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WO2012140901A1 - Procédé de production de composition de résine, film optique, plaque polarisante et dispositif d'affichage à cristaux liquides - Google Patents

Procédé de production de composition de résine, film optique, plaque polarisante et dispositif d'affichage à cristaux liquides Download PDF

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Publication number
WO2012140901A1
WO2012140901A1 PCT/JP2012/002557 JP2012002557W WO2012140901A1 WO 2012140901 A1 WO2012140901 A1 WO 2012140901A1 JP 2012002557 W JP2012002557 W JP 2012002557W WO 2012140901 A1 WO2012140901 A1 WO 2012140901A1
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Prior art keywords
resin
optical film
resin composition
acrylic
film
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English (en)
Japanese (ja)
Inventor
大介 北條
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Konica Minolta Advanced Layers Inc
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Konica Minolta Advanced Layers Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for producing a resin composition containing an acrylic resin and a cellulose ester resin, and an optical film produced by the production method.
  • the present invention also relates to a polarizing plate and a liquid crystal display device provided with the optical film.
  • a liquid crystal display device is composed of a liquid crystal cell in which a transparent electrode, a liquid crystal layer, a color filter and the like are sandwiched between glass plates, and two polarizing plates provided on both sides thereof.
  • Each polarizing plate has a configuration in which a polarizer (also referred to as a “polarizing film”) is sandwiched between two optical films (polarizer protective film).
  • a polarizer also referred to as a “polarizing film”
  • polarizer protective film As such an optical film, a cellulose ester film is usually used.
  • liquid crystal display devices have diversified. Applications include, for example, use as a large display installed in a street or shop, use as an advertising display in a public place using a display device called digital signage, and the like.
  • display devices such as liquid crystal display devices have become active devices in various places. For example, they have been introduced into environmental test rooms that actively create inferior environments in the field of industrial research. Has been. Therefore, the durability of display device (display) members such as optical films is increasingly required.
  • an optical film in which a cellulose ester resin and an acrylic resin are mixed is suitably used in an inferior use environment such as direct sunlight, rainy weather, and high temperature such as outdoor digital signage or in-vehicle use (see, for example, Patent Document 1). ).
  • the present invention has been made in view of the above-described conventional problems, and a method for producing a resin composition having improved compatibility between an acrylic resin and a cellulose ester resin, an optical film obtained by the production method, a polarizing plate, and a liquid crystal
  • An object is to provide a display device.
  • a method for producing a resin composition according to one aspect of the present invention is a method for producing a resin composition containing an acrylic resin and a cellulose ester resin, wherein the acrylic resin and the cellulose ester resin are mixed in the presence of a supercritical fluid. And a step of discharging the supercritical fluid from an extruder, and a step of molding the molten resin composition obtained by the melt-kneading.
  • FIG. 1 is a schematic diagram of an apparatus for preparing a molten resin composition of an acrylic resin and a cellulose ester resin.
  • FIG. 2 is a schematic diagram of an apparatus for producing an acrylic resin / cellulose ester resin-containing film.
  • the method for producing a resin composition of the present invention is a method for producing a resin composition containing an acrylic resin and a cellulose ester resin, wherein the acrylic resin and the cellulose ester resin are melt-kneaded in the presence of a supercritical fluid. And a step of discharging the supercritical fluid from an extruder, and a step of molding the molten resin composition obtained by the melt-kneading.
  • the molten resin composition is formed into a film shape, and the steps from extrusion to conveyance / winding of the molten resin composition are continuously performed. It is preferable that it is an aspect to perform.
  • the production method of the present invention can be suitably used as a production method for optical films.
  • the optical film can be suitably included in a polarizing plate and a liquid crystal display device.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the method for producing a resin composition of the present invention is a method for producing a resin composition containing an acrylic resin and a cellulose ester resin, wherein the acrylic resin and the cellulose ester resin are melt-kneaded in the presence of a supercritical fluid. And a step of discharging the supercritical fluid from an extruder, and a step of molding the molten resin composition obtained by the melt-kneading.
  • supercritical fluid refers to a fluid that is in a state of being above the critical temperature and above the critical pressure.
  • a supercritical fluid can be understood as a high-density fluid having high kinetic energy, and exhibits a liquid behavior in terms of dissolving a solute, and a gas behavior in terms of density variability.
  • Supercritical fluids have important properties in that they are low-viscosity, highly diffusive, and have excellent permeability to solid materials (see: "Science and Technology of Supercritical Fluids", supervised by Shozaburo Saito, Sankyo Business, 1996. ).
  • phase diagram phase diagram showing the transition of the gas-liquid solid tristate
  • supercritical region the temperature / pressure region that gives the supercritical fluid
  • a high-density region in a temperature range slightly lower than the critical temperature is generally called a subcritical region.
  • the subcritical region has a temperature equal to or higher than the boiling point of the solvent and a pressure of 10 kgf / cm 2.
  • the region is defined as (1.013 MPa) or more.
  • the substance When the temperature and pressure are increased for a certain substance, the substance becomes a fluid having a property intermediate between a liquid and a gas when a certain condition is satisfied.
  • a substance in a region exceeding the critical temperature (also referred to as “supercritical temperature”) Tc and the critical pressure (also referred to as “supercritical pressure”) Pc is referred to as a supercritical fluid, and this state is referred to as a supercritical state.
  • the supercritical fluid in the supercritical state has a diffusion coefficient more than 100 times that of a normal liquid and has a viscosity comparable to that of a gas.
  • Supercritical fluids in the supercritical state are widely used in extraction processes for foods, fragrances and pharmaceuticals, in the molding process of fine ceramics, in the production of ultrafine foamed polymers, decomposition of refractory compounds and harmful substances, and recovery of raw materials. Applied. In these applications, the property that a material in a supercritical state diffuses into another material is used.
  • the present inventor has intensively studied a method for dissolving an acrylic resin and a cellulose ester resin in a uniform state, and conventionally, a cellulose ester resin or the like dissolved in a large amount of an organic solvent such as methylene chloride or methyl acetate. Can be dissolved in the supercritical fluid by using the supercritical fluid, and the volatile components can be removed together by volatilizing the supercritical fluid.
  • the present inventors have found that the breakage during film formation due to the influence of the nonuniformity of the agent can be remarkably reduced, and that variations in the optical properties of the finished film can be improved, and the present invention has been completed.
  • the present inventor has found that a supercritical fluid can be used even when a substance is placed in a state exceeding either Tc or Pc, even if the region does not exceed both Tc and Pc (region beyond the supercritical point). It was confirmed that the same behavior was exhibited and the same effect was exhibited.
  • either the region exceeding Tc or the region exceeding Pc, or the region above the supercritical point exceeding both the regions of Tc and Pc is collectively referred to as “supercritical region”.
  • a state in which a substance is in that region is called a “supercritical state”.
  • the fluid generated in this region is collectively referred to as “supercritical fluid”.
  • a substance that becomes a supercritical fluid may be referred to as “supercritical fluid” or “supercritical substance”.
  • the supercritical material is normally a gas or a liquid. Typical examples are air (-140.7, 3.77), methane (-82.6, 4.60), ethylene (9.2, 5.04), carbon dioxide (31.1, 7 .38), ethane (32.1, 4.87), propane (96.7, 4.25), ammonia (132.4, 11.28), butane (152.0, 3.80), methanol ( 239.4, 8.09), ethanol (240.7, 6.14), benzene (289.0, 4.90), toluene (318.6, 4.11), water (374.1, 22.2. 12) and the like.
  • the numerical values in parentheses indicate Tc (° C.) and Pc (MPa), respectively.
  • the supercritical material is not particularly limited.
  • the supercritical material ethylene, carbon dioxide, ethane, and propane are preferable from the viewpoint of Tc and Pc, and the temperature and pressure are within a range that is easy to use, tasteless, odorless, nonflammability, chemical stability, Carbon dioxide is particularly preferred from the viewpoints of resources, low cost, and no supercritical material remaining in the product. Carbon dioxide is generally used for applications such as extraction of heavy oil from coal, extraction of residual monomers from polymers, and spray solvents.
  • Carbon dioxide has a critical temperature of 31.1 ° C., a critical pressure of 75.3 kgf / cm 2 (7.38 MPa), is relatively easy to handle, is an inert gas at atmospheric pressure, remains Is suitable for the reason that it is harmless to the human body and a high-purity fluid is inexpensive and easily available.
  • the pressure of carbon dioxide in the supercritical state (including subcritical state) used in the present invention is 80 to 500 kgf / cm 2 (7.8 to 49 MPa), preferably 90 to 400 kgf / cm 2 (8.8 to 39 MPa), more preferably 100 to 200 kgf / cm 2 (9.8 to 19.6 MPa).
  • the temperature of the carbon dioxide gas in the supercritical state is 32 to 200 ° C., preferably 35 to 100 ° C., more preferably 40 to 80 ° C. Within these ranges, a supercritical state (including a subcritical state) is preferably obtained by appropriately selecting and combining the temperature and pressure.
  • solubilizing agent one kind or two or more kinds of lower alcohol, glycol, glycol ether and the like may be used in combination.
  • the supercritical fluid separates the resin molecules at the molecular level of the resin, so that the solvation of the solvent is promoted and a substantially uniform solution is obtained. Is possible.
  • the solubility can be improved not only with a good solvent but also with a solvent that cannot normally be a good solvent.
  • a resin that is difficult to dissolve such as a heat resistant resin
  • a solution can be obtained by dissolving in a supercritical state.
