D3](厚さ10μm);幅450mm)を作製した。
(1)低密度ポリエチレン
製品名「ノバテック(登録商標)LF443」、日本ポリエチレン社製
(2)高密度ポリエチレン
製品名「ノバテック(登録商標)HY430」、日本ポリエチレン社製
(3)エチレン・酢酸ビニル共重合体
製品名「ノバテック(登録商標)LV430」、酢酸ビニル含有率15重量%、日本ポリエチレン社製
(4)ポリプロピレン
製品名「ノバテック(登録商標)FB3HAT」、日本ポリエチレン社製
(5)ポリエチレンテレフタレート
製品名「TRN-8550FF」、帝人社製
参考例1で得られたブロック共重合体水素化物[D1]のペレットを、空気を流通させた熱風乾燥機を用いて70℃で、4時間加熱処理を行った。この加熱処理後のペレットを使用し、リーフディスク形状のポリマーフィルター(ろ過精度10μm)を設置した40mmφのスクリューを備えた単軸押出し機を有するTダイ式フィルム溶融押出し成形機(Tダイ幅600mm)、キャストロール(直径250mm)及び保護フィルム供給装置を備えたフィルム成形機を用いて、樹脂温度250℃、キャストロール温度105℃、引取り速度0.35m/sの条件で溶融押出し成形し、光学用フィルム[G1]を成形した。
得られた光学用フィルム[G1]は、スリッターで耳部を切除し、幅450mmにして保護フィルムは使用せずにロール状に巻き取り回収した。
ブロック共重合体水素化物[D1]のペレットを使用し、比較例1と同様にして溶融押出し成形し、光学用フィルム[G2]を成形した。得られた光学用フィルム[G2]は、スリッターで耳部を切除し、幅450mmにして、参考例4で作製した保護フィルム[F1]を重ねてロール状に巻き取った。
ブロック共重合体水素化物[D1]のペレットを使用し、実施例1と同様にして光学用フィルム[G3]を成形し、参考例5で作製した保護フィルム[F2]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G3]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットを使用し、実施例1と同様にして光学用フィルム[G4]を成形し、参考例6で作製した保護フィルム[F3]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G4]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットを使用し、実施例1と同様にして光学用フィルム[G5]を成形し、参考例7で作製した保護フィルム[F4]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G5]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットを使用し、実施例1と同様にして光学用フィルム[G6]を成形し、参考例8で作製した保護フィルム[F5]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G6]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットを使用し、実施例1と同様して光学用フィルム[G7]を成形し、参考例9で作製した保護フィルム[F6]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G7]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットに代えて参考例2で作成したブロック共重合体水素化物[D2]を使用する以外は、比較例1と同様にして光学用フィルム[G8]を成形し、保護フィルムを使用せずにロール状に巻き取った。ロール状に巻き取ったフィルムから比較例1と同様にして試験片を採取し、光学用フィルム[G8]の表面粗さRa及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットに代えて参考例2で作成したブロック共重合体水素化物[D2]を使用する以外は、実施例1と同様にして光学用フィルム[G9]を成形し、参考例4で作製した保護フィルム[F1]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G9]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットに代えて参考例2で作成したブロック共重合体水素化物[D2]を使用する以外は、実施例1と同様にして光学用フィルム[G10]を成形し、参考例5で作製した保護フィルム[F2]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G10]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットに代えて参考例2で作成したブロック共重合体水素化物[D2]を使用する以外は、実施例1と同様にして光学用フィルム[G11]を成形し、参考例6で作製した保護フィルム[F3]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G11]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットに代えて参考例2で作成