WO2011065584A1 - 光学フィルムおよび複合偏光板 - Google Patents
光学フィルムおよび複合偏光板 Download PDFInfo
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- WO2011065584A1 WO2011065584A1 PCT/JP2010/071625 JP2010071625W WO2011065584A1 WO 2011065584 A1 WO2011065584 A1 WO 2011065584A1 JP 2010071625 W JP2010071625 W JP 2010071625W WO 2011065584 A1 WO2011065584 A1 WO 2011065584A1
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- resin
- film
- optical film
- polarizing plate
- saturated hydrocarbon
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
Definitions
- the present invention relates to an optical film and a composite polarizing plate using the same.
- One such liquid crystal display device is a vertical alignment (VA) mode liquid crystal display device in which rod-like liquid crystal molecules having positive or negative dielectric anisotropy are aligned perpendicularly to a substrate.
- VA vertical alignment
- the polarization state of incident light passes through the liquid crystal layer without change. Therefore, if linear polarizing plates are arranged on the front and back of the liquid crystal cell so that the absorption axes thereof are orthogonal to each other, the front surface of the liquid crystal display device using the same is almost completely black and exhibits a high contrast ratio.
- a laminated composite type polarizing plate in which an optical film is laminated via a pressure-sensitive adhesive (adhesive) on a linear polarizing plate comprising a protective film made of a triacetyl cellulose film on both sides of a polarizing film.
- the board is on the market.
- composite polarizing plates using a film having the function of the optical film as a protective film laminated on the polarizing film are also on the market.
- one triacetyl cellulose film and one pressure-sensitive adhesive layer, which are protective films can be reduced from the laminated composite polarizing plate, the cost can be reduced and the thickness can be reduced.
- an optical film made of a resin having a small photoelastic coefficient there is an advantage that a deterioration in display quality called white spot can be suppressed.
- JPH08-43812-A and JPH09-325216-A describe that at least one of the protective films of the polarizing plate is composed of a birefringent film.
- JP07-287123-A and JP2002-221619-A describe that a protective film for a polarizing plate is composed of a cyclic olefin resin having a small photoelastic coefficient.
- a material having a small birefringence accompanying deformation of the film that is, photoelasticity of the cyclic olefin resin or the like is used.
- a material having a small coefficient may be selected.
- photoelasticity and orientation birefringence when a material with a small photoelastic coefficient is selected to suppress white spots, most materials have low orientation birefringence at the same time. Since the expression of the retardation value due to stretching is too low, it was necessary to use a relatively thick film in order to express the desired retardation value.
- JP2007-316603-A and JP2009-134257-A since the photoelastic coefficient is small and the expression rate of the retardation value is high, an optical film (a retardation film) using a polypropylene-based resin capable of thinning the film.
- a retardation film using a polypropylene-based resin is subject to in-plane retardation value fluctuations over time, such that the in-plane retardation value gradually increases even after heat stretching treatment after stretching, In some cases, the in-plane retardation value is difficult to stabilize.
- An object of the present invention is to provide an optical film that exhibits a desired retardation value even when the film thickness is small and has a small in-plane retardation value variation over time, and a composite polarizing plate using the same. is there.
- the present invention includes the following.
- optical film Nz coefficient (n x -n z) / Nz coefficient defined by (n x -n y) is within the range of 0.9 1-3.
- optical film according to [1] which has a thickness of 35 ⁇ m or less.
- the resin film containing a polypropylene resin and an alicyclic saturated hydrocarbon resin is a stretched film of a resin composition containing a polypropylene resin and an alicyclic saturated hydrocarbon resin, and the resin composition Is an optical film as described in [1] or [2] containing 0.1 to 30% by weight of an alicyclic saturated hydrocarbon resin.
- a composite polarizing plate comprising a polarizing film and the optical film according to any one of [1] to [6] laminated on one side of the polarizing film.
- the composite polarizing plate according to [7] further comprising a transparent protective layer on the surface opposite to the surface on which the optical film is laminated.
- the present invention it is possible to provide an optical film and a composite polarizing plate in which the in-plane retardation value variation with time after production is sufficiently suppressed.
- a composite polarizing plate including an optical film having a small in-plane retardation value variation with time the stability of the display performance of the liquid crystal display device can be improved.
- the optical film of the present invention is a birefringent resin film containing a polypropylene resin and an alicyclic saturated hydrocarbon resin. Typically, as will be described in detail later, a polypropylene resin and an alicyclic ring are typically used. It is a stretched film that expresses a retardation produced by uniaxially stretching or biaxially stretching a raw film containing a group saturated hydrocarbon resin.
- the in-plane retardation value R 0 of the optical film of the present invention is in the range of 40 to 500 nm, preferably 50 to 300 nm, and the thickness direction retardation value R th is in the range of 20 to 500 nm, preferably 25 to 400 nm. Range.
- the Nz coefficient is in the range of 0.9 to 3.
- the Nz coefficient is preferably in the range of 0.9 to 2.
- the Nz coefficient is preferably in the range of 1.0 to 3. Even in the case of a biaxially stretched film, the Nz coefficient can approach 1 if the longitudinal and lateral stretch ratios differ greatly.
- the in-plane slow axis direction of the refractive index of the film n x the refractive index n y in-plane fast axis direction (direction orthogonal with the slow axis and the plane), the refractive index in the thickness direction n z
- the in-plane retardation value R 0 the thickness direction retardation value R th , and the Nz coefficient are defined by the following equations (I), (II), and (III), respectively.
- the thickness can be 35 ⁇ m or less, and further 30 ⁇ m or less. Thinning can be achieved.
- the thickness of the optical film is preferably 5 ⁇ m or more, and more preferably 8 ⁇ m or more. If the thickness is less than 5 ⁇ m, wrinkles and the like are likely to occur in the film, and handling properties at the time of winding and bonding may be reduced.
- the alicyclic saturated hydrocarbon resin constituting the optical film of the present invention is a resin classified as a petroleum resin.
- the petroleum resin is a thermoplastic resin obtained by polymerizing and solidifying a cracked oil fraction generated by thermal decomposition of petroleum, for example, an aliphatic petroleum resin using a C5 fraction as a raw material; a C9 fraction as a raw material.
- an alicyclic saturated hydrocarbon resin is particularly used among the above petroleum resins.
- the alicyclic saturated hydrocarbon resin is typically a polymer obtained using cyclopentadiene (CPD) or dicyclopentadiene (DCPD) as a raw material, or a hydrogenated petroleum resin obtained by hydrogenating an aromatic petroleum resin.
- CPD cyclopentadiene
- DCPD dicyclopentadiene
- hydrogenated petroleum resin obtained by hydrogenating an aromatic petroleum resin.
- it can be represented by the following structural formulas (1) to (3).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents a hydrogen atom or a methyl group
- m represents 0 to 16
- n represents 0 to 16
- m + n is 3 to 16.
- the alicyclic saturated hydrocarbon resin has a high effect of suppressing fluctuation of the in-plane retardation value with time, is colorless and transparent, and has advantageous characteristics as an optical film material that is excellent in weather resistance.
- the alicyclic saturated hydrocarbon resin used in the present invention preferably has a softening point of 110 ° C. or higher and 145 ° C. or lower. More preferably, it is 115 degreeC or more and 135 degreeC or less.
- the softening point is lower than 110 ° C, the heat resistance of the optical film tends to be lowered.
- the softening point is higher than 145 ° C, the stretchability of the original film is deteriorated, and the productivity of the optical film is lowered. It is in.
- a commercially available product can also be used as the alicyclic saturated hydrocarbon resin.
- Examples of such commercially available products include the “Arcon” series manufactured by Arakawa Chemical Industries, Ltd.
- the optical film of the present invention contains an alicyclic saturated hydrocarbon resin in a range of usually 0.1 to 30% by weight, preferably 3 to 20% by weight. contains. If the content of the alicyclic saturated hydrocarbon resin is less than 0.1% by weight, the effect of suppressing the fluctuation of the in-plane retardation value over time cannot be sufficiently obtained, and if it exceeds 30% by weight, the optical film There is a concern that bleedout of the alicyclic saturated hydrocarbon resin may occur over time.