  • crystallization is likely to be hindered even when crystals grow due to the presence of impurities in the solution.
  • the solution viscosity is low in the supercritical state, and can be easily transported and filtered, and can be dissolved by adding a plasticizer instead of a solvent as described above. Therefore, the object can be easily achieved in the use which has been difficult.
  • the concentration of the resin in the solution (the mass ratio of the resin to the mass of the solution) is 5 to 60% by mass, preferably 10 to 50% by mass.
  • FIG. 1 is a schematic view of an apparatus for preparing a molten resin composition (solution) containing an acrylic resin and a cellulose ester resin.
  • the apparatus of FIG. 1 is a batch type apparatus, and for example, carbon dioxide can be used as a supercritical material.
  • the pressure-resistant dissolution vessel 6 used in the present invention can be used without limitation as long as it has a pressure resistance of about 50 to 500 atm.
  • the pressure-resistant dissolution vessel 6 only needs to be able to withstand 150 atm when carbon dioxide is used as a supercritical substance.
  • the order of introducing the acrylic resin, cellulose ester resin, solvent, other additives, supercritical material, filling gas, etc. into the pressure-resistant dissolution vessel 6 is not particularly limited, but the acrylic resin and cellulose ester resin may be introduced first. preferable.
  • Acrylic resin and cellulose ester resin followed by a solvent or other additive (the charging means is not shown in FIG. 1), and the air in the pressure-resistant dissolution vessel 6 is replaced with nitrogen or carbon dioxide gas. Then, the melting temperature is heated to be higher than the supercritical temperature of the supercritical substance (the heating means is not shown in FIG. 1).
  • the carbon dioxide gas is introduced from the carbon dioxide cylinder 1 into the pressurizing device 3 through the conduit 2, is heated by the heater (heat exchanger) 4 to become a supercritical fluid, and is introduced into the pressure-resistant dissolution vessel 6 through the valve 5. .
  • the valve 5 is closed.
  • the solvent mixed with the supercritical fluid, the acrylic resin and the cellulose ester resin are stirred for a predetermined time. (The stirring means is not shown in FIG. 1) During stirring, carbon dioxide is maintained in a supercritical state.
  • the control valve 7 is opened.
  • the uniform solution is introduced into the filtration device 9 through the conduit 8 while being filtered while maintaining the supercritical pressure and temperature, and then introduced into the gas-liquid separation vessel 11 through the pressure reducing valve 10.
  • Carbon dioxide gas is introduced into the decompression regulator 14 via the valve 12 and the conduit 13 and opened.
  • Reference numeral 15 indicates the flow of carbon dioxide gas released. Carbon dioxide is recycled.
  • the solution of the acrylic resin and the cellulose ester resin accumulates below the gas-liquid separation container 11 and is sent from the valve 16 through the conduit 17 toward the drying device, for example, as necessary.
  • a normal filtration method can be employed.
  • a filter press method using a filter paper as a filter medium a leaf disk filter method using a stainless steel wire, or the like can be employed as a filtration method.
  • dissolution thing of the acrylic resin and cellulose-ester resin of a supercritical state is especially preferable when using it as a raw material of the acrylic resin and cellulose-ester resin of a melt casting, since the fracture
  • filtration may be performed by removing a large foreign matter by installing a coarse filtration device at the front stage and removing a fine foreign matter by installing a fine-eye filtration device at the rear stage.
  • Filtration of the solution of acrylic resin and cellulose ester resin in the present invention is performed in a supercritical state.
  • the solution viscosity becomes low even when the concentration of acrylic resin and cellulose ester resin is high, so there is almost no pressure loss of the filter, and it can be continued easily and for a long time.
  • a filtration process can be performed.
  • the supercritical substance is removed from the system to the system to make a true solution.
  • a means for removing it is preferable to adopt a means that allows the carbon dioxide gas to be adjusted under reduced pressure by introducing it into the gas-liquid separation container 11 having a relatively large volume after passing through the pressure reducing valve.
  • the temperature at which the supercritical substance (carbon dioxide gas) is discharged out of the system is 0 to 120 ° C.
  • the molten resin composition of acrylic resin and cellulose ester resin obtained by reducing the pressure is made 40 to 120 ° C., and the residue is volatilized and dried. Let The pressure at that time may be reduced to 1 atm or less.
  • the temperature to be lowered is set to a critical temperature or lower, but it is preferable to adjust the temperature close to the temperature at which it is used in the subsequent steps.
  • the acrylic resin and the cellulose ester resin can be dissolved and prepared by a continuous preparation apparatus.
  • a molten resin composition of an acrylic resin and a cellulose ester resin is prepared using a molten resin composition of an acrylic resin and a cellulose ester resin in a supercritical state and a solvent
  • the obtained acrylic resin and cellulose Remove the solvent and other volatile components from the molten resin composition with the ester resin using a cylindrical concentrating dryer, etc., extrude into a strand form from the extruder, cool and pelletize and collect the pellets obtained. Water or residual volatile components can be further removed using the following dryer.
  • drying apparatus examples include an air dryer, a spray dryer, a vacuum freeze dryer, and a vacuum dryer. Of these, an air dryer is preferable.
  • drying device for secondary drying examples include a vibrating air dryer, a stationary shelf dryer, a mobile shelf dryer, a fluidized bed dryer, a rotary dryer, and a stirring dryer. Among these, a vibration air dryer is preferable.
  • a molten resin composition of an acrylic resin and a cellulose ester resin is made into a liquid with a supercritical fluid, and then the dried acrylic resin and the cellulose ester resin-containing melt are melt cast. It is characterized by forming a film.
  • melt casting refers to, for example, melting a melt containing an acrylic resin and a cellulose ester resin without using a solvent to a temperature showing fluidity, and then flowing the acrylic resin and the cellulose ester resin.
  • the melt containing is extruded onto an endless belt or drum to form a film.
  • the acrylic resin and cellulose ester resin melt that may contain various additives used for casting contain almost no volatile solvent.
  • a solvent may be used in a part of the process of preparing the acrylic resin and cellulose ester resin melt. If the gas (carbon dioxide) used in the supercritical fluid, volatile components such as solvent, moisture, etc. remain, foaming may cause failure, so it can be reduced in the drying process to the extent that foaming does not occur. desirable.
  • FIG. 2 is a schematic view of a manufacturing apparatus for forming a film containing an acrylic resin and a cellulose ester resin by a melt casting film forming method.
  • a molten resin composition obtained by melt-kneading (dissolving) a molten resin composition containing an acrylic resin and a cellulose ester resin with a preparation device is used as it is or pelletized as necessary, and is made by melt casting. It is sent to the extrusion die 21 of the membrane device.
  • the melted molten resin composition (dope 22) is extruded from the extrusion die 21 to a film forming drum 25 (supported by one or more drums).
  • the web 23 is peeled off at a peeling point 24, stretched in a tenter device 26, and wound up as a film by a winder 27.
  • the tenter device 26 can introduce hot air, and the web 23 is stretched while being stretched while the temperature is applied. Further, depending on the intended use of the film, the web 23 may be stretched in the longitudinal direction in the tenter.
  • various apparatuses can be used as an apparatus for producing a molten resin composition containing an acrylic resin and a cellulose ester resin.
  • JP-A-11-263858 can be used.
  • the devices disclosed in Japanese Patent Laid-Open No. 2002-273777, Japanese Patent Laid-Open No. 2005-59370, and the like can be used.
  • the present invention is a method for producing a resin composition containing an acrylic resin and a cellulose ester resin, the step of melt-kneading the acrylic resin and the cellulose ester resin in the presence of a supercritical fluid, It has the process of discharging
  • the resin composition of the present invention can be formed into a film shape, a pellet shape or the like.
  • the molten resin composition is formed into a film, and the process from extrusion to conveyance / winding of the molten resin composition is continuously performed.
  • a method is preferred. By continuously performing the steps from extrusion to conveyance and winding of the molten resin composition, in the method for producing an optical film of the present invention, the production process can be easily automated and the production cost can be reduced.
  • the method for producing an optical film of the present invention is a method for producing an optical film in which a resin composition containing an acrylic resin and a cellulose ester resin in a predetermined mass ratio is melted and extruded from a die and cast on a cooling roll. .
  • the composition constituting the optical film composed of acrylic resin, cellulose ester resin, and other additives used for melt extrusion is usually preferably kneaded in advance and pelletized.
  • Pelletization may be performed by a known method. For example, dry acrylic resin, dry cellulose ester resin and other additives are fed to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder. It can be carried out by adopting a method of extruding into a strand, water cooling or air cooling and cutting.
  • the raw material is preferably dried before extrusion from the viewpoint of preventing decomposition of the raw material.
  • cellulose ester is easy to absorb moisture, it is preferable to dry it at 70 to 140 ° C. for 3 hours or more with a dehumidifying hot air dryer or a vacuum dryer so that the moisture content is 200 ppm or less, further 100 ppm or less.
  • the additives When supplying the additive to the extruder, the additives may be mixed before being supplied to the extruder, and then supplied to the extruder, or may be supplied by individual feeders. A small amount of an additive such as an antioxidant is preferably mixed in advance in order to mix uniformly.
  • the antioxidants may be mixed together in solids or, if necessary, the antioxidant may be dissolved in a solvent and mixed by impregnation or spraying into an acrylic resin or cellulose ester resin.
