WO2013140501A1 - 延伸フィルムの製造方法、延伸フィルムの製造装置および延伸フィルムの製造システム - Google Patents
延伸フィルムの製造方法、延伸フィルムの製造装置および延伸フィルムの製造システム Download PDFInfo
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- WO2013140501A1 WO2013140501A1 PCT/JP2012/057031 JP2012057031W WO2013140501A1 WO 2013140501 A1 WO2013140501 A1 WO 2013140501A1 JP 2012057031 W JP2012057031 W JP 2012057031W WO 2013140501 A1 WO2013140501 A1 WO 2013140501A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/045—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique in a direction which is not parallel or transverse to the direction of feed, e.g. oblique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
- B29K2001/08—Cellulose derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/38—Polymers of cycloalkenes, e.g. norbornene or cyclopentene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/008—Wide strips, e.g. films, webs
Definitions
- the present invention includes a stretched film manufacturing method in which a film is stretched obliquely with respect to the width direction in a stretching zone, a stretched film manufacturing apparatus for stretching the film in the oblique direction, and a manufacturing apparatus for the stretched film.
- the present invention relates to a stretched film manufacturing system.
- a stretched film formed by stretching a resin is used as an optical film that performs various optical functions in various display devices by utilizing its optical anisotropy.
- the stretched film is used as an optical compensation film for optical compensation such as anti-coloring and viewing angle expansion, or by bonding the stretched film and a polarizer, It is known to use as a retardation film that also serves as a polarizing plate protective film.
- a self-luminous display device such as an organic EL (electroluminescence) display device has attracted attention as a new display device.
- the self-luminous display device has a room for suppressing power consumption with respect to the liquid crystal display device in which the backlight is always turned on.
- a self-luminous display device such as an organic EL display device in which a light source corresponding to each color is turned on, it is not necessary to install a color filter that causes a reduction in contrast, so that the contrast can be further increased. .
- a reflector such as an aluminum plate is provided on the back side of the display in order to increase the light extraction efficiency. Therefore, external light incident on the display is reflected by the reflector and the image is reflected. There is a problem that the contrast of the image is lowered.
- the stretched film and a polarizer are bonded to form a circularly polarizing plate, and this circularly polarizing plate is used on the surface side of the display.
- the circularly polarizing plate is obtained by laminating the polarizer and the stretched film so that the in-plane slow axis of the stretched film is inclined at a desired angle with respect to the transmission axis of the polarizer. It is formed.
- a general polarizer (polarizing film) is obtained by stretching at a high magnification in the transport direction, and its transmission axis coincides with the width direction.
- a conventional retardation film is produced by longitudinal stretching or transverse stretching, and in principle, the in-plane slow axis is in the direction of 0 ° or 90 ° with respect to the longitudinal direction of the film. For this reason, in order to incline the transmission axis of the polarizer and the slow axis of the stretched film at a desired angle as described above, the long polarizing film and / or the stretched film are cut out at a specific angle and the film pieces are separated from each other.
- a batch method in which sheets are bonded one by one has to be employed, and problems such as deterioration in productivity and reduction in product yield due to adhesion of chips and the like have been cited as problems.
- the film is stretched in a desired angle direction (obliquely) with respect to the long direction, and the direction of the slow axis is not 0 ° or 90 ° with respect to the long direction of the film.
- Various methods for producing a long retardation film that can be freely controlled have been proposed.
- the resin film is unwound from a direction different from the winding direction of the stretched film, and both ends of the resin film are gripped and transported by a pair of gripping tools. And the resin film is extended
- the elongate stretched film which has a slow axis in the desired angle of more than 0 degree and less than 90 degrees with respect to the elongate direction is manufactured.
- a long polarizing film and a stretched film are attached in a roll-to-roll manner instead of conventional batch-type bonding.
- a circularly polarizing plate can be manufactured. As a result, the productivity of the circularly polarizing plate can be dramatically improved, and the yield can be greatly improved.
- a stretching apparatus stretched film manufacturing apparatus
- the film is passed in the order of a preheating zone, a stretching zone, and a heat setting zone that individually control the temperature, and the film is stretched in the stretching zone.
- the film transport speed is increased (for example, when the film is transported at 30 m / min)
- the air in the upstream zone moves into the downstream zone as the film is transported.
- the temperature is uneven in each zone (particularly in the vicinity of the film), and the optical value (orientation angle, retardation Ro) of the film varies due to the temperature unevenness.
- the obliquely stretched film is applied to a circularly polarizing plate for preventing external light reflection in a very high contrast image display device such as a large organic EL television (OLED (Organic light-Emitting Diode) -TV).
- OLED Organic light-Emitting Diode
- a so-called reflected light amount unevenness occurs in which the degree of light leakage of reflected light from the outside varies depending on the position of the display screen.
- Patent Document 1 it is possible to change the angle formed by the width direction of the partition wall and the film transport direction for separating the zones adjacent to each other in the film transport direction, and the partition wall has a gap (the film passes through).
- the orientation axis (slow phase axis) has a constant inclination (for example, 15 ° or 45 °) with respect to the width direction. It is stated that the orientation axis is oriented with high accuracy even when the film is stretched obliquely.
- Patent Document 1 does not mention any heating in the vicinity of the film. For this reason, when the conveyance speed of a film is increased, the temperature nonuniformity in the film vicinity cannot be suppressed and it cannot suppress that an optical value varies.
- Japanese Patent No. 4777646 (refer to claim 1, paragraphs [0008], [0018], [0057], FIG. 6 etc.)
- the purpose of the present invention is to suppress temperature unevenness in the orientation direction in the vicinity of the film for each film having different orientation directions, even when a stretched film is produced by transporting the film at high speed.
- An object of the present invention is to provide a stretched film manufacturing method and manufacturing apparatus capable of realizing good optical characteristics, and a stretched film manufacturing system equipped with the manufacturing apparatus.
- a method for producing a film Of the zones that include the stretching zone and are located further downstream in the transport direction, at least one zone is positioned to face the film to be transported, and in the transport direction within the plane of the film
- the crossing angle ⁇ of the heating region is adjusted so that the orientation direction of the stretched film and the crossing direction of the heating region with respect to the transport direction of the film are substantially parallel to each other.
- a partition provided between the zone where the heating unit is disposed and the upstream zone has a gap through which the film can pass, depending on the orientation direction of the stretched film.
- both ends of the film in the width direction are gripped by each gripping tool, the film is transported while moving each gripping tool, and the film transporting direction is changed in the middle, thereby the film
- a plurality of zones are arranged along the film conveyance direction, and temperature control for heating or cooling the film is performed, and the film is stretched in the width direction in the stretching zones included in the plurality of zones.
- An apparatus for producing a stretched film comprising: an adjusting mechanism that adjusts the crossing angle ⁇ of the heating region in accordance with the orientation direction of the film stretched in the stretching zone.
- the adjustment mechanism adjusts the crossing angle ⁇ of the heating region so that the orientation direction of the stretched film and the crossing direction of the heating region with respect to the transport direction of the film are substantially parallel to each other.
- the adjustment mechanism has a gap through which the film can pass, and a partition wall provided between a zone where the heating unit is disposed and a zone on the upstream side thereof depends on the orientation direction of the stretched film.
- the stretched film manufacturing apparatus according to 7 or 8, wherein the crossing angle ⁇ of the heating region is adjusted in conjunction with the moving operation.
- the heating area of the heating unit is formed by arranging at least one rod-shaped lamp heater so that the longitudinal direction thereof is along the direction intersecting with the film conveyance direction at an intersection angle ⁇ . 12.
- the stretched film manufacturing apparatus according to any one of 7 to 11 above.
- the heating region of the heating unit includes a plurality of rod-shaped lamp heaters such that the longitudinal direction thereof is along the film transport direction and the direction connecting the ends of at least two lamp heaters is the film.
- the stretched film manufacturing apparatus according to any one of 7 to 11, wherein the stretched film is formed in parallel so as to be along a direction intersecting with the transport direction at an intersection angle ⁇ .
- the heating region of the heating unit is formed by arranging a panel heater so that a side of the panel heater extends along a direction intersecting the film conveyance direction at an intersection angle ⁇ . 11.
- the heating unit is A punch plate nozzle in which a plurality of blowing holes for blowing hot air are two-dimensionally formed; A windshield having an opening extending in one direction, provided on the blow hole side of the punch plate nozzle, and blocking a part of hot air blown from the plurality of blow holes in a region other than the opening. Prepared, The heating region is formed by arranging the wind shielding plate so that the one direction in which the opening extends extends along a direction intersecting the film transport direction at an intersection angle ⁇ .