したブロック共重合体水素化物[D2]を使用する以外は、実施例1と同様にして光学用フィルム[G12]を成形し、参考例7で作製した保護フィルム[F4]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G12]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットに代えて参考例2で作成したブロック共重合体水素化物[D2]を使用する以外は、実施例1と同様にして光学用フィルム[G13]を成形し、参考例8で作製した保護フィルム[F5]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G13]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D1]のペレットに代えて参考例2で作成したブロック共重合体水素化物[D2]を使用する以外は、実施例1と同様にして光学用フィルム[G14]を成形し、参考例9で作製した保護フィルム[F6]を重ねてロール状に巻き取った。ロール状に巻き取ったフィルムから実施例1と同様にして試験片を採取し、光学用フィルム[G14]の表面粗さRaの測定及び外観の評価を行った。評価結果を表2に示す。
ブロック共重合体水素化物[D]からなる光学用フィルムは、特定の値以下の曲げ弾性率有し、且つ、粘着性の低い樹脂により表面が構成された保護フィルムを接触させてロール状に巻いた場合に擦り傷の発生を抑止できる(実施例1~6)。
一方、ブロック共重合体水素化物[D]から成形された光学用フィルムは、単独でロール状に巻き取ると、擦り傷が発生する(比較例1、比較例5)。
片方の面が、曲げ弾性率が十分低い樹脂からなるものであるが、特定値以上の粘着性を有するものであって、もう片方の面が、特定値以下の粘着性を有するものであるが、曲げ弾性率が大きい樹脂からなるものである保護フィルムを使用した場合は、擦り傷は抑止できず、かつ、保護フィルムを剥離した際の剥離跡が生じ、偏光板にクロスニコルで挟んだ際に光漏れが生じる(比較例2、3、7)。
曲げ弾性率が十分低い樹脂からなる保護フィルムを使用しても、ブロック共重合体水素化物[D]の光学用フィルムに対して特定値以上の粘着性を有する保護フィルムを使用した場合は、擦り傷は抑止できるが、保護フィルムを剥離した際の剥離跡が生じ、偏光板にクロスニコルで挟んだ際に光漏れが生じる(比較例4、比較例8)。
また、ブロック共重合体水素化物[D]の光学用フィルムは、それより低い曲げ弾性率を有する樹脂からなる保護フィルムと接触させてロール状に巻いた場合でも擦り傷が発生する場合がある(比較例6;曲げ弾性率:「D2」>ポリプロピレン)。
本発明の製造方法により得られる光学用フィルムは、偏光板保護フィルム、位相差フィルム、透明粘着フィルム用の基材フィルム、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、プリズムシート等として好適である。
Claims (3)
- (1)芳香族ビニル化合物由来の繰り返し単位を主成分とする、少なくとも2つの重合体ブロック[A]と、鎖状共役ジエン化合物由来の繰り返し単位を主成分とする、少なくとも1つの重合体ブロック[B]とからなり、全重合体ブロック[A]のブロック共重合体全体に占める重量分率をwAとし、全重合体ブロック[B]のブロック共重合体全体に占める重量分率をwBとしたときに、wAとwBとの比(wA:wB)が60:40~90:10であるブロック共重合体[C]の、全不飽和結合の90%以上を水素化したブロック共重合体水素化物[D]からなる光学用フィルムの製造方法であって、
前記ブロック共重合体水素化物[D]を押出し成形して得られる光学用フィルムと、少なくとも一方の表面部が、23℃における曲げ弾性率が1500MPa以下であり、ブロック共重合体水素化物[D]からなる光学用フィルムに対する粘着性が、23℃における剥離強度で0.1N/cm以下である樹脂[E]からなる保護フィルムとを、前記保護フィルムの樹脂[E]からなる表面部と前記光学用フィルムとが対向するように重ね合せて巻き取ることを特徴とする光学用フィルムの製造方法。 - 前記保護フィルムが、前記樹脂[E]からなる単層フィルム、前記樹脂[E]からなる層を最表面に有する多層フィルム、又は、曲げ弾性率が1500MPaを超える樹脂[E]以外の樹脂からなるフィルムの両面に、樹脂[E]からなる層が形成されてなる多層フィルムである、請求項1に記載の光学用フィルムの製造方法。
- 前記樹脂[E]が、ポリエチレン、ポリプロピレン、エチレン・α-オレフィン共重合体、エチレン・酢酸ビニル共重合体、ポリウレタン、及びポリエステルエラストマーからなる群から選ばれる少なくとも一種である、請求項1又は2に記載の光学用フィルムの製造方法。
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JP7092133B2 (ja) * | 2017-07-31 | 2022-06-28 | 日本ゼオン株式会社 | 光学フィルム |
KR20210025006A (ko) * | 2018-06-28 | 2021-03-08 | 니폰 제온 가부시키가이샤 | 편광 필름 및 그 제조 방법 |
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