  • a vacuum nauter mixer or the like is preferable because drying and mixing can be performed simultaneously. Also, if such an outlet from the feeder unit and the die touches the air, it is preferable that the atmosphere such as dehumidified air and dehumidified N 2 gas.
  • the resin When the resin is kneaded using an extruder, it should be processed at as low a temperature as possible within the temperature range that can be pelletized so that the shear force is suppressed and the resin does not deteriorate (decrease in molecular weight, coloring, gel formation, etc.). Is preferred.
  • processing by an extruder for example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. In view of homogeneity of kneading, it is preferable to use a meshing type extruder.
  • the resin composition prepared by the above preparation method was filtered with a leaf disk type filter or the like to remove foreign matters using a uniaxial or biaxial type extruder with a melting temperature Tm of about 200 to 300 ° C. Thereafter, it is coextruded into a film form from a T die, solidified on a cooling roll, and cast while being pressed with an elastic touch roll.
  • Tm is the temperature of the die exit portion of the extruder.
  • a streak-like defect (sometimes called a die line) may occur in the obtained optical film.
  • the piping from the extruder to the die has a structure in which the resin retention portion is minimized.
  • the inner surface that contacts the molten resin composition is subjected to surface processing that makes it difficult for the molten resin composition to adhere to the surface by reducing the surface roughness or using a material with low surface energy. It is preferable. Specifically, it is preferable that the inner surface in contact with the molten resin composition is a hard chrome plated or ceramic sprayed surface polished to have a surface roughness of 0.2 S or less.
  • the cooling roll is not particularly limited, but it is preferable to have a structure in which a heat medium or a coolant body capable of controlling the temperature flows with a highly rigid metal roll.
  • the size of the cooling roll is not particularly limited as long as it is large enough to cool the melt-extruded film, and the diameter of the cooling roll is usually about 0.1 to 1 m.
  • Carbon steel, stainless steel, aluminum, titanium, etc. can be used as the surface material of the cooling roll.
  • the surface of the cooling roll is subjected to surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, ceramic spraying, etc. It is preferable to become.
  • the surface roughness of the surface of the cooling roll is preferably Ra of 0.1 ⁇ m or less, and more preferably 0.05 ⁇ m or less.
  • the smoother the roll surface the smoother the surface of the resulting optical film.
  • the surface processed surface is preferably further polished to have the above-described surface roughness.
  • examples of the elastic touch roll include Japanese Patent Laid-Open No. 03-124425, Japanese Patent Laid-Open No. 08-224772, Japanese Patent Laid-Open No. 07-1000096, Japanese Patent Laid-Open No. 10-272676, International Publication No. 97-028950, A silicon rubber roll having a surface covered with a thin-film metal sleeve as described in JP-A-11-235747, JP-A-2002-36332, JP-A-2005-172940 and JP-A-2005-280217. Can be used.
  • the optical film obtained as described above can be further stretched 1.01 to 3.0 times in at least one direction after undergoing the step of contacting the cooling roll.
  • the optical film is preferably stretched 1.1 to 2.0 times in both the longitudinal (film transport direction) and lateral (width direction) directions.
  • the stretching method a method using a known roll stretching machine or tenter can be employed.
  • the stretching direction is the width direction so that the polarizing film and the roll can be laminated.
  • the slow axis of the optical film becomes the width direction by stretching in the width direction.
  • the draw ratio is 1.1 to 3.0 times, preferably 1.2 to 1.5 times
  • the drawing temperature is usually Tg to Tg + 50 ° C. of the resin constituting the film, preferably Tg to Tg + 50 ° C. Temperature range.
  • the stretching is preferably performed under a uniform temperature distribution controlled in the longitudinal direction or the width direction.
  • the stretching is preferably performed while controlling the temperature within ⁇ 2 ° C., more preferably within ⁇ 1 ° C., particularly preferably within ⁇ 0.5 ° C.
  • the film may be contracted in the longitudinal direction or the width direction for the purpose of reducing retardation and reducing the dimensional change rate of the optical film produced by the above method.
  • a method of contracting in the longitudinal direction for example, there is a method of contracting the film by temporarily clipping out the width stretching and relaxing in the longitudinal direction, or by gradually narrowing the interval between adjacent clips of the transverse stretching machine.
  • the uniformity in the slow axis direction is important, and in the entire width of the film, the angle of the slow axis with respect to the film width direction is preferably -5 to + 5 °, more preferably in the range of -1 to + 1 °. Preferably, it is in the range of -0.5 to + 0.5 °, more preferably in the range of -0.1 to + 0.1 °. By optimizing the stretching conditions, it is possible to keep the variation within the above range.
  • the height from the top of the adjacent mountain to the bottom of the valley is 300 nm or more and that there is no streak continuous in the longitudinal direction with an inclination of 300 nm / mm or more.
  • the shape of streaks can be measured using a surface roughness meter.
  • the shape of the streak is SV-3100S4 manufactured by Mitutoyo Co., Ltd., which has a conical shape with a tip of 60 ° and a stylus having a tip radius of curvature of 2 ⁇ m (diamond needle) with a measuring force of 0. It can be calculated by scanning in the width direction of the film at a measurement speed of 1.0 mm / sec while applying a weight of 75 mN, measuring the cross-sectional curve with a Z-axis (thickness direction) resolution of 0.001 ⁇ m.
  • the height of the streak reads the vertical distance (H) from the top of the mountain to the bottom of the valley.
  • the slope of the streak is obtained by reading the horizontal distance (L) from the top of the mountain to the bottom of the valley and dividing the vertical distance (H) by the horizontal distance (L).
  • the optical film of the present invention is preferably a long film, specifically a long film of about 100 m to 5000 m, and is usually provided in a roll shape.
  • the film width is preferably 1.3 to 4 m, more preferably 1.4 to 2 m.
  • the film thickness of the optical film of the present invention is not particularly limited, but when used for a polarizing plate protective film described later, it is preferably 20 to 200 ⁇ m, more preferably 25 to 100 ⁇ m, and 30 to 80 ⁇ m. It is particularly preferred.
  • the optical film of the present invention is produced by a melt casting film forming method, the amount of the solvent contained is 0.01% by mass or less when wound up as a roll film.
  • the amount of the solvent can be measured by the following method.
  • Each sample is placed in a 20 ml sealed glass container, treated under the following headspace heating conditions, and then a calibration curve is prepared and measured for the solvent used in advance by the following gas chromatography.
  • the amount of solvent contained is expressed in parts by mass relative to the total mass of the optical film.
  • the acrylic resin used in the present invention includes a methacrylic resin.
  • the resin is not particularly limited, but a resin comprising 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith is preferable.
  • alkyl methacrylates having 2 to 18 carbon atoms in the alkyl group examples include alkyl methacrylates having 2 to 18 carbon atoms in the alkyl group, alkyl acrylates having 1 to 18 carbon atoms in the alkyl group, acrylic acid, and methacrylic acid.
  • Unsaturated group-containing divalent carboxylic acids such as saturated acid, maleic acid, fumaric acid and itaconic acid, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, Examples thereof include maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride, and the like. These can be used alone or in combination of two or more monomers.
  • methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
  • n-Butyl acrylate is particularly preferred.
  • the weight average molecular weight (Mw) of the acrylic resin used in the optical film of the present invention is 110,000 to 150,000 in view of particularly improving the brittleness as an optical film and improving the transparency when it is compatible with the cellulose ester resin. It is preferably 1000000.
  • the weight average molecular weight (Mw) of the acrylic resin is most preferably in the range of 130,000 to 300,000.
  • the weight average molecular weight of the acrylic resin of the present invention can be measured by gel permeation chromatography (hereinafter abbreviated as GPC).
  • GPC gel permeation chromatography
  • the production method of the acrylic resin in the present invention is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used.
  • a polymerization initiator a normal peroxide polymerization initiator and an azo polymerization initiator can be used, and a redox polymerization initiator can also be used.
  • suspension polymerization or emulsion polymerization can be performed at 30 to 100 ° C
  • bulk polymerization or solution polymerization can be performed at 80 to 160 ° C.
  • polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.
  • acrylic resins can be used as the acrylic resin of the present invention.
  • an acrylic resin Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dynal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) ) Etc.
  • Two or more acrylic resins can be used in combination.
  • the cellulose ester resin according to the present invention has a total acyl group substitution degree (T) of 2.0 to 3.0, particularly from the viewpoint of improving brittleness and excellent transparency when it is compatible with an acrylic resin.
  • the substitution degree of the acyl group having 3 to 7 carbon atoms is preferably 1.2 to 3.0. That is, the cellulose ester resin of the present invention is preferably a cellulose ester resin substituted with an acyl group having 3 to 7 carbon atoms.
  • the acyl group having 3 to 7 carbon atoms propionyl, butyryl and the like are preferably used, and a propionyl group is particularly preferably used.
  • the total substitution degree of the acyl group of the cellulose ester resin is less than 2.0, that is, when the residual degree of the hydroxy group (hydroxyl group) at the 2,3,6-position of the cellulose ester molecule is more than 1.0, When the acrylic resin and the cellulose ester resin are not sufficiently compatible and used as an optical film, haze may occur.
  • the substitution degree of the acyl group having 3 to 7 carbon atoms is less than 1.2, still sufficient compatibility cannot be obtained, Brittleness will decrease.
  • the substitution degree of the acyl group having 2 carbon atoms, that is, the acetyl group is high, and the substitution degree of the acyl group having 3 to 7 carbon atoms is 1.