- the apparatus for producing a stretched film according to any one of 7 to 11 above.
- the heating unit is A slit nozzle formed with a single blowout hole for blowing hot air; An opening extending in one direction, provided on the blowing hole side of the slit nozzle, and including a wind shielding plate that blocks a part of the hot air blown from the blowing hole in a region other than the opening, The heating region is formed by arranging the wind shielding plate so that the one direction in which the opening extends extends along a direction intersecting the film transport direction at an intersection angle ⁇ .
- the apparatus for producing a stretched film according to any one of 7 to 11 above.
- the heating unit has a slit extending in one direction as the heating region, and includes a slit nozzle that blows hot air from the slit to heat the film,
- the said slit nozzle is provided so that the said one direction where the said slit extends may be along the direction which cross
- the said any one of 7 to 11 characterized by the above-mentioned.
- both ends of the film in the width direction are gripped by each gripping tool, the film is transported while moving each gripping tool, and the film transporting direction is changed in the middle, thereby the film Is stretched in an oblique direction with respect to the width direction.
- the stretched film manufacturing apparatus according to any one of 7 to 17 above.
- a stretched film manufacturing system comprising: a stretched film manufacturing apparatus; and a film feeding unit for feeding a film to be stretched.
- the heating unit is disposed in at least one zone after the stretching zone so as to face the film to be conveyed. Can be heated. As a result, even when a film is transported at a high speed to produce a stretched film, the upstream zone air is drawn into the downstream zone as the film is transported, and temperature unevenness occurs near the film. Can be suppressed. Therefore, it can suppress that the optical value (orientation angle, retardation Ro) of a film varies by such temperature nonuniformity.
- the heating region of the heating unit is provided along the direction intersecting with the film transport direction at the intersection angle ⁇ , but the intersection angle ⁇ of the heating region is adjusted according to the orientation direction of the stretched film.
- the crossing angle ⁇ is adjusted for each film, and the film can be heated uniformly in the orientation direction.
- FIG. 9 is a cross-sectional view taken along line L-L ′ in FIG. 8.
- FIG. 9 is a cross-sectional view taken along line M-M ′ in FIG. 8.
- film when it is not necessary to distinguish between the film before stretching and the film after stretching, these are collectively referred to as “film”, and when the two are distinguished, the former is referred to as “long film” or The film may be described as “film before stretching”, and the latter may be described as “stretched film” or “film after stretching”.
- the method for producing a stretched film (long stretched film) according to the present embodiment has an in-plane slow axis at an arbitrary angle with respect to the width direction of the stretched film by obliquely stretching the long film. It is a manufacturing method of a stretched film.
- the “long” means a film having a length of at least about 5 times the width of the film, preferably a length of 10 times or more, and specifically wound in a roll shape. It is possible to have a length (film roll) that can be stored or transported. In the manufacturing method of a long film, a film can be manufactured to desired arbitrary length by manufacturing a film continuously.
- the manufacturing method of a elongate stretched film after forming a elongate film, this is wound up around a core once, and it is set as a wound body (long film original fabric), and a long film is slanted from this wound body
- An obliquely stretched film may be produced by supplying it to the stretching process, or by continuously feeding the obliquely stretched film from the film forming process to the obliquely stretched process without winding up the long film after film formation. It may be manufactured. Performing the film forming step and the oblique stretching step continuously can feed back the film thickness and optical value results of the stretched film, change the film forming conditions, and obtain a desired long stretched film. Therefore, it is preferable.
- a long stretched film having a slow axis at an angle of more than 0 ° and less than 90 ° with respect to the width direction of the film is produced.
- the angle with respect to the width direction of the film is an angle in the film plane.
- the slow axis is usually expressed in the stretching direction or a direction perpendicular to the stretching direction, the production method according to this embodiment performs stretching at an angle of more than 0 ° and less than 90 ° with respect to the width direction of the film.
- the angle formed by the width direction of the long stretched film and the slow axis that is, the orientation angle, can be arbitrarily set to a desired angle in the range of more than 0 ° and less than 90 °.
- the present inventors have uniformly heated the vicinity of the film in the orientation direction within at least one zone after the stretching zone for stretching the film obliquely. I found that I can achieve. And further examination was advanced and it came to complete this invention based on these knowledge.
- the embodiment according to the present invention is arranged in a stretching zone included in a plurality of zones arranged along the conveyance direction of the film (long film) and performing temperature control for heating or cooling the film.
- an embodiment according to the present invention includes a plurality of zones arranged in the transport direction of the film (long film) and performing temperature control for heating or cooling the film.
- the stretched film manufacturing apparatus stretches the film in an oblique direction with respect to the width direction, and includes the stretched zone and is located on the downstream side in the transport direction from this, The film is disposed in at least one zone so as to face the film to be conveyed, and by a heating region located along a direction intersecting the conveyance direction and an intersection angle ⁇ in the plane of the film.
- the long film to be stretched in the stretched film manufacturing apparatus of the present embodiment is not particularly limited as long as it is a film composed of a thermoplastic resin.
- a film made of a resin having a property transparent to a desired wavelength is preferable.
- resins include polycarbonate resins, polyether sulfone resins, polyethylene terephthalate resins, polyimide resins, polymethyl methacrylate resins, polysulfone resins, polyarylate resins, polyethylene resins, polyvinyl chloride resins.
- resins include resins, olefin polymer resins having an alicyclic structure (alicyclic olefin polymer resins), and cellulose ester resins.
- polycarbonate resins, alicyclic olefin polymer resins, and cellulose ester resins are preferable from the viewpoints of transparency and mechanical strength.
- alicyclic olefin polymer resins and cellulose ester resins which can easily adjust the phase difference when an optical film is used, are more preferable.
- the structure about an alicyclic olefin polymer type resin and a cellulose-ester type resin is shown below.
- alicyclic olefin polymer resin examples include cyclic olefin random multi-component copolymers described in JP-A No. 05-310845, hydrogenated polymers described in JP-A No. 05-97978, and JP-A No. 11 And thermoplastic dicyclopentadiene ring-opening polymers and hydrogenated products thereof described in JP-A-124429.
- the alicyclic olefin polymer resin will be described more specifically.
- the alicyclic olefin polymer resin is a polymer having an alicyclic structure such as a saturated alicyclic hydrocarbon (cycloalkane) structure or an unsaturated alicyclic hydrocarbon (cycloalkene) structure.
- the number of carbon atoms constituting the alicyclic structure is not particularly limited, but when it is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, the mechanical strength, The properties of heat resistance and film formability are highly balanced and suitable.
- the proportion of the repeating unit containing the alicyclic structure in the alicyclic olefin polymer-based resin may be appropriately selected, but is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90%. % By weight or more.
- a stretched film an optical material such as a retardation film obtained from the long obliquely stretched film (hereinafter also referred to as a stretched film) of the present embodiment are improved. Therefore, it is preferable.
- alicyclic olefin polymer resins examples include norbornene resins, monocyclic olefin resins, cyclic conjugated diene resins, vinyl alicyclic hydrocarbon resins, and hydrides thereof.
- norbornene-based resins can be suitably used because of their good transparency and moldability.
- Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, a hydride thereof, and a norbornene structure. And an addition copolymer of a monomer having a norbornene structure and an addition copolymer of another monomer or a hydride thereof.
- a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly preferable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, and lightness. It can be used suitably.
- Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.12,5] deca-3,7-diene ( Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.12,5] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0.12, 5.17,10] dodec-3-ene (common name: tetracyclododecene), and derivatives of these compounds (for example, those having a substituent in the ring).
- examples of the substituent include an alkyl group, an alkylene group, and a polar group. Moreover, these substituents may be the same or different and a plurality may be bonded to the ring. Monomers having a norbornene structure can be used singly or in combination of two or more.
- Examples of the polar group include heteroatoms or atomic groups having heteroatoms.
- Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom.
- Specific examples of the polar group include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.
- monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; and cyclic such as cyclohexadiene and cycloheptadiene. And conjugated dienes and derivatives thereof.
- a ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.
- monomers that can be copolymerized with a monomer having a norbornene structure include, for example, ethylene, propylene, ⁇ -olefins having 2 to 20 carbon atoms such as 1-butene and derivatives thereof; cyclobutene, cyclopentene And cycloolefins such as cyclohexene and derivatives thereof; and non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene.
- ⁇ -olefin is preferable, and ethylene is more preferable.
- An addition polymer of a monomer having a norbornene structure and an addition copolymer of a monomer having a norbornene structure with another monomer copolymerizable with a monomer having a norbornene structure are prepared in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.