- the polypropylene resin constituting the optical film of the present invention may be a resin consisting essentially of a propylene homopolymer, or a resin consisting of a copolymer of propylene and another copolymerizable comonomer. Also good.
- the homopolymer of propylene is advantageous in that the film rigidity and yield strength can be further increased because the degree of crystallinity is higher than the copolymer of propylene and other copolymerizable comonomers. . Therefore, it becomes possible to further improve the handleability in the optical film preparation step and the polarizing plate formation step by using a resin consisting essentially of a propylene homopolymer as the polypropylene resin.
- the “substantially propylene homopolymer” is a polymer having a propylene unit content of 100% by weight, or about 0.6% by weight or less for the purpose of improving the productivity of the raw film.
- Propylene / ethylene copolymers containing ethylene units in the range are also included.
- the polypropylene resin composed of a copolymer of propylene and another copolymerizable comonomer is preferably one in which propylene is the main component and one or two or more types of comonomer copolymerizable therewith are copolymerized in a small amount.
- the polypropylene resin comprising such a copolymer is a resin containing a comonomer unit in a range of, for example, 20% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less. be able to.
- the comonomer unit content in the copolymer is at least more than 0.6% by weight, preferably 1% by weight or more, more preferably 3% by weight or more.
- the content of the comonomer unit By setting the content of the comonomer unit to 1% by weight or more, processability and transparency can be significantly improved. On the other hand, when the content of the comonomer unit exceeds 20% by weight, the melting point of the polypropylene resin is lowered and the heat resistance tends to be lowered. In addition, when setting it as the copolymer of 2 or more types of comonomer, and propylene, it is preferable that the total content of the unit derived from all the comonomer contained in the copolymer is the said range.
- the comonomer copolymerized with propylene can be, for example, an unsaturated hydrocarbon such as ethylene or an ⁇ -olefin having 4 to 20 carbon atoms.
- an unsaturated hydrocarbon such as ethylene or an ⁇ -olefin having 4 to 20 carbon atoms.
- Specific examples of the ⁇ -olefin include the following.
- ⁇ -olefins having 4 to 12 carbon atoms are preferable.
- 1-octene 5-methyl-1-heptene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2,3 , 4-Trimethyl-1-pente , 2-propyl-1
- the copolymer may be a random copolymer or a block copolymer.
- Preferred copolymers include propylene / ethylene copolymers and propylene / 1-butene copolymers.
- the ethylene unit content and the 1-butene unit content are, for example, those of “Polymer Analysis Handbook” (1995, published by Kinokuniya Shoten) Infrared (IR) spectrum measurement can be performed by the method described on page 616.
- the copolymer is preferably a random copolymer of propylene mainly composed of propylene and the unsaturated hydrocarbon, and a random copolymer of propylene and ethylene. More preferably, it is a polymer.
- the content of the ethylene unit in the propylene / ethylene random copolymer is preferably 1 to 20% by weight, more preferably 1 to 10% by weight, and 3 to 7% by weight. Is more preferable.
- the stereoregularity of the polypropylene resin may be isotactic, syndiotactic or atactic, but syndiotactic or isotactic polypropylene resin is preferably used from the viewpoint of heat resistance of the optical film. It is done.
- the polypropylene resin used for the optical film of the present invention has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K 7210, particularly 0.1 to 200 g / 10 min. It is preferably in the range of 0.5 to 50 g / 10 minutes.
- the polypropylene resin constituting the optical film of the present invention can be produced by a method of homopolymerizing propylene or a method of copolymerizing propylene and another copolymerizable comonomer using a known polymerization catalyst.
- known polymerization catalysts include the following. (1) a Ti—Mg-based catalyst comprising a solid catalyst component containing magnesium, titanium, and halogen as essential components; (2) a catalyst system in which a solid catalyst component containing magnesium, titanium, and halogen as essential components is combined with an organoaluminum compound and, if necessary, a third component such as an electron donating compound, (3) Metallocene catalysts.
- Examples of the solid catalyst component containing magnesium, titanium, and halogen as essential components in the catalyst systems (1) and (2) above include JPS61-218606-A, JPS61-287904-A, and JPH07-216017-A. Mention may be made of the catalyst systems described.
- the organoaluminum compound in the catalyst system of (2) above triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, tetraethyldialumoxane and the like are preferably used, and the electron donating compound is cyclohexylethyl.
- Dimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylethyldimethoxysilane, dicyclopentyldimethoxysilane and the like are preferably used.
- examples of the metallocene catalyst of (3) above include catalyst systems described in JP2588251-B2, JP2627669-B2, JP2668732-B2, and the like.
- the catalyst system of the above (2) is most commonly used in the present invention.
- Polypropylene resins are, for example, solution polymerization methods using an inert solvent typified by hydrocarbon compounds such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and liquid monomers as solvents. It can be produced by a bulk polymerization method to be used or a gas phase polymerization method in which a gaseous monomer is polymerized as it is. Polymerization by these methods may be carried out batchwise or continuously.
- an inert solvent typified by hydrocarbon compounds such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and liquid monomers as solvents. It can be produced by a bulk polymerization method to be used or a gas phase polymerization
- the optical film of the present invention is produced by producing a raw film from a resin composition containing a polypropylene resin and an alicyclic saturated hydrocarbon resin, and stretching the obtained raw film to develop a retardation. Obtainable.
- the raw film is produced by forming a resin composition containing a polypropylene resin and an alicyclic saturated hydrocarbon resin.
- the method for preparing the resin composition is not particularly limited as long as at least the alicyclic saturated hydrocarbon resin is uniformly dispersed in the obtained resin composition.
- a polypropylene resin is prepared. Examples thereof include a method of adding an alicyclic saturated hydrocarbon resin to the polymerization reaction mixture during or immediately after the polymerization reaction in the polymerization step.
- the alicyclic saturated hydrocarbon resin may be added as a solution dissolved in a solvent, or may be pulverized into a powder form so that it can be easily dispersed, added as a powder, or heated and melted. May be added.
- the resin composition can also be obtained by a method in which an alicyclic saturated hydrocarbon resin is added while melt-kneading a polypropylene resin, and then melt-kneading. These melt-kneading can be performed using, for example, a kneader such as a ribbon blender, a mixing roll, a Banbury mixer, a roll, various kneaders, a single-screw extruder, or a twin-screw extruder.
- the resin composition thus obtained may be subjected to a molding process into a raw film without being cooled after being melt-kneaded, or after being cooled into a molded article such as a pellet body. This may be heated again to be used for forming a raw film. Moreover, after cooling, it can also shape
- the content of the alicyclic saturated hydrocarbon resin in the resin composition is usually in the range of 0.1 to 30% by weight, preferably 3 to 20% by weight when the weight of the resin composition is 100% by weight. %. If the content of the alicyclic saturated hydrocarbon resin is less than 0.1% by weight, the effect of suppressing the fluctuation of the in-plane retardation value over time cannot be sufficiently obtained, and if it exceeds 30% by weight, the optical film There is a concern that bleedout of the alicyclic saturated hydrocarbon resin may occur over time.
- the said resin composition may contain a well-known additive in the range which does not inhibit the effect of this invention.
- the additive include an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a nucleating agent, an antifogging agent, and an antiblocking agent.
- the resin composition can contain one or more additives.
- antioxidants include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, hindered amine light stabilizers, and the like, and for example, phenolic antioxidant mechanisms in one molecule. It is also possible to use a composite antioxidant having a unit having both a phosphorus-based antioxidant mechanism and a phosphorus-based antioxidant mechanism.
- UV absorber include UV absorbers such as 2-hydroxybenzophenone and hydroxyphenylbenzotriazole, and benzoate UV blockers.
- the antistatic agent may be polymer type, oligomer type or monomer type.
- the lubricant examples include higher fatty acid amides such as erucic acid amide and oleic acid amide, higher fatty acids such as stearic acid, and salts thereof.