  • the compatibility is lowered and the haze is increased.
  • the acyl substitution degree of the cellulose ester resin of the present invention is such that the total substitution degree (T) is 2.0 to 3.0, and the substitution degree of the acyl group having 3 to 7 carbon atoms is 1.2 to 3.0.
  • the total substitution degree of acyl groups other than those having 3 to 7 carbon atoms, that is, acetyl groups or acyl groups having 8 or more carbon atoms, is more preferably 1.3 or less.
  • the total substitution degree (T) of the acyl group of the cellulose ester resin is more preferably in the range of 2.5 to 3.0.
  • the acyl group may be an aliphatic acyl group or an aromatic acyl group. In the case of an aliphatic acyl group, it may be linear or branched and may further have a substituent.
  • the number of carbon atoms of the acyl group in the present invention includes an acyl group substituent.
  • the number of substituents X substituted on the aromatic ring is preferably 0 to 5. Also in this case, the substitution degree of the acyl group having 3 to 7 carbon atoms including the substituent needs to be 1.2 to 3.0. For example, since the benzoyl group has 7 carbon atoms, when it has a substituent containing carbon, the benzoyl group has 8 or more carbon atoms and is not included in the acyl group having 3 to 7 carbon atoms.
  • the number of substituents substituted on the aromatic ring is 2 or more, they may be the same or different from each other, and are connected to each other to form a condensed polycyclic compound (for example, naphthalene, indene, indane, phenanthrene, quinoline, isoquinoline, chromene). , Chromane, phthalazine, acridine, indole, indoline, etc.).
  • the cellulose ester resin as described above can be used as the cellulose ester resin of the present invention when it has a structure having at least one kind of an aliphatic acyl group having 3 to 7 carbon atoms.
  • the cellulose ester resin of the present invention is preferably at least one selected from cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, and cellulose butyrate, that is, having 3 carbon atoms. Or what has an acyl group of 4 as a substituent is preferable.
  • particularly preferable cellulose ester resins are cellulose acetate propionate and cellulose propionate.
  • the portion not substituted with an acyl group usually exists as a hydroxy group (—OH). These can be synthesized by known methods.
  • substitution degree of the acetyl group and the substitution degree of other acyl groups were determined by the method prescribed in ASTM-D817-96.
  • the weight average molecular weight (Mw) of the cellulose ester resin of the present invention is 75,000 or more, particularly from the viewpoint of improving the compatibility with the acrylic resin and brittleness, and it is required to be in the range of 75,000 to 300,000. Preferably, it is within the range of 100,000 to 240,000, and particularly preferably within the range of 160000 to 240000.
  • Mw weight average molecular weight
  • the important average molecular weight (Mw) of the cellulose ester resin is less than 75,000, the effect of improving heat resistance and brittleness is not sufficient, and the effect of the present invention cannot be obtained.
  • two or more kinds of cellulose resins can be mixed and used.
  • the acrylic resin and the cellulose ester resin are preferably contained in a mass ratio of 95: 5 to 30:70 from the viewpoint of taking advantage of the characteristics of the two resins. More preferably, the mass ratio of the acrylic resin to the cellulose ester resin is 95: 5 to 50:50, and particularly preferably 90:10 to 60:40. In addition, it is preferable that the said resin is contained in a compatible state.
  • Whether the acrylic resin and the cellulose ester resin are in a compatible state can be determined, for example, based on the glass transition temperature Tg.
  • the glass transition temperatures of the two resins are different, when both resins are mixed, there are two or more glass transition temperatures of each mixture because there is a glass transition temperature for each resin, but the two resins are compatible. When this occurs, the glass transition temperature inherent to each resin disappears, and there is a glass transition temperature of the resin that is compatible with one glass transition temperature.
  • the glass transition temperature referred to here is an intermediate value determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a heating rate of 20 ° C./min.
  • the point glass transition temperature (Tmg) is an intermediate value determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a heating rate of 20 ° C./min.
  • the point glass transition temperature (Tmg) The point glass transition temperature (Tmg).
  • the acrylic resin and the cellulose ester resin are each preferably an amorphous resin, and either one may be a crystalline polymer or a partially crystalline polymer.
  • the acrylic resin and the cellulose ester resin are preferably compatible with each other to become an amorphous resin.
  • the weight average molecular weight (Mw) and the degree of substitution of the acrylic resin and cellulose ester resin in the optical film of the present invention can be determined by measuring each after separation using the difference in solubility of both resins in the solvent.
  • fractionated resins can be identified by general structural analysis of polymers.
  • the optical film of the present invention contains a resin other than an acrylic resin or a cellulose ester resin, it can be separated by the same method.
  • the weight average molecular weights (Mw) of the compatible resins are different from each other, they can be separated by gel permeation chromatography (GPC). According to GPC, high molecular weight substances are eluted earlier, and the lower molecular weight substances are eluted after a longer time. Therefore, both resins can be easily separated and the molecular weights of both resins can be measured. It is.
  • the molecular weight of the compatible resin is measured by GPC, and at the same time, the resin solution eluted every time is separated, the solvent is distilled off, and the structure analysis of the dried resin is quantitatively performed.
  • the resin composition for each molecular weight fraction can be detected to identify each compatible resin.
  • each of the dissolved resins can be detected by measuring the molecular weight distribution by GPC.
  • containing acrylic resin or cellulose ester resin in a compatible state means that mixing each resin (polymer) results in a compatible state.
  • a state in which a mixed resin is obtained by polymerizing a precursor of an acrylic resin such as a monomer, dimer, or oligomer with a cellulose ester resin is not included.
  • the optical film of the present invention may contain a resin and additives other than acrylic resin and cellulose ester resin as long as the function as an optical film is not impaired.
  • the optical film of the present invention is a resin composition disclosed in Japanese Patent Application Laid-Open No. 2007-231050, that is, cellulose acylate (acyl cellulose), and a hydroxy acid component is graft-polymerized to the hydroxy group of the cellulose acylate.
  • the hydroxy acid component composed of the graft chains formed and graft-polymerized has an average of 0.1 to 5 mol in terms of hydroxy acid per 1 mol of glucose unit constituting cellulose acylate.
  • a resin composition composed of an acid-modified cellulose acylate and a thermoplastic resin (rubber-containing styrene resin, aromatic polycarbonate resin, aromatic polyester resin, aliphatic polyester resin, etc.) functions as an optical film As long as the above is not impaired, it can be used.
  • the added resin when a resin other than an acrylic resin and a cellulose ester resin is contained, the added resin may be mixed in a compatible state or may be mixed without being compatible.
  • the total mass of the acrylic resin and the cellulose ester resin in the optical film of the present invention is preferably 55% by mass or more of the optical film, more preferably 60% by mass or more, and particularly preferably 70% by mass or more. .
  • the optical film of the present invention may contain acrylic particles.
  • the acrylic particles represent an acrylic component present in a state of particles (also referred to as an incompatible state) in an optical film containing the acrylic resin and the cellulose ester resin in a compatible state.
  • the acrylic particles may be obtained by, for example, collecting a predetermined amount of the produced optical film, dissolving it in a solvent, stirring, and sufficiently dissolving and dispersing the PTFE membrane filter having a pore diameter less than the average particle diameter of the acrylic particles. It is preferable that the weight of the insoluble matter filtered and collected is acrylic particles that are 90% by mass or more of the acrylic particles added to the optical film.
  • the acrylic particles used in the present invention are not particularly limited, but are preferably acrylic particles having a layer structure of two or more layers, and particularly preferably the following multilayer structure acrylic granular composite.
  • the multilayer structure acrylic granular composite is formed by laminating the innermost hard layer polymer, the cross-linked soft layer polymer exhibiting rubber elasticity, and the outermost hard layer polymer from the center to the outer periphery.
  • the multi-layer structure acrylic granular composite is a multi-layer structure acrylic granular composite composed of an innermost hard layer, a crosslinked soft layer, and an outermost hard layer from the center to the outer periphery.
  • this three-layer core-shell structure multilayered acrylic granular composite is preferably used.
  • Preferred embodiments of the multilayer structure acrylic granular composite used in the acrylic resin composition of the present invention include, for example, (a) 80 to 98.9% by mass of methyl methacrylate and 1 to 20% by mass of an alkyl group.
  • An innermost hard layer polymer obtained by polymerizing a mixture of monomers comprising an alkyl acrylate having 1 to 8 carbon atoms and a polyfunctional grafting agent having 0.01 to 0.3% by mass;
  • (b ) In the presence of the innermost hard layer polymer, 75 to 98.5% by mass of an alkyl group having 4 to 8 carbon atoms, an alkyl acrylate of 0.01 to 5% by mass, and a multifunctional crosslinking agent of 0.01 to 5% by mass;
  • a crosslinked soft layer polymer obtained by polymerizing a mixture of monomers comprising 0.5 to 5% by mass of a polyfunctional graft agent; and
  • a three-layer structure comprising an outermost hard layer polymer obtained by polymerizing a mixture of a monomer and a monomer comprising 1 to 20% by mass of an alkyl acrylate having 1 to 20% by mass of an alkyl group.
  • the innermost hard layer polymer (a) of 5 to 40% by mass
  • the soft layer polymer (b) of 30 to 60% by mass
  • 20 to 50% by mass and an acrylic granular composite having an insoluble part when fractionated with acetone, and a degree of swelling of methyl ethyl ketone in the insoluble part of 1.5 to 4.0. It is done.