- X bicyclo [3.3.0] octane-2,4-diyl-ethylene structure
- Y tricyclo [4.3.0.12,5] decane-7, Having a 9-diyl-ethylene structure
- the content of these repeating units is 90% by weight or more based on the total repeating units of the norbornene resin
- the X content ratio and the Y content ratio The ratio is preferably 100: 0 to 40:60 by weight ratio of X: Y.
- the molecular weight used for the norbornene-based resin is appropriately selected according to the purpose of use, but is converted to polyisoprene measured by gel permeation chromatography using cyclohexane (toluene if the thermoplastic resin does not dissolve) as the solvent (the solvent is In the case of toluene, the weight average molecular weight (Mw) in terms of polystyrene is usually 10,000 to 100,000, preferably 15,000 to 80,000, more preferably 20,000 to 50,000. When the weight average molecular weight is in such a range, the mechanical strength and molding processability of the optical material obtained by the stretched film of the present embodiment are highly balanced and suitable.
- the glass transition temperature of the norbornene-based resin may be appropriately selected depending on the purpose of use, but is preferably 80 ° C. or higher, more preferably in the range of 100 to 250 ° C.
- the optical material obtained by the stretched film of the present embodiment can be excellent in durability without causing deformation or stress in use at high temperatures.
- the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the norbornene resin is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 4.0, more preferably 1 The range is from 2 to 3.5.
- the absolute value of the photoelastic coefficient C of norbornene-based resin is preferably 10 ⁇ 10 -12 Pa -1 or less, more preferably 7 ⁇ 10 -12 Pa -1 or less, 4 ⁇ 10 -12 Pa Particularly preferably, it is ⁇ 1 or less.
- thermoplastic resin used in this embodiment is a colorant such as a pigment or dye, a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, an antioxidant, a lubricant, and a solvent.
- the compounding agent such as may be appropriately blended.
- the content of the residual volatile component in the stretched film of norbornene resin is not particularly limited, but is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and further preferably 0.02% by weight or less. is there.
- the content of the volatile component in such a range, the dimensional stability is improved, and the temporal change of the retardation Ro in the in-plane direction and the retardation Rt in the thickness direction of the film can be reduced.
- the deterioration of the retardation film obtained from the stretched film of the present embodiment can be suppressed, and when this is applied to a polarizing plate of a liquid crystal display device or a circularly polarizing plate of an organic EL display device, the display of the display is prolonged. Can be kept stable and good.
- the residual volatile component is a substance having a molecular weight of 200 or less contained in a trace amount in the film, and examples thereof include a residual monomer and a solvent.
- the content of residual volatile components can be quantified by analyzing the film by gas chromatography as the sum of the substances having a molecular weight of 200 or less contained in the film.
- the saturated water absorption of the stretched film of norbornene resin is preferably 0.03% by weight or less, more preferably 0.02% by weight or less, and particularly preferably 0.01% by weight or less.
- the saturated water absorption is within the above range, the change in retardation Ro ⁇ Rt with time can be reduced. Furthermore, the deterioration of the retardation film obtained from the stretched film of the present embodiment can be suppressed, and when this is applied to a polarizing plate of a liquid crystal display device or a circularly polarizing plate of an organic EL display device, the display of the display is prolonged. Can be kept stable and good.
- the saturated water absorption is a value expressed as a percentage of the mass of the test piece before immersion, after the film specimen is immersed in water at a constant temperature for a certain period of time. Usually, it is measured by immersing in 23 ° C. water for 24 hours.
- the saturated water absorption rate in the stretched film of the present embodiment can be adjusted to the above value by, for example, reducing the amount of polar groups in the thermoplastic resin, but is preferably a resin having no polar groups. It is desirable.
- a production method such as a solution casting method (solution casting method) or a melt casting method (for example, melt extrusion method) described later is preferred.
- the melt extrusion method include an inflation method using a die, but a method using a T die is preferable in terms of excellent productivity and thickness accuracy.
- a sheet-like thermoplastic resin extruded from a die is brought into close contact with a cooling drum under a pressure of 50 kPa or less; 2) melting When producing a long film by extrusion, the enclosure member covers from the die opening to the first cooling drum that is in close contact, and the distance from the enclosure member to the die opening or the first contact cooling drum is 100 mm or less.
- Method 3) Method of heating the temperature of the atmosphere within 10 mm from the sheet-like thermoplastic resin extruded from the die opening to a specific temperature when producing a long film by the melt extrusion method; 4) Melting When producing a long film by the extrusion method, the speed difference from the take-up speed of the cooling drum that first adheres to the sheet-like thermoplastic resin extruded from the die opening is 0.2 m. s method of spraying the following wind; and the like.
- cellulose ester-based resin films include those containing cellulose acylate satisfying the following formulas (1) and (2) and containing a compound represented by the following general formula (A).
- Formula (1) 2.0 ⁇ Z1 ⁇ 3.0
- Formula (2) 0 ⁇ X ⁇ 3.0 In formulas (1) and (2), Z1 represents the total acyl substitution degree of cellulose acylate, and X represents the sum of the propionyl substitution degree and butyryl substitution degree of cellulose acylate.)
- L 1 and L 2 each independently represent a single bond or a divalent linking group.
- L 1 and L 2 include the following structures. (The following R represents a hydrogen atom or a substituent.)
- L 1 and L 2 are preferably —O—, —COO—, and —OCO—.
- R 1 , R 2 and R 3 each independently represent a substituent.
- substituent represented by R 1 , R 2 and R 3 include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group (methyl group, ethyl group, n-propyl group, Isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl group (vinyl group, allyl group, etc.) , Cycloalkenyl groups (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl groups (ethynyl group, propargyl group, etc.),
- Sulfamoyl group N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfamoyl group, N- (N′phenylcarbamoyl) ) Sulf Moyl group, etc.), sulfo group, acyl group (acetyl group, pivaloylbenzoyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-di-n-) Octylcarbamoyl group, N- (methylsulfonyl) carbamoyl group and the like.
- R 1 and R 2 are preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted cyclohexyl group, more preferably a substituted phenyl group or a substituted cyclohexyl group, Preferred are a phenyl group having a substituent at the 4-position and a cyclohexyl group having a substituent at the 4-position.
- R 3 is preferably a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, cyano group, amino group, More preferably, they are a hydrogen atom, a halogen atom, an alkyl group, a cyano group, and an alkoxy group.
- Wa and Wb represent a hydrogen atom or a substituent, (I) Wa and Wb may be bonded to each other to form a ring; (II) At least one of Wa and Wb may have a ring structure, or (III) At least one of Wa and Wb may be an alkenyl group or an alkynyl group.
- substituent represented by Wa and Wb include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl groups (methyl group, ethyl group, n-propyl group, isopropyl group, tert- Butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl group (vinyl group, allyl group, etc.), cycloalkenyl group ( 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl group (ethynyl group, propargyl group etc.), aryl group (phenyl group, p-tolyl group, naphthyl group etc.),
- the ring is preferably a nitrogen-containing 5-membered ring or a sulfur-containing 5-membered ring.
- the general formula (A) is particularly preferably a compound represented by the following general formula (1) or general formula (2).
- a 1 and A 2 each independently represent —O—, —S—, —NRx— (Rx represents a hydrogen atom or a substituent) or —CO—.
- Rx represents a hydrogen atom or a substituent
- the example of the substituent represented by Rx is synonymous with the specific example of the substituent represented by said Wa and Wb.
- Rx is preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
- X represents a nonmetallic atom belonging to Groups 14-16.
- X is preferably ⁇ O, ⁇ S, ⁇ NRc, ⁇ C (Rd) Re.
- Rc, Rd, and Re represent substituents, and examples thereof are synonymous with specific examples of the substituents represented by Wa and Wb.
- L 1, L 2, R 1 , R 2, R 3, n is L 1, L 2, R 1 , same meanings as R 2, R 3, n in the general formula (A).
- Q 1 is —O—, —S—, —NRy— (Ry represents a hydrogen atom or a substituent), —CRaRb— (Ra and Rb represent a hydrogen atom or a substituent) or Represents —CO—.
- Ry, Ra, and Rb represent substituents, and examples thereof are synonymous with the specific examples of the substituents represented by Wa and Wb.
- Y represents a substituent.
- substituent represented by Y it is synonymous with the specific example of the substituent represented by said Wa and Wb.
- Y is preferably an aryl group, a heterocyclic group, an alkenyl group, or an alkynyl group.
- Examples of the aryl group represented by Y include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group.
- a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
- heterocyclic group examples include heterocyclic groups containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group.
- a heterocyclic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group.