- the anti-blocking agent fine particles having a spherical shape or a shape close thereto can be used regardless of inorganic type or organic type.
- the nucleating agent may be either an inorganic nucleating agent or an organic nucleating agent.
- the inorganic nucleating agent include talc, clay, calcium carbonate and the like.
- the organic nucleating agent include metal salts such as aromatic carboxylic acid metal salts and aromatic phosphoric acid metal salts, high-density polyethylene, poly-3-methylbutene-1, polycyclopentene, and polyvinylcyclohexane. It is done. Among these, organic nucleating agents are preferable, and the above metal salts and high density polyethylene are more preferable.
- the addition amount of the nucleating agent is preferably within a range of 0.01 to 3% by weight with respect to 100% by weight of the polypropylene resin contained in the resin composition, and is preferably 0.05 to 1.5% by weight. More preferably within the range.
- the original resin film can be formed by forming the resin composition by any method.
- This raw film is transparent and has substantially no in-plane retardation.
- film forming methods include 1) a method of extruding a resin composition in a molten state (which may be once made into a pellet and then heated to a molten state), and 2) a resin composition containing a solvent. Casting a product (a solvent may be separately added to the resin composition) on a flat plate, removing the solvent to form a film, and 3) a method of press molding the resin composition Can do.
- the resin composition is melt-kneaded by rotation of a screw in an extruder and extruded from a T die into a sheet.
- the temperature of the extruded molten sheet can be about 180 to 300 ° C.
- the spreadability is not sufficient, the thickness of the obtained raw film becomes non-uniform, and there is a possibility that the film has uneven retardation.
- the extruder may be a single screw extruder or a twin screw extruder.
- a ratio of the length L and the diameter D of the screw L / D of about 24-36, a thread groove in the space volume V 1 and the resin metering section of the screw groove in the resin supply section
- a screw of a compression ratio V 1 / V 2 which is a ratio to the space volume V 2 , of about 1.5 to 4 and having a full flight type, a barrier type or a Maddock type kneading part. .
- the barrier type of L / D is 28 to 36 and the compression ratio V 1 / V 2 is 2.5 to 3.5 It is more preferable to use a screw.
- the inside of the extruder is preferably a nitrogen atmosphere or a vacuum.
- Increasing the resin pressure at the tip of the extruder at the orifice means increasing the back pressure at the tip, thereby improving the stability of extrusion.
- the diameter of the orifice to be used is more preferably 2 mm ⁇ or more and 4 mm ⁇ or less.
- the T-die used for extrusion preferably has no fine steps or scratches on the surface of the flow path of the resin composition, and the lip portion is plated with a material having a low friction coefficient with the molten resin composition.
- a sharp edge shape that is coated and further polished to a lip tip of 0.3 mm ⁇ or less is preferable.
- the material having a small friction coefficient include tungsten carbide type and fluorine type special plating.
- the lip width of the T die is less than 1500 mm: the thickness direction length of the T die> 180 mm, (2) When the lip width of the T die is 1500 mm or more: the thickness direction length of the T die> 220 mm, (3) When the lip width of the T die is less than 1500 mm: the length in the height direction of the T die> 250 mm, (4) When the lip width of the T die is 1500 mm or more: Length in the height direction of the T die> 280 mm.
- the flow of the molten resin composition inside the T-die can be adjusted, and the lip portion can be extruded while suppressing thickness unevenness. It is possible to obtain an original film which is excellent in accuracy and made more uniform at a level where the in-plane retardation is extremely low.
- a gear pump through an adapter between the extruder and the T die from the viewpoint of suppressing the extrusion fluctuation of the resin composition.
- a leaf disk filter In order to remove foreign substances in the resin composition, it is preferable to attach a leaf disk filter.
- the molten sheet extruded from the T-die is between a metal cooling roll (also called a chill roll or a casting roll) and a touch roll including an elastic body that rotates in pressure contact with the circumferential direction of the metal cooling roll. It is pinched and cooled and solidified by both rolls to form a raw film.
- the touch roll may be one in which an elastic body such as rubber is directly on the surface, or may be one in which the surface of the elastic body roll is covered with an outer cylinder made of a metal sleeve.
- cooling is usually performed by directly sandwiching a molten sheet of the resin composition between the metal cooling roll and the touch roll.
- a biaxially stretched film of a thermoplastic resin may be interposed between the molten sheet of the resin composition and the touch roll to sandwich the pressure.
- both the cooling roll and the touch roll have their surface temperatures lowered, and the molten sheet
- the surface temperature of both rolls is preferably adjusted to a range of 0 ° C. or higher and 30 ° C. or lower. When these surface temperatures exceed 30 ° C, it takes time to cool and solidify the molten sheet, so that the crystal component in the molten sheet grows, and the transparency of the resulting raw film may be lowered. .
- the surface temperature of both rolls is more preferably less than 30 ° C, still more preferably less than 25 ° C. On the other hand, if the surface temperature of both rolls is less than 0 ° C., dew condensation occurs on the surface of the metallic cooling roll, and water droplets adhere to the surface of the roll, which may deteriorate the appearance of the raw film.
- the surface of the metal cooling roll used is transferred to the surface of the original film, if the surface is uneven, the thickness accuracy of the resulting original film may be lowered. Therefore, the surface of the metal cooling roll is preferably as close to a mirror surface as possible as the film can be peeled off. Specifically, the roughness of the surface of the metal cooling roll is preferably 0.4 S or less, more preferably 0.05 S to 0.2 S, expressed as a standard sequence of the maximum height.
- the touch roll forming the nip portion with the metal cooling roll has a surface hardness of 65 to 80 as a value measured by a spring type hardness test (A type) defined in JIS K 6301. It is preferably 70-80.
- a type spring type hardness test
- the pressure (linear pressure) when sandwiching the molten sheet is determined by the pressure for pressing the touch roll against the metal cooling roll.
- the linear pressure is preferably 50 N / cm or more and 300 N / cm or less, and more preferably 100 N / cm or more and 250 N / cm or less.
- the thermoplastic resin constituting the biaxially stretched film is a molten sheet and Any resin that does not strongly heat-seal can be used. Specific examples include polyester, polyamide, polyvinyl chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and polyacrylonitrile. Among these, polyesters that have little dimensional change due to humidity, heat, and the like are most preferable.
- the thickness of the biaxially stretched film is usually about 5 to 50 ⁇ m, preferably 10 to 30 ⁇ m.
- the distance (air gap) from the lip of the T die to the pressure between the metal cooling roll and the touch roll is preferably 200 mm or less, and more preferably 160 mm or less.
- the molten sheet extruded from the T-die is stretched from the lip to the roll, and orientation tends to occur. By shortening the air gap as described above, a raw film having a smaller orientation can be obtained.
- the lower limit value of the air gap is determined by the diameter of the metal cooling roll to be used, the diameter of the touch roll, and the tip shape of the lip to be used, and is usually 50 mm or more.
- the processing speed of the raw film is determined by the time required for cooling and solidifying the molten sheet.
- the diameter of the metal cooling roll to be used is increased, the distance at which the molten sheet is in contact with the cooling roll becomes longer, so that production at higher speed is possible.
- the processing speed is about 5 to 20 m / min at the maximum.
- the raw film obtained by being sandwiched between a metal cooling roll and a touch roll and cooled and solidified is usually wound into a roll by a winder after slitting the end as necessary.
- the biaxially stretched film can be used as one surface protective film.
- the optical film of this invention can be obtained by extending
- the stretching method is not particularly limited, and longitudinal uniaxial stretching, lateral uniaxial stretching, sequential biaxial stretching, simultaneous biaxial stretching, or the like can be employed.
- the uniaxial stretching in the machine direction is a method in which the raw film of the resin composition is preheated in the machine direction by a series of heating rolls and subsequently or simultaneously stretched by the difference in peripheral speed between the heating rolls to produce a longitudinally stretched film. is there.
- both ends of the raw film are fixed with two rows of chucks or pins aligned in the flow direction, and the two rows of chucks are heated in a heating furnace including a preheating portion, a stretching portion, and a heat treatment portion.