  • the innermost hard layer polymer (a) constituting the multilayer structure acrylic granular composite has 80 to 98.9% by mass of methyl methacrylate and 1 to 20% by mass of alkyl groups having 1 to Those obtained by polymerizing a mixture of monomers consisting of 8 alkyl acrylates and 0.01 to 0.3% by weight of a polyfunctional grafting agent are preferred.
  • examples of the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like. And n-butyl acrylate are preferably used.
  • the ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass.
  • the thermal decomposability of the polymer is increased.
  • the glass transition temperature of the innermost hard layer polymer (a) is decreased, resulting in three layers.
  • the impact resistance imparting effect of the structural acrylic granular composite tends to decrease.
  • polyfunctional grafting agent examples include polyfunctional monomers having different polymerizable functional groups, such as allyl esters of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, and allyl methacrylate is preferably used.
  • the polyfunctional grafting agent is used to chemically bond the innermost hard layer polymer and the soft layer polymer.
  • the ratio of the polyfunctional grafting agent used during the innermost hard layer polymerization is, for example, 0.01 to 0.3% by mass.
  • crosslinked soft layer polymer (b) constituting the acrylic granular composite 75 to 98.5% by mass of alkyl groups having 1 to 8 carbon atoms in the presence of the innermost hard layer polymer (a) are used.
  • Preferred is one obtained by polymerizing a mixture of a monomer comprising an alkyl acrylate of 0.01 to 5% by mass of a polyfunctional crosslinking agent and 0.5 to 5% by mass of a polyfunctional grafting agent. .
  • n-butyl acrylate or 2-ethylhexyl acrylate is preferably used as the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group.
  • Examples of other monofunctional monomers that can be copolymerized include styrene and substituted styrene derivatives.
  • the glass transition temperature of the polymer (b) decreases, that is, it can be softened.
  • the refractive index of the soft layer polymer (b) at room temperature is set to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard heat. It is preferable to approach the plastic acrylic resin, and the ratio between the two is selected in consideration of these.
  • the polyfunctional grafting agent those mentioned in the section of the innermost layer hard polymer (a) can be used.
  • the polyfunctional grafting agent is used to chemically bond the soft layer polymer (b) and the outermost hard layer polymer (c), and the proportion used during the innermost hard layer polymerization gives impact resistance. In view of the above, 0.5 to 5% by mass is preferable.
  • polyfunctional crosslinking agent generally known crosslinking agents such as divinyl compounds, diallyl compounds, diacrylic compounds, dimethacrylic compounds and the like can be used, but polyethylene glycol diacrylate (molecular weight 200 to 600) is preferably used.
  • the multifunctional cross-linking agent is used to generate a cross-linked structure at the time of polymerization of the soft layer polymer (b) and to exhibit an effect of imparting impact resistance.
  • the polyfunctional crosslinking agent is not an essential component.
  • the proportion of the polyfunctional crosslinking agent used during the soft layer polymerization is preferably 0.01 to 5% by mass from the viewpoint of imparting impact resistance.
  • the outermost hard layer polymer (c) constituting the multilayer structure acrylic granular composite is 80 to 99% by weight in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). Those obtained by polymerizing a mixture of monomers consisting of methyl methacrylate and an alkyl acrylate having 1 to 20% by mass of an alkyl group having 1 to 8 carbon atoms are preferred.
  • acrylic alkylate those described above are used, and methyl acrylate and ethyl acrylate are preferably used.
  • the proportion of the alkyl acrylate unit in the outermost hard layer polymer (c) is preferably 1 to 20% by mass.
  • an alkyl mercaptan or the like can be used as a chain transfer agent in order to adjust the molecular weight for the purpose of improving compatibility with the acrylic resin.
  • the outermost hard layer is provided with a gradient such that the molecular weight gradually decreases from the inside toward the outside in order to improve the balance between elongation and impact resistance.
  • the outermost hard layer is divided by a method of dividing the monomer mixture for forming the outermost hard layer into two or more and sequentially increasing the amount of chain transfer agent added each time. It is possible to employ a method of decreasing the molecular weight of the polymer forming the polymer from the inside to the outside of the multilayer structure acrylic granular composite.
  • the molecular weight of the complex formed at this time can also be examined by polymerizing a mixture of monomers used each time under the same conditions and measuring the molecular weight of the obtained polymer.
  • the particle diameter of the acrylic particles preferably used in the present invention is not particularly limited, but is preferably 10 to 1000 nm, more preferably 20 to 500 nm, and particularly 50 to 400 nm. Most preferred.
  • the mass ratio of the core and the shell is not particularly limited, but when the entire multilayer structure polymer is 100 parts by mass,
  • the core layer is preferably 50 to 90 parts by mass, and more preferably 60 to 80 parts by mass.
  • the core layer here is an innermost hard layer.
  • Examples of commercially available products of such a multilayer structure acrylic granular composite include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., Ltd., “Kane Ace” manufactured by Kaneka Co., Ltd., “Paralloid” manufactured by Kureha Co., Ltd., and ROHM. Examples include “Acryloid” manufactured by Andhers, “Staffyroid” manufactured by Gantz Kasei Co., Ltd., and “Parapet SA” manufactured by Kuraray Co., Ltd., and these can be used alone or in combination of two or more.
  • acrylic particles that are graft copolymers preferably used in the present invention include an unsaturated carboxylic acid ester monomer, an unsaturated carboxylic acid monomer in the presence of a rubbery polymer, Examples thereof include a graft copolymer obtained by copolymerizing a mixture of an aromatic vinyl monomer and, if necessary, a monomer composed of another vinyl monomer copolymerizable therewith.
  • the rubbery polymer used for the acrylic particles as the graft copolymer but diene rubber, acrylic rubber, ethylene rubber, and the like can be used. Specific examples include polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer, Butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer, and ethylene-methyl acrylate copolymer A polymer etc. are mentioned. These rubbery polymers can be used alone or in a mixture of two or more.
  • the refractive index of the mixture of the acrylic resin and the cellulose ester resin is close to the refractive index of the acrylic particles in terms of obtaining a highly transparent film.
  • the refractive index difference between the acrylic particles and the acrylic resin is preferably 0.05 or less, more preferably 0.02 or less, and still more preferably 0.01 or less.
  • a method of adjusting the monomer unit composition ratio of the acrylic resin and / or a composition ratio of the rubbery polymer or monomer used in the acrylic particles is prepared. Depending on the method, the refractive index difference can be reduced, and an optical film excellent in transparency can be obtained.
  • the difference in refractive index means that the optical film of the present invention is sufficiently dissolved in a solvent in which the acrylic resin is soluble to obtain a cloudy solution, which is dissolved in a solvent by an operation such as centrifugation. After separating into a part and an insoluble part and purifying the soluble part (acrylic resin) and the insoluble part (acrylic particles), the difference in the measured refractive index (23 ° C., measurement wavelength: 550 nm) is shown.
  • the method of blending the acrylic particles with the acrylic resin is not particularly limited, and after blending the acrylic resin and other optional components in advance, usually at 200 to 350 ° C. while adding the acrylic particles, uniaxial or biaxial A method of uniformly melt-kneading with a shaft extruder is preferably used.
  • a method such as in-line addition can be used.
  • acrylic particles can also be used as the acrylic particles of the present invention.
  • acrylic particles of the present invention examples include Metablen W-341 (Mitsubishi Rayon Co., Ltd.), Chemisnow MR-2G, MS-300X (Soken Chemical Co., Ltd.), and the like.
  • the optical film of the present invention preferably contains 0.5 to 30% by mass of acrylic particles, more preferably in the range of 1.0 to 15% by mass, based on the total mass of the resin constituting the film. It is preferable to contain acrylic particles.
  • the optical film of the present invention includes a plasticizer for imparting processability to the film, an antioxidant for preventing deterioration of the film, an ultraviolet absorber for imparting an ultraviolet absorbing function, and fine particles (matting agent) for imparting slipperiness to the film. It is preferable to contain additives such as
  • the optical film of the present invention preferably contains an acrylic oligomer having a weight average molecular weight Mw of 500 to 30,000.
  • the optical film of the present invention can achieve both brittleness and bleed-out by combining acrylic oligomers.
  • the molecular weight of the acrylic oligomer is less than 500, there is a tendency to bleed out.
  • the molecular weight of the acrylic oligomer is larger than 30000, there is a tendency that a remarkable effect is not seen in improving brittleness.
  • the monomer as a monomer unit constituting the acrylic oligomer useful in the present invention is exemplified below, but the monomer that can be used in the present invention is not limited to the following.
  • Monomers that can be used in the present invention include, for example, vinyl acetate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl myristate, Vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl octylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, etc .; acrylic acid ester, methyl acrylate, ethyl acrylate Propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (N-, i-), non
  • the acrylic oligomer is a homopolymer or copolymer of the above monomer.
  • the acrylic acid methyl ester monomer unit is preferably 30% by mass or more, and the methacrylic acid methyl ester monomer unit is preferably 40% by mass or more.
  • a homopolymer of methyl acrylate or methyl methacrylate is preferred.
  • a method capable of aligning the molecular weight as much as possible.
  • examples of such a polymerization method include a method using a peroxide polymerization initiator such as cumene peroxide and t-butyl hydroperoxide, a method using a polymerization initiator in a larger amount than normal polymerization, and a polymerization initiator.
  • an oligomer having a hydroxy group (hydroxyl group) in the side chain can also be preferably used.