- Group, pyrrolyl group, thienyl group, pyridinyl group and thiazolyl group are preferred.
- aryl groups or heterocyclic groups may have at least one substituent.
- substituents include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, and 1 carbon atom.
- 1 to 6 fluoroalkyl groups 1 to 6 carbon atoms alkoxy groups, 1 to 6 carbon atoms alkylthio groups, 1 to 6 carbon atoms N-alkylamino groups, 2 to 12 carbon atoms N, N-dialkylamino groups And an N-alkylsulfamoyl group having 1 to 6 carbon atoms and an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
- L 1, L 2, R 1 , R 2, R 3, n is L 1, L 2, R 1 , same meanings as R 2, R 3, n in the general formula (A).
- Q 3 represents ⁇ N— or ⁇ CRz— (Rz represents a hydrogen atom or a substituent), and Q 4 represents a nonmetallic atom belonging to Groups 14-16.
- Z represents a nonmetallic atom group forming a ring together with Q 3 and Q 4 .
- the ring formed from Q 3 , Q 4 and Z may be condensed with another ring.
- the ring formed from Q 3 , Q 4 and Z is preferably a nitrogen-containing 5-membered or 6-membered ring condensed with a benzene ring.
- L 1, L 2, R 1 , R 2, R 3, n is L 1, L 2, R 1 , same meanings as R 2, R 3, n in the general formula (A).
- Wa and Wb are preferably a vinyl group having a substituent or an ethynyl group.
- the compound represented by general formula (3) is particularly preferable.
- the compound represented by the general formula (3) is superior in heat resistance and light resistance to the compound represented by the general formula (1), and is an organic solvent compared to the compound represented by the general formula (2).
- the solubility with respect to and the compatibility with a polymer are favorable.
- the compound represented by the general formula (A) can be contained by appropriately adjusting the amount for imparting desired wavelength dispersibility and anti-bleeding property.
- the content is preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass. If it is in this range, sufficient wavelength dispersibility and bleeding prevention property can be imparted to the cellulose derivative.
- general formula (A), general formula (1), general formula (2), and general formula (3) can be obtained by referring to known methods. Specifically, it can be synthesized with reference to Journal of Chemical Crystallography (1997); 27 (9); 512-526), JP2010-31223, JP2008-107767, and the like.
- the cellulose acylate film according to this embodiment contains cellulose acylate as a main component.
- the cellulose acylate film according to this embodiment preferably contains cellulose acylate in the range of 60 to 100% by mass with respect to the total mass (100% by mass) of the film.
- the total acyl group substitution degree of cellulose acylate is 2.0 or more and less than 3.0, and more preferably 2.2 to 2.7.
- cellulose acylate examples include esters of cellulose and aliphatic carboxylic acids and / or aromatic carboxylic acids having about 2 to 22 carbon atoms, and in particular, esters of cellulose and lower fatty acids having 6 or less carbon atoms. Preferably there is.
- the acyl group bonded to the hydroxyl group of cellulose may be linear or branched, and may form a ring. Furthermore, another substituent may be substituted.
- the degree of substitution is the same, birefringence decreases when the number of carbon atoms described above is large. Therefore, the number of carbon atoms is preferably selected from acyl groups having 2 to 6 carbon atoms.
- the degree of propionyl substitution and the degree of butyryl substitution are preferred. Is a sum of 0 or more and less than 3.0.
- the cellulose acylate preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
- cellulose acylate includes propionate group, butyrate group or phthalyl group in addition to acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate or cellulose acetate phthalate.
- Bound cellulose mixed fatty acid esters can be used.
- the butyryl group forming butyrate may be linear or branched.
- cellulose acetate, cellulose acetate butyrate, or cellulose acetate propionate is particularly preferably used as the cellulose acylate.
- the cellulose acylate preferably satisfies the following mathematical formulas (i) and (ii) at the same time.
- Y represents the degree of substitution of the acetyl group
- X represents the degree of substitution of the propionyl group or butyryl group or a mixture thereof.
- the mixing ratio is preferably 1:99 to 99: 1 (mass ratio).
- cellulose acetate propionate is particularly preferably used as the cellulose acylate.
- 0 ⁇ Y ⁇ 2.5 and 0.5 ⁇ X ⁇ 3.0 are preferable (where 2.0 ⁇ X + Y ⁇ 3.0), More preferably, 0.5 ⁇ Y ⁇ 2.0 and 1.0 ⁇ X ⁇ 2.0 (where 2.0 ⁇ X + Y ⁇ 3.0).
- the degree of substitution of acyl groups can be measured according to ASTM-D817-96, which is one of the standards formulated and issued by ASTM (American Society for Testing and Materials).
- the number average molecular weight of cellulose acylate is preferably in the range of 60,000 to 300,000, since the mechanical strength of the resulting film becomes strong. More preferably, cellulose acylate having a number average molecular weight of 70,000 to 200,000 is used.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of cellulose acylate are measured using gel permeation chromatography (GPC).
- the measurement conditions are as follows.
- this measuring method can be used also as a measuring method of the other polymer in this embodiment.
- the residual sulfuric acid content in the cellulose acylate is preferably in the range of 0.1 to 45 mass ppm in terms of elemental sulfur. These are considered to be contained in the form of salts. If the residual sulfuric acid content exceeds 45 ppm by mass, there is a tendency to break during hot stretching or slitting after hot stretching.
- the residual sulfuric acid content is more preferably in the range of 1 to 30 ppm by mass.
- the residual sulfuric acid content can be measured by the method prescribed in ASTM-D817-96.
- the free acid content in the cellulose acylate is preferably 1 to 500 ppm by mass.
- the above range is preferable because it is difficult to break as described above.
- the free acid content is preferably in the range of 1 to 100 ppm by mass, and is more difficult to break.
- the range of 1 to 70 ppm by mass is particularly preferable.
- the free acid content can be measured by the method prescribed in ASTM-D817-96.
- the residual alkaline earth metal content, residual sulfuric acid content, and residual acid content are within the above ranges. And is preferable.
- a cellulose acylate has few bright spot foreign materials when it is made into a film.
- Bright spot foreign matter means that when two polarizing plates are placed in a crossed Nicol state, an optical film or the like is placed between them, light is applied from one polarizing plate side, and observation is performed from the other polarizing plate side. It means a point (foreign matter) where light from the opposite side appears to leak.
- the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm 2 or less, more preferably 100 / cm 2 or less, and 50 / cm 2 or less. Is more preferably 30 pieces / cm 2 or less, particularly preferably 10 pieces / cm 2 or less, and most preferably none.
- the bright spot having a diameter of 0.005 to 0.01 mm or less is also preferably 200 pieces / cm 2 or less, more preferably 100 pieces / cm 2 or less, and 50 pieces / cm 2 or less. More preferably, it is more preferably 30 pieces / cm 2 or less, particularly preferably 10 pieces / cm 2 or less, and most preferably none.
- cellulose as a raw material for cellulose acylate, but examples include cotton linters, wood pulp, and kenaf. Moreover, the cellulose acylate obtained from them can be mixed and used at an arbitrary ratio.
- Cellulose acylate can be produced by a known method. Specifically, for example, it can be synthesized with reference to the method described in JP-A-10-45804.
- cellulose acylate is also affected by trace metal components in cellulose acylate.
- trace metal components are considered to be related to water used in the production process, but it is preferable that there are few components that can become insoluble nuclei.
- metal ions such as iron, calcium and magnesium may form an insoluble matter by forming a salt with a polymer decomposition product or the like which may contain an organic acidic group, and it is preferable that the amount of the metal ion is small.
- the calcium (Ca) component easily forms a coordination compound (that is, a complex) with an acidic component such as a carboxylic acid or a sulfonic acid, and many ligands. Insoluble starch, turbidity) may be formed, so it is preferable that the amount be small.
- the content in cellulose acylate is preferably 1 mass ppm or less.
- the content in the cellulose acylate is preferably 60 ppm by mass or less, more preferably 0 to 30 ppm by mass.
- the magnesium (Mg) component too much content will cause insoluble matter, so the content in the cellulose acylate is preferably 0 to 70 ppm by mass, particularly preferably 0 to 20 ppm by mass. .
- the content of metal components such as the content of iron (Fe) component, the content of calcium (Ca) component, the content of magnesium (Mg) component, etc.
- ICP-AES Inductively Coupled Plasma Atomic Emission Spectrometer
- the long stretched film obtained by the production method according to the present embodiment may be obtained by appropriately mixing polymer components other than the cellulose ester described later.