- This is a method for producing a transversely stretched film by stretching in the transverse direction by widening the interval.
- the raw film is preheated in the machine direction by a series of heating rolls and subsequently or simultaneously stretched longitudinally due to the difference in peripheral speed between the heating rolls. Both ends are fixed by two rows of chucks or pins aligned along the flow direction, and the two rows of chucks are widened in a heating furnace consisting of a preheating section, a stretching section and a heat treatment section, and then stretched in the transverse direction.
- This is a method for producing a biaxially stretched film.
- both ends of the raw film are respectively fixed by two rows of chucks or pins arranged in the flow direction, and the two rows are formed in a heating furnace including a preheating portion, a stretching portion, and a heat treatment portion. This is a method for producing a biaxially stretched film by stretching simultaneously in the longitudinal direction and the transverse direction by widening the chuck interval and the individual chuck intervals in the row.
- the optical film obtained by stretching is subjected to corona treatment or the like as necessary on the surface or slit at both ends, and is usually wound into a roll by a winder.
- the surface protective film for temporarily protecting the surface of the optical film may be wound up in a state of being bonded to one side or both sides, and the film with the pressure-sensitive adhesive layer may be wound on one side or through the pressure-sensitive adhesive layer. You may wind up in the state bonded on both surfaces.
- FIG. 1 is a schematic sectional view showing a preferred example of the composite polarizing plate of the present invention.
- the composite polarizing plate 100 of the present invention includes a polarizing film 101 and an optical film 102 according to the present invention laminated on one surface of the polarizing film 101.
- the composite polarizing plate 100 of the present invention may further include a transparent protective layer 103 on the surface opposite to the surface on which the optical film 102 is laminated.
- the optical film 102 and the transparent protective layer 103 can be bonded to the polarizing film 101 using an adhesive. In this case, the optical film 102 and the transparent protective layer 103 are bonded to the adhesive layer (the adhesive layers 104 and 105 in FIG. 1).
- the stability of the display performance of the liquid crystal display device can be improved by using the optical film of the present invention in which the in-plane retardation value variation over time is suppressed. Moreover, since the composite polarizing plate of this invention uses the optical film of this invention, thickness reduction is achieved.
- the optical film 102 functions as a wave plate or a viewing angle compensation film.
- the angle formed by the slow axis of the optical film 102 and the absorption axis of the polarizing film 101 is appropriately selected according to the function of the optical film 102.
- the angle is 5 to 85 °
- the viewing angle In the case of a compensation film, it is substantially 0 ° or substantially 90 °.
- polarizing film 101 a film obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film and imparting a predetermined polarizing property can be used.
- dichroic dye iodine or a dichroic organic dye is used.
- the polarizing film 101 specifically, an iodine polarizing film in which iodine is adsorbed and oriented on a polyvinyl alcohol resin film, a dye polarizing film in which a dichroic organic dye is adsorbed and oriented on a polyvinyl alcohol resin film, etc. Can be used.
- the polyvinyl alcohol resin constituting the polarizing film 101 can be obtained by saponifying a polyvinyl acetate resin.
- a polyvinyl acetate-based resin in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable therewith is used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids.
- the polyvinyl alcohol resin may be modified, and for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral and the like modified with aldehydes may be used.
- the polarizing film 101 is usually a humidity adjusting step for adjusting the moisture of the polyvinyl alcohol-based resin film, a step of uniaxially stretching the polyvinyl alcohol-based resin film, a dichroic dyeing of the polyvinyl alcohol-based resin film with a dichroic dye. It is manufactured through a step of adsorbing and orienting the dye, a step of treating the polyvinyl alcohol resin film on which the dichroic dye is adsorbing and orienting with an aqueous boric acid solution, and a washing step of washing off the aqueous boric acid solution. Uniaxial stretching can be performed before dyeing, during dyeing, or during boric acid treatment after dyeing.
- uniaxial stretching may be performed in these several steps.
- the method of uniaxial stretching may be a method of stretching uniaxially between rolls having different peripheral speeds, or a method of stretching uniaxially using a hot roll.
- atmosphere may be sufficient
- stretches in the state swollen with the solvent may be sufficient.
- the draw ratio is usually about 4 to 8 times.
- the thickness of the finally obtained polarizing film 101 can be, for example, about 1 to 50 ⁇ m.
- transparent protective layer examples include (meth) acrylic resins such as methyl methacrylate resins, chain polyolefin resins such as polypropylene resins, cyclic polyolefin resins, polyvinyl chloride resins, cellulose resins, and styrene resins.
- the thickness of the transparent protective film is usually 20 to 200 ⁇ m, preferably 20 to 120 ⁇ m.
- the transparent protective layer 103 may be a coating-type transparent protective layer formed by applying and curing a resin composition containing a curable compound that can be cured by irradiation with active energy rays or heating.
- a curable compound the epoxy compound mentioned later can be used conveniently.
- the thickness of the coating type transparent protective layer is, for example, 0.1 to 10 ⁇ m, and preferably 1 to 5 ⁇ m.
- Adhesive layer examples of the adhesive that forms the adhesive layers 104 and 105 responsible for bonding with the optical film 102 and the transparent protective layer include, for example, epoxy-based, acrylic-based, urethane-based, cyanoacrylate-based, or acrylamide-based adhesives. Or in combination. Even if any of these is used, good adhesive force can be obtained, but among them, epoxy adhesives are particularly preferably used because they exhibit particularly excellent adhesive force.
- the adhesive that bonds the optical film 102 and the polarizing film 101 and the adhesive that bonds the transparent protective layer 103 and the polarizing film 101 may be the same or different, It is preferable to use the same type from the viewpoint of simplifying the manufacturing process of the composite polarizing plate and reducing the types of materials used.
- the epoxy adhesive examples include an adhesive made of a curable resin composition containing an epoxy compound that is cured by irradiation with active energy rays.
- the polarizing film and the optical film can be bonded by irradiating the coating layer of the adhesive with active energy rays and curing the curable epoxy compound contained in the adhesive.
- the resulting adhesive layer is composed of a cured product layer of an active energy ray-curable epoxy adhesive. Curing of the epoxy compound by irradiation with this active energy ray is preferably performed by cationic polymerization.
- the epoxy compound used for the adhesive usually has at least two epoxy groups in the molecule.
- the active energy ray is a concept including visible light, ultraviolet rays, X-rays, electron beams, and the like.
- the epoxy compound contained in the curable epoxy resin composition that is an adhesive is preferably one that does not contain an aromatic ring in the molecule.
- An adhesive using an epoxy compound containing no aromatic ring in the molecule is described in, for example, JP2004-245925-A. Examples of such epoxy compounds that do not contain an aromatic ring in the molecule include hydrogenated epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.
- a hydrogenated epoxy compound can be obtained by subjecting an aromatic polyhydroxy compound, which is a raw material for an aromatic epoxy resin, to selective hydrogenation under pressure in the presence of a catalyst, followed by glycidyl etherification.
- aromatic epoxy resins include bisphenol type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether; phenol novolac epoxy resins, cresol novolac epoxy resins, and hydroxy Examples include novolak-type epoxy resins such as benzaldehyde phenol novolac epoxy resins; glycidyl ethers of tetrahydroxyphenylmethane, glycidyl ethers of tetrahydroxybenzophenone, and polyfunctional epoxy resins such as epoxidized polyvinylphenol.
- aromatic polyhydroxy compounds such as bisphenols, which are raw materials for these aromatic epoxy resins, are subjected to the nuclear hydrogenation reaction as described above, and then reacted with epichlorohydrin to obtain a hydrogenated epoxy compound. It is done.
- the hydrogenated epoxy compound hydrogenated bisphenol A glycidyl ether is preferable.
- the alicyclic epoxy compound means an epoxy resin having at least one epoxy group bonded to the alicyclic ring in the molecule.
- “Epoxy group bonded to alicyclic ring” means a bridged oxygen atom —O— in the structure represented by the following formula, wherein m is an integer of 2 to 5.