  • the monomer unit having a hydroxy group (hydroxyl group) is the same as the monomer described above, but acrylic acid or methacrylic acid ester can be preferably used.
  • 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate can be used.
  • the acrylic acid ester or methacrylic acid ester monomer unit having a hydroxy group (hydroxyl group) is preferably contained in the polymer in an amount of 2 to 20% by mass, more preferably 2 to 10% by mass.
  • the method for forming a hydroxy group (hydroxyl group) at at least one terminal of the main chain of the acrylic oligomer is not particularly limited as long as it is a method for forming a hydroxy group (hydroxyl group) at the terminal of the main chain, but azobis (2-hydroxyethyl) is not limited.
  • a method of using a polymerization terminator having a method, a method of having a hydroxyl group (hydroxyl group) at the terminal by living ion polymerization, and one thiol group as described in JP-A No. 2000-128911 or JP-A No. 2000-344823 And secondary hydroxy group (hydroxyl group) compound, or the compound and organic Genus compounds can be employed a method in which bulk polymerization using a combination polymerization catalyst, in particular Patent favorably adaptation of the methods described in 2000-128911 JP or JP 2000-344823 JP.
  • Polymers produced by the methods described in these publications are commercially available as Actflow series manufactured by Soken Chemical Co., Ltd., and the products can be preferably used.
  • the polymer having a hydroxy group (hydroxyl group) at the terminal and / or the polymer having a hydroxy group (hydroxyl group) in the side chain has an effect of significantly improving the compatibility and transparency of the polymer in the present invention.
  • the hydroxy group (hydroxyl group) value of the acrylic oligomer according to the present invention is preferably 30 to 150 (mgKOH / g).
  • the method for measuring the hydroxy group (hydroxyl group) value is in accordance with JIS K 0070 (1992).
  • This hydroxy group (hydroxyl group) value is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxy group (hydroxyl group) when 1 g of a sample is acetylated.
  • a sample of Xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (20 ml of acetic anhydride added to pyridine and adjusted to 400 ml) is accurately added thereto.
  • Hydroxyl group (hydroxyl group) value ⁇ (BC) ⁇ f ⁇ 28.05 / X ⁇ + D (Wherein B is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the blank test (ml), and C is the amount of 0.5 mol / L potassium hydroxide ethanol solution used in the titration (ml). F is a factor of a 0.5 mol / L potassium hydroxide ethanol solution, D is an acid value, and 28.05 is 1/2 of 1 mol amount of potassium hydroxide (56.11))
  • the weight average molecular weight of the acrylic oligomer of the present invention can be adjusted by a known molecular weight adjusting method.
  • a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like.
  • the polymerization temperature is from room temperature to 130 ° C, preferably from 50 ° C to 100 ° C.
  • the molecular weight can be adjusted by adjusting the polymerization temperature or the polymerization reaction time.
  • the following method can be adopted as a method for measuring the weight average molecular weight.
  • the weight average molecular weight Mw can be measured using gel permeation chromatography.
  • the measurement conditions are as follows.
  • the acrylic oligomer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the optical film of the present invention.
  • plasticizers examples include phthalate ester, fatty acid ester, trimellitic ester, phosphate ester, polyester, and epoxy. Select these plasticizers depending on the application, or By using in combination, it can be applied to a wide range of uses.
  • a lactone, sulfur, phenol, double bond, hindered amine, or phosphorus antioxidant can be preferably used.
  • the phenolic compound preferably has a 2,6-dialkylphenol structure.
  • “Irganox 1076”, “Irganox 1010” commercially available from BASF Japan Ltd., and commercially available from ADEKA Ltd.
  • “ADK STAB AO-50” is preferred.
  • Examples of the phosphorus compounds include “Sumilizer GP” commercially available from Sumitomo Chemical Co., Ltd., “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB” commercially available from ADEKA. “3010”, “IRGAFOS P-EPQ”, “IrgafosXP40”, “IrgafosXP60”, etc. commercially available from BASF Japan Ltd., and “GSY-P101” commercially available from Sakai Chemical Industry Co., Ltd. are preferred.
  • the hindered amine compound is preferably, for example, “Tinuvin 144” and “Tinvin 770” commercially available from BASF Japan, and “ADK STAB LA-52” commercially available from ADEKA.
  • the above-mentioned sulfur compounds are preferably, for example, “Sumilizer TPL-R” and “Sumilizer TP-D” commercially available from Sumitomo Chemical Co., Ltd.
  • the above-mentioned double bond compound is preferably “Sumilizer GM” and “Sumilizer GS” commercially available from Sumitomo Chemical Co., Ltd.
  • the amount of these antioxidants and the like to be added is appropriately determined in accordance with the process for recycling and use, but generally 0.05 to 20% by mass, preferably with respect to the resin as the main raw material of the film Is added in the range of 0.1 to 1% by mass.
  • antioxidants can obtain a synergistic effect by using several different types of compounds in combination rather than using only one kind.
  • a combination of lactone, phosphorus, phenol and double bond compounds is preferred.
  • the colorant refers to a colorant having an effect of making the color tone of a liquid crystal screen a blue tone, adjusting a yellow index, and reducing haze.
  • dyes and pigments can be used as the colorant, and anthraquinone dyes, azo dyes, phthalocyanine pigments and the like are particularly effective.
  • UV absorber used in the present invention is not particularly limited, for example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex compounds, inorganic powders Examples include the body.
  • a polymer type ultraviolet absorber may be employed.
  • ⁇ Matting agent> it is preferable to add a matting agent in order to impart film slipperiness.
  • the matting agent used in the present invention may be either an inorganic compound or an organic compound as long as it does not impair the transparency of the obtained film and has heat resistance during melting.
  • the matting agent include talc, mica, zeolite, diatomaceous earth, calcined siliceous clay, kaolin, sericite, bentonite, smectite, clay, silica, quartz powder, glass beads, glass powder, glass flakes, milled fiber, and wax.
  • These matting agents can be used alone or in combination of two or more.
  • high transparency and slipperiness can be achieved at the same time by using particles having different particle sizes and shapes (for example, needle shape and spherical shape).
  • silicon dioxide having a refractive index close to that of cellulose ester and excellent in transparency (haze) can be particularly preferably used.
  • silicon dioxide examples include Aerosil 200V, Aerosil R972V, Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600, NAX50 (manufactured by Nippon Aerosil Co., Ltd.), Sea Hoster KEP-10, Sea Hoster KEP-30 , Seahoster KEP-50 (manufactured by Nippon Shokubai Co., Ltd.), Silo Hovic 100 (manufactured by Fuji Silysia Chemical Co., Ltd.), Nip Seal E220A (manufactured by Nippon Silica Industry Co., Ltd.), Admafine SO (manufactured by Admatechs) ) And the like can be preferably used.
  • the shape of the particles can be used without particular limitation, such as indefinite shape, needle shape, flat shape, and spherical shape.
  • the use of spherical particles is preferable because the transparency of the resulting film can be improved.
  • the particle size is preferably smaller than the wavelength of visible light, and more preferably 1 ⁇ 2 or less of the wavelength of visible light. . If the size of the particles is too small, the slipperiness may not be improved, so the range of 80 nm to 180 nm is particularly preferable.
  • the particle size means the size of the aggregate when the particle is an aggregate of primary particles.
  • the size of the particles means the diameter of a circle corresponding to the projected area.
  • a hydrogen bonding solvent can be added for the purpose of reducing the melt viscosity.
  • the hydrogen bonding solvent is J.I. N. As described in Israel Ativili, "Intermolecular Forces and Surface Forces” (Takeshi Kondo, Hiroyuki Oshima, Maglow Hill Publishing, 1991) and electrically negative atoms (oxygen, nitrogen, fluorine, chlorine)
  • An organic solvent capable of producing a hydrogen atom-mediated “bond” between an electronegative atom and a covalently bonded hydrogen atom, that is, a bond having a large bond moment and containing hydrogen for example, An organic solvent in which molecules close to each other can be arranged by including OH (oxygen hydrogen bond), NH (nitrogen hydrogen bond), and FH (fluorine hydrogen bond).
  • the melting temperature of the cellulose resin composition can be lowered by the addition of a hydrogen bonding solvent or the cellulose at the same melting temperature than the glass transition temperature of the cellulose resin used alone.
  • the melt viscosity of the cellulose resin composition containing a hydrogen bonding solvent can be lowered than that of the resin.
  • the brittleness index is determined based on the criterion of whether or not it is “an optical film that does not cause ductile fracture”.
  • the ductile fracture is a fracture that occurs due to a stress that is greater than the strength of a certain material, and is defined as a fracture that involves significant elongation or drawing of the material before the final fracture.
  • whether or not it is “an optical film that does not cause ductile fracture” is evaluated based on the fact that no breakage or the like is observed even when a large stress is applied such that the film is folded in two. (This evaluation is called folding resistance).
  • the folding resistance is 50 to 100 times, even when used as a polarizing plate protective film for an enlarged liquid crystal display device, it becomes possible to sufficiently reduce problems such as breakage during production. Further, even when the optical film is used after being once peeled off, the optical film is not broken and the optical film can be sufficiently reduced in thickness. When the folding resistance is less than 50 times, breakage tends to occur during production and the reworkability tends to be inferior. Further, in order for the folding resistance to exceed 100 times, it can be achieved by increasing the film thickness, but there is a tendency that the liquid crystal display device cannot be made thinner. Therefore, in the case of a thin film, an appropriate folding degree is 50 to 100 times.