- the polymer component to be mixed is preferably one having excellent compatibility with the cellulose ester, and the transmittance when formed into a film is preferably 80% or more, more preferably 90% or more, and further preferably 92% or more.
- Additives added to the dope include plasticizers, ultraviolet absorbers, retardation adjusting agents, antioxidants, deterioration inhibitors, peeling aids, surfactants, dyes, fine particles, and the like.
- additives other than the fine particles may be added during the preparation of the cellulose ester solution, or may be added during the preparation of the fine particle dispersion. It is preferable to add a plasticizer, an antioxidant, an ultraviolet absorber, or the like that imparts heat and moisture resistance to the polarizing plate used in the liquid crystal image display device.
- These compounds are preferably contained in an amount of 1 to 30% by mass, preferably 1 to 20% by mass, based on the cellulose ester. Further, in order to suppress bleeding out during stretching and drying, a compound having a vapor pressure at 200 ° C. of 1400 Pa or less is preferable.
- These compounds may be added together with the cellulose ester and the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.
- Retardation adjuster As a compound to be added for adjusting the retardation, an aromatic compound having two or more aromatic rings as described in the specification of European Patent 911,656A2 can be used.
- the aromatic ring of the aromatic compound particularly preferably contains an aromatic hetero ring in addition to the aromatic hydrocarbon ring.
- the aromatic heterocycle is generally an unsaturated heterocycle. Of these, a 1,3,5-triazine ring is particularly preferred.
- the cellulose ester film in the present embodiment has a cellulose ester and a substituent selected from a carboxyl group, a hydroxyl group, an amino group, an amide group, and a sulfonic acid group, and has a weight average molecular weight of 500 to 200,000. It is preferable to contain a polymer or oligomer of a vinyl compound within the range.
- the mass ratio of the content of the cellulose ester and the polymer or oligomer is preferably in the range of 95: 5 to 50:50.
- fine particles can be contained in the stretched film as a matting agent, whereby when the stretched film is a long film, it can be easily conveyed and wound.
- the particle size of the matting agent is preferably primary particles or secondary particles of 10 nm to 0.1 ⁇ m.
- a substantially spherical matting agent having a primary particle acicular ratio of 1.1 or less is preferably used.
- the fine particles those containing silicon are preferable, and silicon dioxide is particularly preferable.
- silicon dioxide is particularly preferable.
- silicon dioxide for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) manufactured by Nippon Aerosil Co., Ltd.
- commercially available products such as Aerosil 200V, R972, R972V, R974, R202, and R812 can be preferably used.
- the polymer fine particles include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferred, and those having a three-dimensional network structure are particularly preferred. Examples of such resins include Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.).
- the fine silicon dioxide particles preferably have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / L or more.
- the average diameter of the primary particles is more preferably 5 to 16 nm, and further preferably 5 to 12 nm. A smaller primary particle average diameter is preferred because haze is low.
- the apparent specific gravity is preferably 90 to 200 g / L or more, and more preferably 100 to 200 g / L or more. Higher apparent specific gravity makes it possible to produce a high-concentration fine particle dispersion, which is preferable because no haze or aggregates are generated.
- the addition amount of the matting agent in the present embodiment is preferably long stretched film 1 m 2 per 0.01 ⁇ 1.0 g, more preferably 0.03 ⁇ 0.3 g, more preferably 0.08 ⁇ 0.16 g.
- thermal stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and alumina, and salts of alkaline earth metals such as calcium and magnesium may be added.
- a surfactant, a peeling accelerator, an antistatic agent, a flame retardant, a lubricant, an oil agent and the like may be added.
- the cellulose ester resin film in the present embodiment is required to withstand use in a higher temperature environment. Therefore, the tension softening point of the cellulose ester resin film is preferably 105 ° C. to 145 ° C. in order to exhibit sufficient heat resistance, and particularly preferably 110 ° C. to 130 ° C.
- a sample film is cut out at 120 mm (length) ⁇ 10 mm (width) and pulled with a tension of 10 N.
- the temperature can be continuously increased at a temperature increase rate of 30 ° C./min, and the temperature at 9 N can be measured three times, and the average value can be obtained.
- the dimensional change rate (%) of the cellulose ester resin film is preferably less than 0.5%, and more preferably less than 0.3%.
- the cellulose ester resin film in the present embodiment preferably has few defects in the film.
- 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 the foreign matter (foreign matter defect) in the film.
- a defect having a diameter of 5 ⁇ m or more in the film plane is 1/10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less.
- the diameter of the above defect indicates the diameter when the defect is circular, and when the defect is not circular, the range of the defect is determined by observing 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 the surface shape, such as transfer of a roll flaw or an abrasion
- the size is confirmed by observing the defect with the reflected light of a differential interference microscope.
- the film When the number of defects is more than 1/10 cm square, for example, when a tension is applied to the film during processing in a later process, the film may be broken with the defect as a starting point and productivity may be reduced. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
- the cellulose ester resin film according to the present embodiment is at least one-way in measurement based on JIS-K7127-1999, which is one of the standards of JIS (Japanese Industrial Standards Committee).
- the breaking elongation is preferably 10% or more, more preferably 20% or more.
- 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 cellulose ester resin film according to this embodiment preferably has a total light transmittance of 90% or more, more preferably 93% or more.
- the practical upper limit of the total light transmittance is about 99%.
- reduce the surface roughness of the film surface by reducing the surface roughness of the film contact part (cooling roll, calender roll, drum, belt, coating substrate in solution casting, transport roll, etc.) during film formation. It is effective to reduce the diffusion and reflection of light on the film surface.
- the long film of this embodiment made of the above-described resin can be formed by either the solution casting method or the melt casting method described below. Hereinafter, each film forming method will be described. In addition, below, although the case where a cellulose ester-type resin film is formed into a film as a long film is demonstrated, for example, it is applicable also to film forming of another resin film.
- Organic solvent An organic solvent useful for forming a dope when the cellulose ester resin film according to this embodiment is produced by a solution casting method is used without limitation as long as it dissolves cellulose acetate and other additives simultaneously. be able to.
- methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
- Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.
- the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
- a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
- the proportion of alcohol in the dope increases, the web gels and becomes easy to peel off from the metal support.
- the proportion of alcohol is small, the role of promoting cellulose acetate dissolution in non-chlorine organic solvent systems There is also.
- the dope composition is dissolved in%.
- linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Of these, ethanol is preferable because the stability of the dope can be ensured, the boiling point is relatively low, and the drying property is good.
- the cellulose ester resin film according to this embodiment can be produced by a solution casting method.
- a step of preparing a dope by dissolving a resin and an additive in a solvent a step of casting the dope on a belt-like or drum-like metal support, and a step of drying the cast dope as a web , A step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.
- the concentration of cellulose acetate in the dope is high because the drying load after casting on the metal support can be reduced. However, if the concentration is too high, the load during filtration increases and the filtration accuracy deteriorates.
- the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
- the metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
- the surface temperature of the metal support in the casting process is set to ⁇ 50 ° C. to a temperature at which the solvent boils and does not foam.
- a higher support temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or the planarity may deteriorate.
- a preferable support temperature is appropriately determined at 0 to 100 ° C., and more preferably 5 to 30 ° C.
- the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use hot water because heat is efficiently transmitted and the time until the temperature of the metal support becomes constant is shortened.
- the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or It is 60 to 130% by mass, and particularly preferably 20 to 30% by mass or 70 to 120% by mass.
- M is the mass (g) of the sample collected at any time during or after the production of the web or film
- N is the mass (g) after heating M at 115 ° C. for 1 hour.
- the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less. Particularly preferably, it is 0 to 0.01% by mass or less.
- a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method of drying while transporting the web by a tenter method are employed.
- melt casting method The melt casting method is preferable from the viewpoint that it becomes easy to reduce the retardation Rt in the thickness direction of the film after oblique stretching, which will be described later, and that the amount of residual volatile components is small and the dimensional stability of the film is excellent. Is the law.
- a composition containing an additive such as a resin and a plasticizer is heated and melted to a temperature showing fluidity, and then a melt containing fluid cellulose acetate is cast to form a film. How to do.
- Methods formed by melt casting can be classified into melt extrusion (molding) methods, press molding methods, inflation methods, injection molding methods, blow molding methods, stretch molding methods, and the like. Among these, the melt extrusion method that can obtain a film having excellent mechanical strength and surface accuracy is preferable.
- the plurality of raw materials used in the melt extrusion method are usually kneaded and pelletized in advance.
- the pelletization may be performed by a known method. For example, dry cellulose acetate, plasticizer, and other additives are fed to the extruder with a feeder, kneaded using a single or twin screw extruder, extruded into a strand from a die, water-cooled or air-cooled, and cut. Can be pelletized.
- Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders. Moreover, in order to mix a small amount of additives, such as particle
- the extruder is preferably processed at as low a temperature as possible so that it can be pelletized so as to suppress the shearing force and prevent the resin from deteriorating (molecular weight reduction, coloring, gel formation, etc.).
- a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
- Film formation is performed using the pellets obtained as described above.
- the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.
- the melting temperature at the time of extrusion is about 200 to 300 ° C, filtered through a leaf disk type filter, etc. to remove foreign matter, and then formed into a film from the T die. Then, the film is nipped between the cooling roll and the elastic touch roll and solidified on the cooling roll.
- the extrusion flow rate is preferably carried out stably by introducing a gear pump.
- a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.
- the stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated. The density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.
- Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.
- the film temperature on the touch roll side when the film is nipped between the cooling roll and the elastic touch roll is preferably Tg (glass transition temperature) or higher and Tg + 110 ° C. or lower.
- Tg glass transition temperature
- a known roll can be used as the roll having an elastic surface used for such a purpose.
- the elastic touch roll is also called a pinching rotator.
- As the elastic touch roll a commercially available one can be used.
- the long film formed by each film forming method described above may be a single layer or a laminated film of two or more layers.
- the laminated film can be obtained by a known method such as a coextrusion molding method, a co-casting molding method, a film lamination method, or a coating method. Of these, the coextrusion molding method and the co-casting molding method are preferable.
- the length of the long film in this embodiment is preferably 30 to 200 ⁇ m, more preferably 40 to 150 ⁇ m.
- the thickness unevenness ⁇ m in the flow direction (conveying direction) of the long film supplied to the stretching zone described later maintains the film take-up tension at the oblique stretching tenter inlet described later, and the orientation angle. From the viewpoint of stabilizing optical properties such as retardation and retardation, it is necessary to be less than 0.30 ⁇ m, preferably less than 0.25 ⁇ m, and more preferably less than 0.20 ⁇ m.
- the thickness unevenness ⁇ m in the flow direction of the long film is 0.30 ⁇ m or more, variations in optical properties such as retardation and orientation angle of the long stretched film are remarkably deteriorated.
- a film having a thickness gradient in the width direction may be supplied as the long film.
- the thickness gradient of the long film is empirically determined by stretching a film with various thickness gradients experimentally so that the film thickness at the position where the stretching in the subsequent process is completed can be made the most uniform. Can be sought.
- the gradient of the thickness of the long film can be adjusted, for example, so that the end portion on the thick side is thicker by about 0.5 to 3% than the end portion on the thin side.
- the width of the long film is not particularly limited, but can be 500 to 4000 mm, preferably 1000 to 2000 mm.
- the preferable elastic modulus at the stretching temperature at the time of oblique stretching of the long film is 0.01 MPa or more and 5000 MPa or less, more preferably 0.1 MPa or more and 500 MPa or less, expressed as Young's modulus. If the elastic modulus is too low, the shrinkage rate during and after stretching becomes low and wrinkles are difficult to disappear. On the other hand, if the elastic modulus is too high, the tension applied during stretching increases, and it is necessary to increase the strength of the portions that hold the side edges of the film, which increases the load on the tenter in the subsequent step.
- a non-oriented film may be used, or a film having an orientation in advance may be supplied. Further, if necessary, the distribution in the width direction of the orientation of the long film may be bow-shaped, so-called bowing. In short, the orientation state of the long film can be adjusted so that the orientation of the film at the position where the subsequent stretching has been completed can be made desirable.
- FIG. 1 is a plan view schematically showing a schematic configuration of a stretched film manufacturing system 1.
- FIG. 2 is a plan view schematically showing another configuration of the manufacturing system 1
- FIG. 3 is a plan view schematically showing still another configuration of the manufacturing system 1.
- the manufacturing system 1 includes, in order from the upstream side in the transport direction of a long film, a film feeding unit 2, a transport direction changing unit 3, a guide roll 4, and a stretching unit 5.
- a guide roll 6, a conveyance direction changing unit 7, and a film winding unit 8 are provided.
- stretching part 5 is a manufacturing apparatus of the stretched film of this embodiment, the detail is mentioned later.
- the film feeding unit 2 feeds the above-described long film to be stretched to the stretching unit 5.
- This film supply part 2 may be comprised separately from the film-forming apparatus of a long film, and may be comprised integrally.
- a long film is wound around a core after film formation, and a wound body (long film original fabric) is loaded into the film unwinding section 2 so that the film unwinds from the film unwinding section 2. The film is paid out.
- the film feeding unit 2 feeds the long film to the stretching unit 5 without winding the long film after the long film is formed.
- the conveyance direction changing unit 3 changes the conveyance direction of the long film fed from the film feeding unit 2 to a direction toward the entrance of the stretching unit 5 as an oblique stretching tenter.
- a conveyance direction change part 3 is comprised including the turntable which rotates the turn bar which changes the conveyance direction by, for example, returning while conveying a film, and the turn bar in the surface parallel to a film.
- the width of the entire manufacturing system 1 can be made narrower, and the film feed position and angle are finely controlled.
- the film feeding unit 2 and the conveyance direction changing unit 3 can be moved (slidable and turnable), the left and right clips (gripping tools) sandwiching both ends of the long film in the width direction in the stretching unit 5 can be used. It is possible to effectively prevent the biting into the film.
- the above-described film feeding unit 2 may be slidable and turnable so that a long film can be fed out at a predetermined angle with respect to the entrance of the stretching unit 5.
- FIGS. 2 and 3 it is possible to adopt a configuration in which the installation of the transport direction changing unit 3 is omitted.
- At least one guide roll 4 is provided on the upstream side of the stretching portion 5 in order to stabilize the track during running of the long film.
- the guide roll 4 may be comprised by a pair of upper and lower rolls which pinch
- the guide roll 4 closest to the entrance of the extending portion 5 is a driven roll that guides the travel of the film, and is rotatably supported via a bearing portion (not shown).
- a known material can be used as the material of the guide roll 4.
- one of the rolls upstream of the guide roll 4 closest to the entrance of the extending portion 5 is nipped by pressing the rubber roll.
- a pair of bearing portions at both ends (left and right) of the guide roll 4 closest to the entrance of the extending portion 5 includes a first tension detecting device as a film tension detecting device for detecting the tension generated in the film in the roll,
- a second tension detecting device is provided.
- a load cell can be used as the film tension detection device.
- the load cell a known tensile or compression type can be used.
- a load cell is a device that detects a load acting on an applied point by converting it into an electrical signal using a strain gauge attached to the strain generating body.
- the load cell is installed in the left and right bearing portions of the guide roll 4 closest to the entrance of the extending portion 5, whereby the force of the running film on the roll, that is, in the film traveling direction generated in the vicinity of both side edges of the film.
- the tension is detected independently on the left and right.
- a strain gauge may be directly attached to a support that constitutes the bearing portion of the roll, and a load, that is, a film tension may be detected based on the strain generated in the support. The relationship between the generated strain and the film tension is measured in advance and is known.
- the position and the transport direction of the film are changed by, for example, the transport direction changing unit 3 so that the difference in film tension between the left and right sides of the guide roll 4 closest to the entrance of the stretching unit 5 becomes equal.
- the film can be stably held by the gripping tool at the entrance of the stretching portion 5, and the occurrence of obstacles such as detachment of the gripping tool can be reduced.
- the physical properties in the width direction of the film after oblique stretching by the stretching portion 5 can be stabilized.
- At least one guide roll 6 is provided on the downstream side of the stretching portion 5 in order to stabilize the trajectory during travel of the film (long oblique stretching film) that is obliquely stretched in the stretching portion 5.
- the transport direction changing unit 7 changes the transport direction of the stretched film transported from the stretching unit 5 to a direction toward the film winding unit 8.
- the film traveling direction at the entrance of the stretching portion 5 and the film traveling direction at the exit of the stretching portion 5 It is necessary to adjust the angle between the two.
- the traveling direction of the formed film is changed by the transport direction changing unit 3 to guide the film to the inlet of the stretching unit 5 and / or the traveling direction of the film from the outlet of the stretching unit 5 Needs to be changed by the transport direction changing unit 7 to return the film to the direction of the film winding unit 8.
- the film formation and oblique stretching are continuously performed.