- a compound in which a group in a form in which one or a plurality of hydrogen atoms in (CH 2 ) m in the above formula are removed is bonded to another chemical structure can be an alicyclic epoxy compound.
- One or more hydrogen atoms in (CH 2 ) m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group.
- the alicyclic epoxy compound used preferably below is specifically illustrated, it is not limited to these compounds.
- examples of the aliphatic epoxy compound include an aliphatic polyhydric alcohol or a polyglycidyl ether of an alkylene oxide adduct thereof. More specifically, 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; glycerin triglycidyl ether; trimethylolpropane triglycidyl ether; polyethylene glycol diglycidyl ether; propylene Diglycidyl ether of glycol; Polyglycidyl of polyether polyol obtained by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol or glycerin Examples include ether.
- the epoxy compound may be used alone or in combination of two or more.
- the epoxy equivalent of the epoxy compound used for the adhesive is usually in the range of 30 to 3,000 g / equivalent, preferably 50 to 1,500 g / equivalent.
- the epoxy equivalent is less than 30 g / equivalent, the flexibility of the composite polarizing plate after curing may be reduced, or the adhesive strength may be reduced.
- it exceeds 3,000 g / equivalent the compatibility with other components contained in the adhesive may be lowered.
- cationic polymerization is preferably used as the curing reaction of the epoxy compound.
- the curable epoxy resin composition which is an adhesive agent contains a cationic polymerization initiator.
- the cationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates an epoxy group polymerization reaction.
- active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams
- the latent that is, a function of initiating polymerization by receiving energy (external stimulus) from others is provided.
- a cationic polymerization initiator that generates a cationic species or a Lewis acid by irradiation of active energy rays and initiates a polymerization reaction of an epoxy group is referred to as a “photo cationic polymerization initiator”.
- the method of curing the adhesive by irradiating active energy rays using a cationic photopolymerization initiator enables curing at room temperature, reducing the need to consider the distortion due to heat resistance or expansion of the polarizing film, and the optical film And it is advantageous in that the transparent protective layer and the polarizing film can be favorably bonded.
- the cationic photopolymerization initiator acts catalytically by light, it is excellent in storage stability and workability even when mixed with an epoxy compound.
- photocationic polymerization initiator examples include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes. These photocationic polymerization initiators may be used alone or in combination of two or more. Among these, aromatic sulfonium salts are particularly preferable because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and thus can provide a cured product having excellent curability and good mechanical strength and adhesive strength. Used.
- photocationic polymerization initiators can be easily obtained as commercial products.
- “Kayarad PCI-220” and “Kayarad PCI-620” Nippon Kayaku Co., Ltd.
- “UVI-6990” manufactured by Union Carbide
- “Adekaoptomer SP-150” and “Adekaoptomer SP-170” manufactured by ADEKA Corporation
- the amount of the cationic photopolymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 part by weight or more, and preferably 15 parts by weight or less with respect to 100 parts by weight of the epoxy compound.
- the curable epoxy resin composition which is an adhesive, can further contain a photosensitizer or a photosensitizer as necessary.
- a photosensitizer By using a photosensitizer, the reactivity of cationic polymerization is improved, and the mechanical strength and adhesive strength of the cured product can be improved.
- the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreductive dyes.
- the photosensitizer is preferably contained within a range of 0.1 to 20 parts by weight in 100 parts by weight of the curable epoxy resin composition.
- naphthalene-based photosensitization aid as the photosensitization aid improves the curability of the adhesive composition as compared with the case where it is not blended.
- the naphthalene photosensitizing assistant is preferably contained in the range of 0.1 to 5 parts by weight in 100 parts by weight of the curable epoxy resin composition.
- the curable epoxy resin composition may contain a compound that promotes cationic polymerization, such as an oxetane compound or a polyol compound.
- the adhesive comprising the curable epoxy resin composition containing the epoxy compound as described above to the polarizing film, the optical film, the adhesive surface of the transparent protective layer, or both adhesive surfaces.
- the composite polarizing plate can be obtained by pasting on the processed surface and curing the uncured adhesive layer by irradiating active energy rays.
- an adhesive coating method for example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
- the adhesive composed of the curable epoxy resin composition can basically be used as a solventless adhesive that does not substantially contain a solvent component, but each coating method has an optimum viscosity range. Therefore, a solvent may be included for viscosity adjustment. It is preferable to use a solvent that dissolves the epoxy resin composition well without degrading the optical performance of the polarizing film.
- a solvent that dissolves the epoxy resin composition well without degrading the optical performance of the polarizing film.
- hydrocarbons represented by toluene esters represented by ethyl acetate, and the like.
- organic solvents such as
- the light source used for irradiation with active energy rays is not particularly limited, but an ultraviolet light source such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a black light lamp, or a metal halide lamp is preferably used.
- the irradiation intensity and irradiation amount of the active energy ray are such that the cationic photopolymerization initiator can be sufficiently activated and do not adversely affect the cured adhesive layer, polarizing film, optical film, and transparent protective layer. Adjust as appropriate.
- the thickness of the adhesive layer after curing is usually 0.1 to 50 ⁇ m, preferably 0.5 to 20 ⁇ m, more preferably 1 to 10 ⁇ m.
- the composite polarizing plate of this invention may have the adhesive layer laminated
- this pressure-sensitive adhesive layer can be suitably used, for example, for bonding with a liquid crystal cell.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer those using a base polymer such as an acrylic ester, methacrylic ester, butyl rubber, or silicone can be used. Among them, one or more (meth) acrylates selected from butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
- a pressure-sensitive adhesive containing a polymer or copolymer having a main structural unit as a base polymer is preferably used. In the base polymer, a polar monomer is usually copolymerized together with the main structural unit.
- Examples of the polar monomer include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, Mention may be made of monomers having a carboxyl group, a hydroxyl group, an amino group, an epoxy group and the like, such as glycidyl (meth) acrylate.
- the pressure-sensitive adhesive usually contains one or more crosslinking agents in addition to the base polymer.
- Examples of the crosslinking agent include divalent or polyvalent metal salts that form a carboxylic acid metal salt with a carboxyl group, and polyisocyanate compounds that form an amide bond with a carboxyl group.
- the thickness of the pressure-sensitive adhesive layer can be about 3 to 50 ⁇ m.
- the optical film surface may be subjected to a surface treatment such as a corona treatment.
- a surface treatment such as a corona treatment.
- a viewing angle compensation film can be laminated on the optical film.
- the pressure-sensitive adhesive layer used for bonding with the liquid crystal cell can be provided on the viewing angle compensation film.
- Measurement of retardation value of optical film Measurement was performed at a measurement wavelength of 590 nm using a phase difference measurement device KOBRA-WR (manufactured by Oji Scientific Instruments).
- the in-plane retardation value fluctuation ⁇ R 0 is 140 / R to the difference between R 0 2 and R 0 1 in order to eliminate the influence of the magnitude of the in-plane retardation value.
- the fluctuation rate of the in-plane retardation value was converted when the in-plane retardation value immediately after the production was 140 nm.
- alicyclic saturated hydrocarbon resin Arakawa Chemical Industries
- Stretching is performed at a line speed of 5 m / min, first through a preheating zone in which the temperature is adjusted to 144 ° C., and then in the stretching zone in which the temperature is adjusted to 134 ° C., the final draw ratio is 5 times. It was done.
- the in-plane retardation value R 0 1, thickness direction retardation value R th , Nz coefficient, and thickness immediately after production of the obtained stretched film (optical film) were measured. Further, as the stability evaluation of the in-plane retardation value, the in-plane retardation value R 0 2 21 days after the production was measured, and the in-plane retardation value variation ⁇ R 0 was obtained by the above formula (V).
- Example 2 Except that the amount of the polypropylene resin and alicyclic saturated hydrocarbon resin used is 80 parts and 20 parts, respectively, and the temperature of the preheating zone and the stretching zone of the tenter transverse stretching machine is adjusted to 139 ° C. and 129 ° C., respectively. An optical film was produced in the same manner as in Example 1, and the retardation characteristics and thickness were measured.