  • the tension softening point is used as an index of heat resistance.
  • the tension softening point is 105 ° C. to 145 ° C., it can be determined that sufficient heat resistance is exhibited. More preferably, the tension softening point is controlled to be 110 ° C to 130 ° C. When the tension softening point is lower than 105 ° C., the heat amount generated by the backlight light source cannot be endured, and the film tends to be deformed or light leakage tends to occur.
  • the tension softening point is suitably from 105 ° C to 145 ° C.
  • the tension softening point was 9 N, which was obtained by cutting the optical film at 120 mm (length) ⁇ 10 mm (width) and pulling it with a tension of 10 N at a heating rate of 30 ° C./min.
  • the temperature at the time can be measured three times and the average value can be calculated.
  • the optical film preferably has a glass transition temperature (Tg) of 110 ° C. or higher. More preferably, the glass transition temperature (Tg) is 120 ° C. or higher. Particularly preferably, the glass transition temperature (Tg) is 150 ° C. or higher.
  • the glass transition temperature referred to here is an intermediate value determined according to JIS K7121 (1987) using a differential scanning calorimeter (DSC-7 model manufactured by Perkin Elmer) at a heating rate of 20 ° C./min. Point glass transition temperature (Tmg).
  • Haze value is used as an index for judging the transparency of the optical film in the present invention.
  • liquid crystal display devices used outdoors are required to have sufficient brightness and high contrast even in a bright place. Therefore, the haze value is required to be 1.0% or less, and 0.5% or less. More preferably.
  • the optical film of the present invention containing an acrylic resin and a cellulose ester resin, high transparency can be obtained, but when using acrylic particles for the purpose of improving another physical property, a resin (acrylic resin) And cellulose ester resin) and the refractive index difference between acrylic particles can be reduced to prevent an increase in haze value.
  • the surface roughness also affects the haze value as the surface haze, it is also effective to suppress the particle size and addition amount of acrylic particles within the above ranges, and to reduce the surface roughness of the film contact portion during film formation. It is.
  • bleed-out can be detected by visually observing white turbidity or dirt generated on the film under a fluorescent lamp or a green lamp.
  • the absorption spectrum of the obtained cellulose ester film was measured using a spectrophotometer U-3310 manufactured by Hitachi High-Technologies Corporation, and tristimulus values X, Y, Z And yellowness YI can be calculated from these tristimulus values X, Y, and Z based on JIS-K7103.
  • the optical film of the present invention preferably has a defect with a diameter of 5 ⁇ m or more in the film plane of 1 piece / 10 cm 2 or less. More preferably, the number of defects is 0.5 piece / 10 cm 2 or less, and further preferably, the number of defects is 0.1 piece / 10 cm 2 or less.
  • the diameter of the defect indicates the diameter when the defect is circular, and when the defect is not circular, it is determined by observing the range of the defect with a microscope according to the following method, and the maximum diameter (diameter of circumscribed circle) is determined. .
  • the range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object.
  • the defect is a change in surface shape such as transfer of a roll flaw or an abrasion
  • the size of the defect is observed with reflected light from a differential interference microscope.
  • the coating agent may not be formed uniformly, resulting in defects (coating defects).
  • the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign matter in the film forming stock solution, or a foreign matter mixed in the film forming. This refers to foreign matter (foreign matter defect) in the film.
  • the optical film of the present invention preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more in the measurement based on JIS-K7127-1999.
  • the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
  • the thickness of the optical film of the present invention is preferably 20 ⁇ m or more. More preferably, the thickness of the optical film is 30 ⁇ m or more.
  • the optical film of the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more. As a practical upper limit, the total light transmittance is about 99%. In order to achieve such excellent transparency expressed by the total light transmittance, it is necessary not to introduce an additive or a copolymer component that absorbs visible light, or to accurately filter foreign substances in the polymer. It is effective to reduce the diffusion and absorption of light inside the film.
  • the optical film of the present invention can be particularly preferably used as a polarizing plate protective film for a large-sized liquid crystal display device or a liquid crystal display device for outdoor use as long as the above physical properties are satisfied.
  • a polarizing plate When using the optical film of this invention as a protective film for polarizing plates, a polarizing plate can be produced by a general method. It is preferable that an adhesive layer is provided on the back side of the optical film of the present invention, and is bonded to at least one surface of a polarizer produced by immersion and stretching in an iodine solution.
  • the optical film of the present invention may be used, or another polarizing plate protective film may be used.
  • another polarizing plate protective film for example, a commercially available cellulose ester film (for example, Konica Minoltak KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, KC4UE, KC4FR-3, KC4FR-4, KC4HR-1, KC8UY-HA, KC8UX-RHA, manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.
  • a polarizer which is a main component of a polarizing plate, is an element that passes only light having a polarization plane in a certain direction.
  • a typical polarizer known at present is a polyvinyl alcohol polarizing film, which includes a polyvinyl alcohol film dyed with iodine and a dichroic dye dyed.
  • the polarizer is formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing the film by uniaxial stretching or dyeing or uniaxially stretching, and then performing a durability treatment with a boron compound.
  • a pressure-sensitive adhesive having a storage elastic modulus at 25 ° C. in the range of 1.0 ⁇ 10 4 to 1.0 ⁇ 10 9 Pa in at least a part of the pressure-sensitive adhesive layer is used. It is preferable.
  • a curable pressure-sensitive adhesive that forms a high molecular weight body or a crosslinked structure by various chemical reactions after applying and bonding the pressure-sensitive adhesive is suitably used.
  • urethane adhesives examples include, for example, urethane adhesives, epoxy adhesives, aqueous polymer-isocyanate adhesives, curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • anaerobic pressure-sensitive adhesives such as ester-based methacrylate types and oxidized polyether methacrylates, cyanoacrylate-based instantaneous pressure-sensitive adhesives, and acrylate-peroxide-based two-pack type instantaneous pressure-sensitive adhesives.
  • the above-mentioned pressure-sensitive adhesive may be a one-component type or a type in which two or more components are mixed before use.
  • the pressure-sensitive adhesive may be a solvent system using an organic solvent as a medium, or an aqueous system such as an emulsion type, a colloidal dispersion type, or an aqueous solution type, which is a medium containing water as a main component. It may be a solventless type.
  • concentration of the pressure-sensitive adhesive liquid may be appropriately determined depending on the film thickness after adhesion, the coating method, the coating conditions, and the like, and is usually 0.1 to 50% by mass.
  • the polarizing plate bonded with the optical film of the present invention into a liquid crystal display device, various liquid crystal display devices with excellent visibility can be produced.
  • the optical film of the present invention is preferably used for a liquid crystal display device for outdoor use such as a large-sized liquid crystal display device or digital signage.
  • the polarizing plate of the present invention is bonded to a liquid crystal cell via the adhesive layer or the like.
  • the polarizing plate of the present invention is a reflection type, transmission type, transflective LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type (including FFS type), etc. It is preferably used in LCDs of various driving methods. In particular, in a large-screen liquid crystal display device having a screen size of 30 or more, particularly 30 to 54, the effect is maintained for a long time without white spots at the periphery of the screen.
  • the liquid crystal display device using the polarizing plate of the present invention has an effect that there is little color unevenness, glare and wavy unevenness, and eyes are not tired even during long-time viewing.
  • optical film manufacturing method optical film manufacturing method
  • optical film polarizing plate
  • liquid crystal display device The technical characteristics of the optical film manufacturing method, optical film, polarizing plate, and liquid crystal display device are summarized below.
  • a method for producing a resin composition according to one aspect of the present invention is a method for producing a resin composition containing an acrylic resin and a cellulose ester resin, wherein the acrylic resin and the cellulose ester resin are mixed in the presence of a supercritical fluid. And a step of discharging the supercritical fluid from an extruder, and a step of molding the molten resin composition obtained by the melt-kneading.
  • a resin composition in which the compatibility of both resins is improved can be provided.
  • the molten resin composition is formed into a film and the steps from extrusion to conveyance and winding of the molten resin composition are continuously performed. According to this configuration, the present invention can easily automate the manufacturing process and reduce the manufacturing cost.
  • An optical film according to another aspect of the present invention is manufactured by the above-described method for manufacturing a resin composition.
  • the said optical film is an optical film which improved the performance degradation by the worsening environment.
  • the optical film is manufactured by kneading an acrylic resin and a cellulose ester resin in the presence of a supercritical fluid, the compatibility of both resins is improved, and the improvement in the compatibility Moisture resistance and heat resistance are improved and durability is improved.
  • the optical film preferably has a hard coat layer.
  • the optical film of the present invention has a hard coat layer, the additive bleed out (elution) from the base film and the compatibility of the resin used for the base film are improved. Adhesion is also improved. Therefore, when the optical film of the present invention is used as a hard coat film, moisture resistance and heat resistance are greatly improved, and peeling of the hard coat layer and an increase in haze can be prevented over a long period of time.
  • the optical film preferably has an antireflection layer on the hard coat layer.
  • the adhesiveness of a base film and a hard-coat layer can be improved. Therefore, even when an antireflection layer is further provided, moisture resistance and heat resistance are greatly improved, and peeling of the hard coat layer and an increase in haze can be prevented over a long period of time.
  • a polarizing plate according to another aspect of the present invention is characterized in that the optical film described above is provided. Since the above-mentioned optical film is provided in the polarizing plate, performance deterioration due to deterioration in the environment is improved. Further, as described above, since the optical film included in the polarizing plate has improved moisture resistance and heat resistance and improved durability, the resulting polarizing plate also has improved moisture resistance, heat resistance and durability.