- the traveling direction of the film is changed by the transport direction changing unit 3 and / or the transport direction changing unit 7, and the film is formed by the film forming process and the winding process. 1, that is, as shown in FIGS. 1 and 3, the traveling direction (feeding direction) of the film fed from the film feeding unit 2 and the film just before being wound by the film winding unit 8
- the traveling direction (feeding direction) of the film fed from the film feeding unit 2 and the film just before being wound by the film winding unit 8 By matching the traveling direction (winding direction), the width of the entire apparatus with respect to the film traveling direction can be reduced.
- the film traveling direction and the film winding process do not necessarily coincide with each other in the film forming process and the film winding process, but the transport direction changing unit 3 and the film feeding unit 2 and the film winding unit 8 are arranged so that the film feeding unit 2 and the film winding unit 8 do not interfere with each other. It is preferable that the traveling direction of the film is changed by the transport direction changing unit 7.
- the transport direction changing units 3 and 7 as described above can be realized by a known method such as using an air flow roll or an air turn bar.
- the film take-up unit 8 takes up a film conveyed from the stretching unit 5 via the conveyance direction changing unit 7, and includes, for example, a winder device, an accumulator device, and a drive device. It is preferable that the film winding unit 8 has a structure that can be slid in the horizontal direction in order to adjust the film winding position.
- the film take-up unit 8 can finely control the film take-up position and angle so that the film can be taken at a predetermined angle with respect to the outlet of the stretching unit 5. As a result, it is possible to obtain a long stretched film with small variations in film thickness and optical value. In addition, it is possible to effectively prevent wrinkling of the film and to improve the winding property of the film, so that the film can be wound up in a long length.
- the take-up tension T (N / m) of the film after stretching is preferably adjusted between 100 N / m ⁇ T ⁇ 300 N / m, preferably 150 N / m ⁇ T ⁇ 250 N / m.
- the take-up tension When the take-up tension is 100 N / m or less, sagging and wrinkles of the film are likely to occur, and the retardation and orientation angle profile in the film width direction are also deteriorated. On the other hand, when the take-up tension is 300 N / m or more, the variation of the orientation angle in the film width direction is deteriorated, and the width yield (taken efficiency in the width direction) is deteriorated.
- the fluctuation of the take-up tension T it is preferable to control the fluctuation of the take-up tension T with an accuracy of less than ⁇ 5%, preferably less than ⁇ 3%.
- the variation in the take-up tension T is ⁇ 5% or more, the variation in the optical characteristics in the width direction and the flow direction (conveying direction) increases.
- the load applied to the first roll (guide roll 6) on the outlet side of the stretching section 5, that is, the film tension is measured, and the value becomes constant.
- the method of controlling the rotational speed of a take-up roll (winding roll of the film winding part 8) by a general PID control system is mentioned.
- Examples of the method for measuring the load include a method in which a load cell is attached to the bearing portion of the guide roll 6 and a load applied to the guide roll 6, that is, a film tension is measured.
- a load cell a known tensile type or compression type can be used.
- the stretched film is released from the outlet of the stretching unit 5 by being held by the gripping tool of the stretching unit 5 and trimmed at both ends (both sides) of the film that has been gripped by the gripping tool. It is wound up by (winding roll) and becomes a wound body of a long stretched film. Note that the above trimming may be performed as necessary.
- the masking film may be overlapped with the long stretched film and wound simultaneously, or at least of the long stretched film overlapping by winding. You may wind up, sticking a tape etc. on the edge of one (preferably both).
- the masking film is not particularly limited as long as it can protect the long stretched film, and examples thereof include a polyethylene terephthalate film, a polyethylene film, and a polypropylene film.
- FIG. 4 is a plan view schematically showing an example of the rail pattern of the extending portion 5.
- this is an example, and the present invention is not limited to this.
- the production of the long stretched film according to the present embodiment is performed using a tenter (an oblique stretching machine) capable of oblique stretching as the stretching section 5.
- This tenter is an apparatus that heats a long film to an arbitrary temperature at which it can be stretched and obliquely stretches it.
- This tenter is composed of a heating zone Z, a pair of rails Ri and Ro on the left and right, and a number of gripping tools Ci and Co that travel along the rails Ri and Ro (in FIG. 4, a set of gripping tools). Only). Details of the heating zone Z will be described later.
- Each of the rails Ri and Ro is configured by connecting a plurality of rail portions with connecting portions (white circles in FIG. 4 are examples of connecting portions).
- the gripping tool Ci / Co is composed of a clip that grips both ends of the film in the width direction.
- the feeding direction D1 of the long film is different from the winding direction D2 of the stretched long stretched film, and forms a feeding angle ⁇ i with the winding direction D2.
- the feeding angle ⁇ i can be arbitrarily set to a desired angle in the range of more than 0 ° and less than 90 °.
- the rail pattern of the tenter has an asymmetric shape on the left and right. And according to orientation angle (theta) given to the elongate stretched film which should be manufactured, a draw ratio, etc., a rail pattern can be adjusted now manually or automatically.
- orientation angle (theta) given to the elongate stretched film which should be manufactured, a draw ratio, etc.
- a rail pattern can be adjusted now manually or automatically.
- the positions of the rail portions and the rail connecting portions constituting the rails Ri and Ro can be freely set and the rail pattern can be arbitrarily changed.
- the tenter gripping tool Ci ⁇ Co travels at a constant speed with a constant interval from the front and rear gripping tools Ci ⁇ Co.
- the traveling speed of the gripping tool Ci / Co can be selected as appropriate, but is usually 1 to 150 m / min, preferably 15 to 150 m / min.
- the difference in travel speed between the pair of left and right grippers Ci / Co is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less of the travel speed. This is because if there is a difference in the traveling speed between the left and right sides of the film at the exit of the stretching process, wrinkles and shifts will occur at the exit of the stretching process, so the speed difference between the right and left gripping tools is required to be substantially the same speed.
- a rail that regulates the trajectory of the gripping tool is often required to have a high bending rate, particularly in a portion where the film is transported obliquely.
- the obliquely stretched tenter used for imparting the oblique orientation to the long film can freely set the orientation angle of the film by changing the rail pattern in various ways, and further, the orientation axis of the film It is preferred that the tenter be capable of orienting the (slow axis) in the left and right direction with high precision across the film width direction and controlling the film thickness and retardation with high precision.
- Both ends of the long film are gripped by the left and right grippers Ci ⁇ Co, and are conveyed in the heating zone Z as the grippers Ci • Co travel.
- the left and right grips Ci / Co are opposed to a direction substantially perpendicular to the film traveling direction (feeding direction D1) at the entrance portion (position A in the drawing) of the extending portion 5, and are asymmetric rails.
- Each travels on Ri and Ro, and the film gripped at the exit portion (position B in the figure) at the end of stretching is released.
- the film released from the gripping tool Ci ⁇ Co is wound around the core by the film winding portion 8 described above.
- Each of the pair of rails Ri and Ro has an endless continuous track, and the grippers Ci and Co that have released the film at the exit portion of the tenter travel on the outer rail and sequentially return to the entrance portion. It is supposed to be.
- the left and right gripping tools Ci and Co which are opposed to each other at the position A in the drawing, move along the rails Ri and Ro.
- the gripping tool Ci traveling on the Ri side (in-course side) has a positional relationship preceding the gripping tool Co traveling on the rail Ro side (out-course side).
- one gripping tool Ci is first in position B at the end of film stretching.
- the straight line connecting the gripping tools Ci and Co is inclined by an angle ⁇ L with respect to the direction substantially perpendicular to the film winding direction D2.
- the long film is obliquely stretched at an angle of ⁇ L with respect to the width direction.
- substantially vertical indicates that the angle is in a range of 90 ⁇ 1 °.
- the heating zone Z of the stretching section 5 is composed of a plurality of zones arranged along the transport direction of the film (long film or stretched film) and performing temperature control for heating or cooling the film. In the embodiment, it has a preheating zone Z1, a stretching zone Z2, and a heat fixing zone Z3.
- a heating section that heats the vicinity of the film is provided in the stretching zone Z2 and / or the heat setting zone Z3, and the position of the heating region of the heating section can be adjusted by an adjusting mechanism.
- the film gripped by the gripping tool Ci / Co passes through the preheating zone Z1, the stretching zone Z2, and the heat fixing zone Z3 in this order.
- the preheating zone Z1 refers to a section in which the gripping tool Ci / Co that grips both ends of the film travels at the left and right (in the film width direction) at a constant interval at the entrance of the heating zone Z.
- the stretching zone Z2 refers to a section from when the gap between the gripping tools Ci and Co that grips both ends of the film opens until a predetermined gap is reached. At this time, the oblique stretching as described above is performed, but the stretching may be performed in the longitudinal direction or the transverse direction before and after the oblique stretching as necessary.