- alicyclic saturated hydrocarbon resin Arakawa Chemical Industries ( Co., Ltd. “
- This raw film is preheated and then stretched 1.5 times in the longitudinal direction at a stretching temperature of 138 ° C. due to the difference in roll peripheral speed of the longitudinal stretching machine, followed by a line speed of 2 m / min.
- the film is passed through a preheating zone adjusted to 149 ° C., followed by transverse stretching in a drawing zone adjusted to a temperature of 139 ° C. so that the final draw ratio is 4.4 times.
- About the obtained optical film, retardation characteristics and thickness were measured in the same manner as in Example 1.
- Example 4 The amount of the polypropylene resin and alicyclic saturated hydrocarbon resin used is 80 parts and 20 parts, respectively, the stretching temperature by the longitudinal stretching machine is 133 ° C., the preheating zone of the tenter transverse stretching machine and the temperature of the stretching zone are 144 respectively.
- An optical film was produced in the same manner as in Example 3 except that the temperature was adjusted to ° C and 134 ° C, and the retardation characteristics and thickness were measured.
- Stretching is performed at a line speed of 5 m / min, first through a preheating zone in which the temperature is adjusted to 136 ° C., and then in the stretching zone in which the temperature is adjusted to 126 ° C., the final draw ratio is 4 times. It was done. About the obtained stretched film (optical film), the retardation characteristics and thickness were measured in the same manner as in Example 1.
- ⁇ Comparative Example 2> A 110 ⁇ m-thick original fabric film obtained by the same method as in Comparative Example 1 was preheated, and then stretched 1.7 times in the longitudinal direction at a stretching temperature of 125 ° C. due to the difference in the peripheral speed of the longitudinal stretching machine. First, the film was passed through a preheating zone whose temperature was adjusted to 136 ° C. at a line speed of 2 m / min by a stretching machine, and then the final stretching ratio was 3.0 times in a stretching zone whose temperature was adjusted to 126 ° C. Thus, transverse stretching was performed to obtain a stretched film (optical film). About the obtained optical film, retardation characteristics and thickness were measured in the same manner as in Example 1.
- Table 1 shows the retardation characteristics and thicknesses of the optical films of Examples 1-4 and Comparative Examples 1-2.
- the optical films of Examples 1 and 2 have comparatively different stretching formats and thicknesses as well as the optical films of Comparative Example 1 having the same stretching format and the same thickness.
- the in-plane retardation value variation ⁇ R 0 is small, and the stability of the in-plane retardation value is excellent.
- the optical films of Examples 3 to 4 have the same stretching method and the same thickness as that of Comparative Example 2, but also the optical film of Comparative Example 1 having a different stretching method and thickness.
- the in-plane retardation value fluctuation ⁇ R 0 is small, and the stability of the in-plane retardation value is excellent.
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Abstract
Description
[1] ポリプロピレン系樹脂と脂環族飽和炭化水素樹脂とを含有する樹脂フィルムからなり、面内位相差値R0が40~500nmの範囲内であり、かつ、厚み方向の位相差値Rthが20~500nmの範囲内であり、前記樹脂フィルムの面内遅相軸方向の屈折率をnx、面内進相軸方向の屈折率をny、厚み方向の屈折率をnzとするとき、式:Nz係数=(nx−nz)/(nx−ny)で定義されるNz係数が0.9~3の範囲内である光学フィルム。
[2] 厚みが35μm以下である[1]に記載の光学フィルム。
[4] 上記脂環族飽和炭化水素樹脂の軟化点が110~145℃の範囲内である[1]~[3]のいずれかに記載の光学フィルム。
[6] 上記ポリプリピレン系樹脂が、実質的にプロピレンの単独重合体からなるポリプロピレン系樹脂である[1]~[4]のいずれかに記載の光学フィルム。
[8] 上記光学フィルムが積層される面とは反対側の面に透明保護層をさらに備える[7]に記載の複合偏光板。
[9] 上記光学フィルムは、活性エネルギー線硬化性エポキシ系接着剤の硬化物層を介して偏光フィルムに積層されている[7]または[8]に記載の複合偏光板。
本発明の光学フィルムは、ポリプロピレン系樹脂と脂環族飽和炭化水素樹脂とを含有する複屈折性の樹脂フィルムであり、後で詳述するように、典型的には、ポリプロピレン系樹脂と脂環族飽和炭化水素樹脂とを含有する原反フィルムを一軸延伸または二軸延伸することにより作製される位相差が発現された延伸フィルムである。
Rth=[(nx+ny)/2−nz]×d (II)
Nz=(nx−nz)/(nx−ny) (III)
また、これらの式(I)~(III)から、Nz係数と面内位相差値R0、および厚み方向の位相差値Rthとの関係は、次式(IV):
Nz=Rth/R0+0.5 (IV)
で表すことができる。