  • a liquid crystal display device includes the above-described optical film. Since the liquid crystal display device is provided with the above-described optical film, the performance deterioration due to the poor environment is improved. In addition, as described above, the optical film included in the liquid crystal display device has improved moisture resistance and heat resistance and improved durability, so that the resulting liquid crystal display device also has improved moisture resistance, heat resistance and durability. Yes.
  • Molten resin composition 1 (Molten resin composition 1) In accordance with the molten resin composition 1, acrylic resin, cellulose ester resin, plasticizer, and additives were introduced into a pressure-resistant dissolution vessel in a nitrogen atmosphere, and then nitrogen in the system was replaced with carbon dioxide gas.
  • (Molten resin composition 2) A molten resin composition 2 was obtained in the same manner as described above except that the molten resin composition 1 was changed to the molten resin composition 2 in the production method of the molten resin composition 1.
  • Molten resin composition 3 Acrylic resin, cellulose ester resin, plasticizer, and additives are introduced into a pressure-resistant dissolution vessel in a nitrogen atmosphere in accordance with the molten resin composition 1 and stirred at 250 ° C. for 1 hour to melt and knead to obtain a molten resin composition 3. Obtained.
  • molten resin composition 4 A molten resin composition 4 was obtained in the same manner as described above except that the molten resin composition 1 was changed to the molten resin composition 2 in the production method of the molten resin composition 3.
  • Pellets 2 were obtained in the same manner as described above except that the molten resin composition 1 was changed to the molten resin composition 2 in the production method of the pellets 1.
  • Example 1 (Preparation of optical film 1) The molten resin composition 1 produced above was extruded from an extruder to produce an optical film.
  • Extrusion molding was performed in a clean room of class 10000 or less under molding conditions of a melting temperature of 190 ° C. and a T die temperature of 185 ° C.
  • the obtained film was stretched 1.10 times in the longitudinal direction and then stretched 1.20 times in the width direction using a tenter device, and was an optical film having a film thickness of 80 ⁇ m, a length of 3000 m, and a width of 1.5 m. 1 was obtained.
  • Example 2 (Preparation of optical film 2) An optical film 2 was obtained in the same manner as in Example 1 except that the molten resin composition 1 of Example 1 was changed to the molten resin composition 2.
  • Comparative Example 1 (Preparation of optical film 3) The molten resin composition 3 was kneaded in an extruder heated to 250 ° C., and then molded by melt extrusion to produce an optical film.
  • Extrusion molding was performed in a clean room of class 10000 or less under molding conditions of a melting temperature of 250 ° C. and a T die temperature of 245 ° C.
  • the obtained film was stretched 1.10 times in the longitudinal direction and then stretched 1.20 times in the width direction using a tenter device, and was an optical film having a film thickness of 80 ⁇ m, a length of 3000 m, and a width of 1.5 m. 3 was obtained.
  • Comparative Example 2 (Preparation of optical film 4) An optical film 4 was obtained in the same manner as in Comparative Example 1 except that the molten resin composition 3 in Comparative Example 1 was changed to the molten resin composition 4.
  • Example 3 The pellet 1 produced above was extruded from an extruder to produce an optical film. Extrusion molding was performed in a clean room of class 10000 or less under molding conditions of a melting temperature of 250 ° C. and a T die temperature of 240 ° C. The obtained film was stretched 1.10 times in the longitudinal direction and then stretched 1.20 times in the width direction using a tenter device, and the optical film 5 having a film thickness of 80 ⁇ m, a length of 3000 m, and a width of 1.5 m was obtained. Got.
  • Example 4 An optical film 6 was obtained in the same manner as in Example 3 except that the pellet 1 in Example 3 was changed to pellet 2.
  • the back coat layer composition 1 described below was applied to the surface opposite to the surface coated with the hard coat layer of the optical film by an extrusion coater so as to have a wet film thickness of 14 ⁇ m, and dried at a temperature of 50 ° C.
  • Hard coat films 1 to 6 were produced.
  • Hard coat layer composition 1 The following materials were stirred and mixed to obtain hard coat layer composition 1.
  • Dipentaerythritol hexaacrylate (NK ester A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) 90 parts by mass Pentaerythritol triacrylate 20 parts by mass Pentaerythritol tetraacrylate 60 parts by mass Urethane acrylate (trade name U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd.) 10 parts by mass Irgacure 184 (manufactured by BASF Japan) 8 parts by mass Irgacure 907 (manufactured by BASF Japan) 10 parts by mass Polyether-modified silicone compound (trade name: KF-355A, manufactured by Shin-Etsu Chemical Co., Ltd.) HLB value 12) 9 parts by mass Propylene glycol monomethyl ether 10 parts by mass Ethyl acetate 80 parts by mass Methyl ethyl ketone 100 parts by mass
  • the sample was measured with a haze meter (trade name NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) using a D65 light source. At this time, it evaluated by converting into the value of the haze in case the thickness of a sample is 80 micrometers.
  • ⁇ Less than 0.5% ⁇ : 0.5 to less than 1.0% ⁇ : Less than 1.0 to 1.5 ⁇ : Less than 1.5 to 2.0%
  • the produced hard coat films 1 to 6 were each cut into A4 size and stored for 1000 hours in a high-temperature and high-humidity thermo-machine having a temperature of 60 ° C. and a humidity of 90% RH to prepare a wet heat treatment sample. Next, the wet-heat-treated hard coat film was conditioned for 24 hours under conditions of a temperature of 23 ° C. and a humidity of 55% RH.
  • adhesion of the hard coat film subjected to the wet heat treatment was carried out in accordance with the standard of JIS D 0202-1988.
  • cellophane tape manufactured by Nichiban Co., Ltd.
  • the number of squares not peeled was measured.
  • the ratio of the area where the thin film was peeled off with respect to the tape area applied from the score line was visually observed and evaluated according to the following criteria.
  • the produced hard coat films 1 to 6 were each cut into A4 size and irradiated for 200 hours using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) according to JIS K 6783b. Thereafter, the adhesion after the light irradiation test was evaluated in the same manner as the evaluation after the wet heat durability test.
  • Tables 1 to 3 summarize the various films and the results of various evaluations.
  • the optical film produced by the method for producing the resin composition of the present invention has a haze after the wet heat durability test, a hard coat adhesion after the wet heat durability test and a light resistance test. In the evaluation, it was found to be excellent.
  • a 120- ⁇ m-thick long roll polyvinyl alcohol film is immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched 5 times along the conveying direction at 50 ° C.
  • a polarizer was produced.
  • the optical film 1 produced above was subjected to corona treatment on one side of this polarizer using an acrylic adhesive, and then bonded.
  • Konica Minolta Tack KC8UCR-5 (manufactured by Konica Minolta Opto Co., Ltd.), which is an alkali saponified retardation film, was bonded to the other surface of the polarizer and dried to prepare a polarizing plate P1.
  • polarizing plates P2 to P6 were produced using the optical films 2 to 6.
  • the polarizing plates on both sides of the 32-inch television AQ-32AD5 manufactured by Sharp Corporation were peeled off, and the manufactured polarizing plates P1 to P6 were placed on the glass surface side of the liquid crystal cell, respectively, with Konica Minoltack KC8UCR-5. Then, the liquid crystal display devices 1 to 6 were produced by bonding so that the absorption axis was in the same direction as the polarizing plate previously bonded.
  • the measurement was performed after the backlight of each liquid crystal display device was lit continuously for 1 hour in an environment of 23 ° C. and 55% RH.
  • EZ-Contrast 160D manufactured by ELDIM was used, the luminance from the normal direction of the display screen of white display and black display was measured with a liquid crystal display device, and the ratio was defined as the front contrast. That is, the front contrast was calculated according to the following formula.
  • Front contrast (brightness of white display measured from normal direction of display device) / (brightness of black display measured from normal direction of display device)

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

Un aspect de l'invention porte sur un procédé de production de composition de résine, qui est un procédé pour la production d'une composition de résine comprenant une résine acrylique et une résine d'ester de cellulose, caractérisé en ce qu'il comprend une étape de malaxage à l'état fondu de ladite résine acrylique et de ladite résine d'ester de cellulose en présence d'un fluide supercritique, une étape d'évacuation dudit fluide supercritique à l'aide d'une extrudeuse et une étape de moulage de la composition de résine fondue obtenue par ledit malaxage à l'état fondu. Ledit procédé de production de composition de résine permet un procédé de production d'une composition de résine comprenant une résine acrylique et une résine d'ester de cellulose dans lequel la compatibilité des deux résines a été améliorée. Ledit procédé de production de composition de résine permet également d'obtenir un film optique pour lequel la dégradation de performance dans des environnements difficiles a été améliorée, ainsi qu'une plaque polarisante et un dispositif d'affichage à cristaux liquides dotés dudit film optique.
PCT/JP2012/002557 2011-04-13 2012-04-12 Procédé de production de composition de résine, film optique, plaque polarisante et dispositif d'affichage à cristaux liquides Ceased WO2012140901A1 (fr)

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JP2017113368A (ja) * 2015-12-25 2017-06-29 株式会社クラレ 釘打ち用樹脂シートとその製造方法

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JP2017113368A (ja) * 2015-12-25 2017-06-29 株式会社クラレ 釘打ち用樹脂シートとその製造方法

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