本発明の光学フィルムを構成する脂環族飽和炭化水素樹脂は、石油樹脂に分類される樹脂である。石油樹脂とは、石油類の熱分解により生成する分解油留分を重合し固化させた熱可塑性樹脂であって、たとえば、C5留分を原料とした脂肪族系石油樹脂;C9留分を原料とした芳香族系石油樹脂;C5留分とC9留分の2種を共重合して得られる共重合系石油樹脂;ならびに、脂肪族系石油樹脂、芳香族系石油樹脂、または共重合系石油樹脂を水素化した水素化系石油樹脂等が挙げられる。
脂環族飽和炭化水素樹脂は典型的には、シクロペンタジエン(CPD)あるいはジシクロペンタジエン(DCPD)を原料として得られる重合体か、芳香族系石油樹脂を水素化して得られる水素化系石油樹脂であり、例えば下記(1)~(3)の構造式で表すことができる。
本発明の光学フィルムを構成するポリプロピレン系樹脂は、実質的にプロピレンの単独重合体からなる樹脂であってもよいし、プロピレンと他の共重合性コモノマーとの共重合体からなる樹脂であってもよい。プロピレンの単独重合体は、プロピレンと他の共重合性コモノマーとの共重合体に比べて、結晶化度がより高くなるため、フィルム剛性と降伏強度をより高くすることができる点において有利である。したがって、ポリプロピレン系樹脂として、実質的にプロピレンの単独重合体からなる樹脂を用いることにより、光学フィルム作製工程、偏光板化工程での取り扱い性をより向上させることが可能となる。
1−ペンテン、2−メチル−1−ブテン、3−メチル−1−ブテン(以上C5);
1−ヘキセン、2−エチル−1−ブテン、2,3−ジメチル−1−ブテン、2−メチル−1−ペンテン、3−メチル−1−ペンテン、4−メチル−1−ペンテン、3,3−ジメチル−1−ブテン(以上C6);
1−ヘプテン、2−メチル−1−ヘキセン、2,3−ジメチル−1−ペンテン、2−エチル−1−ペンテン、2−メチル−3−エチル−1−ブテン(以上C7);
1−オクテン、5−メチル−1−ヘプテン、2−エチル−1−ヘキセン、3,3−ジメチル−1−ヘキセン、2−メチル−3−エチル−1−ペンテン、2,3,4−トリメチル−1−ペンテン、2−プロピル−1−ペンテン、2,3−ジエチル−1−ブテン(以上C8);
1−ノネン(C9);1−デセン(C10);1−ウンデセン(C11);1−ドデセン(C12);1−トリデセン(C13);1−テトラデセン(C14);1−ペンタデセン(C15);1−ヘキサデセン(C16);1−ヘプタデセン(C17);1−オクタデセン(C18);1−ノナデセン(C19)など。
好ましい共重合体として、プロピレン/エチレン共重合体やプロピレン/1−ブテン共重合体を挙げることができる。プロピレン/エチレン共重合体やプロピレン/1−ブテン共重合体において、エチレンユニットの含有量や1−ブテンユニットの含有量は、たとえば、「高分子分析ハンドブック」(1995年、紀伊国屋書店発行)の第616頁に記載されている方法により赤外線(IR)スペクトル測定を行ない、求めることができる。
MFRがこの範囲にあるポリプロピレン系樹脂を用いることにより、押出機に大きな負荷をかけることなく、樹脂組成および膜厚が均一な光学フィルム作製用原反フィルムを得ることができる。
(1)マグネシウム、チタン、およびハロゲンを必須成分とする固体触媒成分からなるTi−Mg系触媒、
(2)マグネシウム、チタン、およびハロゲンを必須成分とする固体触媒成分に、有機アルミニウム化合物と、必要に応じて電子供与性化合物等の第三成分とを組み合わせた触媒系、
(3)メタロセン系触媒など。
本発明の光学フィルムは、ポリプロピレン系樹脂と脂環族飽和炭化水素樹脂とを含有する樹脂組成物から原反フィルムを作製し、得られた原反フィルムを延伸して位相差を発現させることにより得ることができる。
原反フィルムは、ポリプロピレン系樹脂と脂環族飽和炭化水素樹脂とを含有する樹脂組成物を製膜することにより作製される。当該樹脂組成物の調製方法は、少なくとも脂環族飽和炭化水素樹脂が、得られる樹脂組成物中に均一に分散される方法である限り特に限定されるものではなく、たとえば、ポリプロピレン系樹脂を調製する重合工程における重合反応途中または重合反応直後の重合反応混合物に脂環族飽和炭化水素樹脂を添加する方法を挙げることができる。脂環族飽和炭化水素樹脂は、溶剤に溶解した溶液として添加してもよいし、容易に分散し得るように粉末状に粉砕し、粉体として添加してもよいし、加熱して溶融状態で添加してもよい。
添加物としては、たとえば、酸化防止剤、紫外線吸収剤、帯電防止剤、滑剤、造核剤、防曇剤、アンチブロッキング剤などを挙げることができる。上記樹脂組成物は、1種または2種以上の添加剤を含有することができる。
(2)Tダイのリップ幅が1500mm以上のとき:Tダイの厚み方向長さ>220mm、
(3)Tダイのリップ幅が1500mm未満のとき:Tダイの高さ方向長さ>250mm、
(4)Tダイのリップ幅が1500mm以上のとき:Tダイの高さ方向長さ>280mm。
本発明の光学フィルムは、上記原反フィルムを延伸して位相差を発現させることにより得ることができる。延伸方法は特に限定されず、縦方向一軸延伸、横方向一軸延伸、逐次二軸延伸または同時二軸延伸などを採用することができる。
図1は、本発明の複合偏光板の好ましい一例を示す概略断面図である。図1に示されるように、本発明の複合偏光板100は、偏光フィルム101と、偏光フィルム101の片面に積層された本発明に係る光学フィルム102とを備える。本発明の複合偏光板100は、光学フィルム102が積層される面とは反対側の面に透明保護層103をさらに備えていてもよい。光学フィルム102および透明保護層103は接着剤を用いて偏光フィルム101に貼合することができ、この場合、光学フィルム102および透明保護層103は接着剤層(図1における接着剤層104,105)を介して偏光フィルム101に積層される。本発明の複合偏光板によれば、経時的な面内位相差値変動が抑制された本発明の光学フィルムを用いていることにより液晶表示装置の表示性能の安定性を向上させることができる。また、本発明の複合偏光板は、本発明の光学フィルムを用いているため、薄型化が達成されている。
偏光フィルム101としては、ポリビニルアルコール系樹脂フィルムに二色性色素を吸着配向させて、所定の偏光特性を付与したものを用いることができる。二色性色素としては、ヨウ素や二色性有機染料が用いられる。すなわち、偏光フィルム101として、具体的には、ポリビニルアルコール系樹脂フィルムにヨウ素を吸着配向させたヨウ素系偏光フィルム、ポリビニルアルコール系樹脂フィルムに二色性有機染料を吸着配向させた染料系偏光フィルムなどを用いることができる。
透明保護層103としては、メタクリル酸メチル系樹脂等の(メタ)アクリル系樹脂、ポリプロピレン系樹脂等の鎖状ポリオレフィン系樹脂、環状ポリオレフィン系樹脂、ポリ塩化ビニル系樹脂、セルロース系樹脂、スチレン系樹脂、アクリロニトリル・ブタジエン・スチレン系共重合樹脂、アクリロニトリル・スチレン系共重合樹脂、ポリ酢酸ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリアミド系樹脂、ポリアセタール系樹脂、ポリカーボネート系樹脂、変性ポリフェニレンエーテル系樹脂、ポリブチレンテフタレート系樹脂、ポリエチレンテフタレート系樹脂、ポリスルホン系樹脂、ポリエーテルスルホン系樹脂、ポリアリレート系樹脂、ポリアミドイミド系樹脂、ポリイミド系樹脂などからなる透明保護フィルムを用いることができる。透明保護フィルムの厚みは、通常、20~200μmであり、好ましくは20~120μmである。
硬化性化合物としては、後述するエポキシ化合物を好適に用いることができる。塗布型透明保護層の厚みは、たとえば0.1~10μmであり、好ましくは1~5μmである。透明保護層103が塗布型透明保護層である場合、接着剤層105を介在させることなく、透明保護層103を直接偏光フィルム101上に積層させることができる。
光学フィルム102および透明保護層との貼合を担う接着剤層104,105を形成する接着剤としては、たとえば、エポキシ系、アクリル系、ウレタン系、シアノアクリレート系もしくはアクリルアミド系接着剤を、それぞれ単独でまたは複数組み合わせて用いることができる。これらいずれを用いても良好な接着力が得られるが、中でもエポキシ系接着剤は特に優れた接着力を示すため、好ましく用いられる。なお、光学フィルム102と偏光フィルム101とを接着する接着剤と、透明保護層103と偏光フィルム101とを接着する接着剤とは、同種であってもよいし、異種であってもよいが、複合偏光板の製造工程の簡略化および使用材料種の削減の観点から同種とすることが好ましい。
3,4−エポキシ−6−メチルシクロヘキシルメチル 3,4−エポキシ−6−メチルシクロヘキサンカルボキシレート、
エチレンビス(3,4−エポキシシクロヘキサンカルボキシレート)、
ビス(3,4−エポキシシクロヘキシルメチル)アジペート、
ビス(3,4−エポキシ−6−メチルシクロヘキシルメチル)アジペート、
ジエチレングリコールビス(3,4−エポキシシクロヘキシルメチルエーテル)、
エチレングリコールビス(3,4−エポキシシクロヘキシルメチルエーテル)、
2,3,14,15−ジエポキシ−7,11,18,21−テトラオキサトリスピロ−[5.2.2.5.2.2]ヘンイコサン(3,4−エポキシシクロヘキサンスピロ−2’,6’−ジオキサンスピロ−3’’,5’’−ジオキサンスピロ−3’’’,4’’’−エポキシシクロヘキサンとも命名できる化合物である)、
3−(3,4−エポキシシクロヘキシル)−8,9−エポキシ−1,5−ジオキサスピロ[5.5]ウンデカン、
4−ビニルシクロヘキセンジオキサイド、
ビス−2,3−エポキシシクロペンチルエーテル、
ジシクロペンタジエンジオキサイドなど。
本発明の複合偏光板は、光学フィルム上に積層された粘着剤層を有していてもよい。この粘着剤層は、複合偏光板を液晶表示装置に適用する場合において、たとえば液晶セルとの貼合に好適に用いることができる。
デジタルマイクロメーターMH−15M((株)ニコン製)を用いて測定した。
位相差測定装置KOBRA−WR(王子計測機器(株)製)を用いて、測定波長590nmで測定した。
上記位相差値の測定と同様にして、製造直後および製造後21日後の面内位相差値を測定した。面内位相差値変動ΔR0は、製造直後の面内位相差値R01および製造後21日後の面内位相差値R02から下記式(V):
ΔR0=(R02−R01)×140/R01 (V)
によって求められる。式(V)に示されるように、面内位相差値変動ΔR0は、面内位相差値の大きさによる影響を排除するために、R02とR01との差に140/R01をかけることにより、面内位相差値の変動率を製造直後の面内位相差値が140nmである場合に換算したものとした。
ポリプロピレン系樹脂(住友化学(株)製「ノーブレンFS2011DG3」、MFR=約2.3g/10分、エチレン含量=約0.5%)90部と、脂環族飽和炭化水素樹脂(荒川化学工業(株)製「アルコン P−125」、軟化点125℃)10部とを単軸押出機を用いて溶融混練し、ついで樹脂温度250℃で溶融押出を行ない、20℃の冷却ロールにて急冷することにより厚さ40μmの原反フィルムを得た。この原反フィルムを、テンター横延伸機で横一軸に延伸した。延伸は、ライン速度5m/分で、まず温度が144℃に調節された予熱ゾーンに通し、続いて、温度が134℃に調節された延伸ゾーンで、最終の延伸倍率が5倍となるようにして行なった。得られた延伸フィルム(光学フィルム)の製造直後の面内位相差値R01、厚み方向位相差値Rth、Nz係数および厚みを測定した。また、面内位相差値の安定性評価として、製造後21日後の面内位相差値R02を測定し、上記式(V)により面内位相差値変動ΔR0を求めた。
ポリプロピレン系樹脂および脂環族飽和炭化水素樹脂の使用量をそれぞれ、80部、20部とし、テンター横延伸機の予熱ゾーン、延伸ゾーンの温度をそれぞれ、139℃、129℃に調節したこと以外は実施例1と同様にして光学フィルムを作製し、位相差特性および厚みを測定した。
ポリプロピレン系樹脂(住友化学(株)製「ノーブレンFS2011DG3」、MFR=約2.3g/10分、エチレン含量=約0.5%)90部と、脂環族飽和炭化水素樹脂(荒川化学工業(株)製「アルコン P−125」、軟化点125℃)10部とを二軸造粒機で溶融混練し、ペレットを得た後、単軸押出機を用いて樹脂温度250℃で溶融押出を行ない、20℃の冷却ロールにて急冷することにより厚さ110μmの原反フィルムを得た。この原反フィルムを、予熱後、縦延伸機のロール周速差により延伸温度138℃で縦方向に1.5倍延伸し、引き続きテンター横延伸機にてライン速度2m/分で、まず温度が149℃に調節された予熱ゾーンに通し、続いて、温度が139℃に調節された延伸ゾーンで、最終の延伸倍率が4.4倍となるようにして横延伸を行ない、延伸フィルム(光学フィルム)を得た。得られた光学フィルムについて、実施例1と同様に位相差特性および厚みを測定した。
ポリプロピレン系樹脂および脂環族飽和炭化水素樹脂の使用量をそれぞれ、80部、20部とし、縦延伸機による延伸温度を133℃、テンター横延伸機の予熱ゾーン、延伸ゾーンの温度をそれぞれ、144℃、134℃に調節したこと以外は実施例3と同様にして光学フィルムを作製し、位相差特性および厚みを測定した。
プロピレン/エチレンランダム共重合体からなるポリプロピレン系樹脂(住友化学(株)製「ノーブレンW151」、MFR=約2.5g/10分、エチレン含量=約5%)を二軸押出機を用いて溶融混練し、樹脂温度250℃で溶融押出を行ない、20℃の冷却ロールにて急冷することにより、厚さ40μmの原反フィルムを得た。この原反フィルムを、テンター横延伸機で横一軸に延伸した。延伸は、ライン速度5m/分で、まず温度が136℃に調節された予熱ゾーンに通し、続いて、温度が126℃に調節された延伸ゾーンで、最終の延伸倍率が4倍となるようにして行なった。得られた延伸フィルム(光学フィルム)について、実施例1と同様に位相差特性および厚みを測定した。
比較例1と同様の方法によって得られた厚さ110μmの原反フィルムを、予熱後、縦延伸機のロール周速差により延伸温度125℃で縦方向に1.7倍延伸し、引き続きテンター横延伸機にてライン速度2m/分で、まず温度が136℃に調節された予熱ゾーンに通し、続いて、温度が126℃に調節された延伸ゾーンで、最終の延伸倍率が3.0倍となるようにして横延伸を行ない、延伸フィルム(光学フィルム)を得た。得られた光学フィルムについて、実施例1と同様に位相差特性および厚みを測定した。
101 偏光フィルム、
102 光学フィルム、
103 透明保護層、
104,105 接着剤層。
Claims (9)
- ポリプロピレン系樹脂と脂環族飽和炭化水素樹脂とを含有する樹脂フィルムからなり、
面内位相差値R0が40~500nmの範囲内であり、かつ、厚み方向の位相差値Rthが20~500nmの範囲内であり、
前記樹脂フィルムの面内遅相軸方向の屈折率をnx、面内進相軸方向の屈折率をny、厚み方向の屈折率をnzとするとき、式:Nz係数=(nx−nz)/(nx−ny)で定義されるNz係数が0.9~3の範囲内である、光学フィルム。 - 厚みが35μm以下である請求の範囲1に記載の光学フィルム。
- ポリプロピレン系樹脂と脂環族飽和炭化水素樹脂とを含有する樹脂フィルムが、ポリプロピレン系樹脂と脂環族飽和炭化水素樹脂とを含有する樹脂組成物の延伸フィルムであり、
前記樹脂組成物は、前記脂環族飽和炭化水素樹脂を0.1~30重量%含有する請求の範囲1または2に記載の光学フィルム。 - 前記脂環族飽和炭化水素樹脂の軟化点が110~145℃の範囲内である請求の範囲1~3のいずれかに記載の光学フィルム。
- 前記ポリプロピレン系樹脂が、10重量%以下のエチレンユニットを含有するプロピレンとエチレンとの共重合体からなるポリプロピレン系樹脂である請求の範囲1~4のいずれかに記載の光学フィルム。
- 前記ポリプロピレン系樹脂が、実質的にプロピレンの単独重合体からなるポリプロピレン系樹脂である請求の範囲1~4のいずれかに記載の光学フィルム。
- 偏光フィルムと、偏光フィルムの片面に積層された請求の範囲1~6のいずれかに記載の光学フィルムとを備える複合偏光板。
- 前記光学フィルムが積層される面とは反対側の面に透明保護層をさらに備える請求の範囲7に記載の複合偏光板。
- 前記光学フィルムは、活性エネルギー線硬化性エポキシ系接着剤の硬化物層を介して前記偏光フィルムに積層されている請求の範囲7または8に記載の複合偏光板。
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KR101392347B1 (ko) | 2013-05-15 | 2014-05-12 | 신화인터텍 주식회사 | 복합 광학 시트 및 이를 포함하는 광원 어셈블리 |
CN106415341B (zh) * | 2014-05-30 | 2020-03-17 | 住友化学株式会社 | 带粘合剂的偏振板及液晶显示装置 |
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WO2015129851A1 (ja) * | 2014-02-28 | 2015-09-03 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム |
JPWO2015129851A1 (ja) * | 2014-02-28 | 2017-03-30 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム |
JP2019147953A (ja) * | 2014-02-28 | 2019-09-05 | 東レ株式会社 | 二軸配向ポリプロピレンフィルム |
JP2017173427A (ja) * | 2016-03-22 | 2017-09-28 | 日東電工株式会社 | 表面保護フィルム付偏光フィルム、及び偏光フィルムの製造方法 |
WO2017164065A1 (ja) * | 2016-03-22 | 2017-09-28 | 日東電工株式会社 | 表面保護フィルム付偏光フィルム、及び偏光フィルムの製造方法 |
US11204447B2 (en) | 2016-03-22 | 2021-12-21 | Nitto Denko Corporation | Surface-protective film-attached polarizing film, and method for producing polarizing film |
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JP5582466B2 (ja) | 2014-09-03 |
KR20120107098A (ko) | 2012-09-28 |
JP2011113026A (ja) | 2011-06-09 |
TW201124276A (en) | 2011-07-16 |
CN102667547A (zh) | 2012-09-12 |
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