- the heat setting zone Z3 refers to a section after the stretching zone Z2 in which the interval between the gripping tools Ci and Co is constant, and the gripping tools Ci and Co at both ends travel in parallel with each other. .
- the stretched film passes through the heat setting zone Z3 and then passes through a section (cooling zone) in which the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg (° C.) of the thermoplastic resin constituting the film. May be.
- a rail pattern that narrows the gap between the gripping tools Ci and Co facing each other in advance may be used.
- the temperature of the preheating zone Z1 is set to Tg to Tg + 30 ° C
- the temperature of the stretching zone Z2 is set to Tg to Tg + 30 ° C
- the temperature of the heat setting zone Z3 is set to Tg-30 to Tg ° C with respect to the glass transition temperature Tg of the thermoplastic resin. Is preferred.
- a temperature difference may be given in the width direction in the stretching zone Z2.
- a method of adjusting the opening degree of the nozzle for sending warm air into the temperature-controlled room so as to make a difference in the width direction, or controlling the heating by arranging the heaters in the width direction, etc. can be used.
- the lengths of the preheating zone Z1, the stretching zone Z2, and the heat setting zone Z3 can be appropriately selected.
- the length of the preheating zone Z1 is usually 100 to 150% with respect to the length of the stretching zone Z2, and the length of the heat setting zone Z3. Is usually 50 to 100%.
- the draw ratio R (W / Wo) in the stretching step is preferably 1.3 to 3. 0, more preferably 1.5 to 2.8.
- the draw ratio is in this range, the thickness unevenness in the width direction of the film is preferably reduced.
- said draw ratio R is equal to a magnification (W2 / W1) when the interval W1 between both ends of the clip held at the tenter inlet portion becomes the interval W2 at the tenter outlet portion.
- the orientation angle ⁇ is inclined in the range of, for example, greater than 0 ° and less than 90 ° with respect to the winding direction, and is at least 1300 mm.
- the width it is preferable that the variation in the in-plane retardation Ro in the width direction is 2 nm or less and the variation in the orientation angle ⁇ is 0.5 ° or less.
- the variation of the in-plane retardation Ro is 2 nm or less and preferably 1 nm or less at least 1300 mm in the width direction.
- the variation in the orientation angle ⁇ is 0.5 ° or less and 0.3 ° or less at least at 1300 mm in the width direction. It is preferably 0.1 ° or less.
- the average thickness of the long stretched film obtained by the production method according to the embodiment of the present invention is preferably 10 to 80 ⁇ m, more preferably 15 to 60 ⁇ m, and particularly preferably 20 to 50 ⁇ m from the viewpoint of mechanical strength and the like. is there. Moreover, since the thickness nonuniformity of the said elongate stretched film affects the propriety of winding, it is preferable that it is 3 micrometers or less, and it is more preferable that it is 2 micrometers or less.
- a polarizing plate protective film, a polarizer, and a ⁇ / 4 retardation film are laminated in this order, and the slow axis of the ⁇ / 4 retardation film and the absorption axis of the polarizer ( Alternatively, the angle formed with the transmission axis is 45 °.
- the polarizing plate protective film, the polarizer, and the ⁇ / 4 retardation film correspond to the protective film 313, the polarizer 312, and the ⁇ / 4 retardation film 311 in FIG. 5, respectively.
- it is preferable that a long polarizing plate protective film, a long polarizer, and a long ⁇ / 4 retardation film (long stretched film) are laminated in this order.
- the circularly polarizing plate of this embodiment is manufactured by using a stretched polyvinyl alcohol doped with iodine or a dichroic dye as a polarizer, and laminating with a configuration of ⁇ / 4 retardation film / polarizer. be able to.
- the thickness of the polarizer is 5 to 40 ⁇ m, preferably 5 to 30 ⁇ m, particularly preferably 5 to 20 ⁇ m.
- the polarizing plate can be produced by a general method.
- the ⁇ / 4 retardation film subjected to the alkali saponification treatment is preferably bonded to one surface of a polarizer produced by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. .
- the polarizing plate can be constituted by further bonding a release film on the opposite surface of the polarizing plate protective film of the polarizing plate.
- the protective film and the release film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate, product inspection, and the like.
- FIG. 5 is a cross-sectional view showing a schematic configuration of the organic EL image display device 100 of the present embodiment.
- the configuration of the organic EL image display device 100 is not limited to this.
- the organic EL image display device 100 is configured by forming a circularly polarizing plate 301 on an organic EL element 101 via an adhesive layer 201.
- the organic EL element 101 includes a metal electrode 112, a light emitting layer 113, a transparent electrode (ITO, etc.) 114, and a sealing layer 115 on a substrate 111 made of glass, polyimide, or the like.
- the metal electrode 112 may be composed of a reflective electrode and a transparent electrode.
- the circularly polarizing plate 301 is formed by laminating a ⁇ / 4 retardation film 311, a polarizer 312, and a protective film 313 in order from the organic EL element 101 side.
- the polarizer 312 is a ⁇ / 4 retardation film 311 and a protective film 313. It is pinched by. The two are bonded so that the angle formed by the transmission axis of the polarizer 312 and the slow axis of the ⁇ / 4 retardation film 311 made of the long stretched film of this embodiment is about 45 ° (or 135 °).
- the circularly polarizing plate 301 is configured.
- a cured layer is laminated on the protective film 313.
- the cured layer not only prevents scratches on the surface of the organic EL image display device, but also has an effect of preventing warpage due to the circularly polarizing plate 301. Further, an antireflection layer may be provided on the cured layer.
- the thickness of the organic EL element 101 itself is about 1 ⁇ m.
- the light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Structures having various combinations such as a laminate of such a light emitting layer and an electron injection layer made of a perylene derivative, a hole injection layer, a light emitting layer, and a laminate of an electron injection layer are known.
- holes and electrons are injected into the light-emitting layer by applying a voltage to the transparent electrode and metal electrode, and the energy generated by the recombination of these holes and electrons excites the fluorescent material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state.
- the mechanism of recombination on the way is the same as that of a general diode, and as can be expected from this, the current and the light emission intensity show strong nonlinearity with rectification with respect to the applied voltage.
- an organic EL image display device in order to extract light emitted from the light emitting layer, at least one of the electrodes must be transparent, and a transparent electrode usually formed of a transparent conductor such as indium tin oxide (ITO) is used as an anode. It is used as.
- ITO indium tin oxide
- metal electrodes such as Mg—Ag and Al—Li are used.
- the light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the light emitting layer transmits light almost completely like the transparent electrode. As a result, the light that is incident from the surface of the transparent substrate when not emitting light, passes through the transparent electrode and the light emitting layer, and is reflected by the metal electrode again exits to the surface side of the transparent substrate.
- the display surface of the EL image display device looks like a mirror surface.
- the circularly polarizing plate of this embodiment is suitable for an organic EL image display device in which such external light reflection is particularly problematic.
- the organic EL element 101 when the organic EL element 101 is not emitting light, outside light incident from the outside of the organic EL element 101 due to indoor lighting or the like is absorbed by the polarizer 312 of the circularly polarizing plate 301 and the other half is transmitted as linearly polarized light. Then, the light enters the ⁇ / 4 retardation film 311.
- the light incident on the ⁇ / 4 retardation film 311 is arranged so that the transmission axis of the polarizer 312 and the slow axis of the ⁇ / 4 retardation film 311 intersect at 45 ° (or 135 °). The light is converted into circularly polarized light by passing through the ⁇ / 4 retardation film 311.
- the phase is inverted by 180 degrees and reflected as reverse circularly polarized light.
- the reflected light is incident on the ⁇ / 4 retardation film 311 and converted into linearly polarized light perpendicular to the transmission axis of the polarizer 312 (parallel to the absorption axis). Will not be emitted. That is, external light reflection at the organic EL element 101 can be reduced by the circularly polarizing plate 301.
- FIG. 6 is a plan view showing the configuration of the heating unit 11 of the present embodiment.
- a heating unit 11 is provided in the heat setting zone Z3 to heat the film F to be conveyed (here, the film after stretching) by a planar region.
- this planar region is referred to as a heating region H.
- the heating region H is positioned so as to face the film F (the surface of the film F) to be transported, and is positioned along the direction intersecting the transport direction D at the intersection angle ⁇ (°) within the surface of the film F. is doing.
- the crossing angle ⁇ is an angle that is larger than 0 ° and smaller than 90 ° with respect to the transport direction D of the film F.
- the heating area H includes, for example, four rod-shaped lamp heaters 12 arranged in parallel (in parallel) in the conveyance direction D of the film F so as to face the film F being conveyed, and each lamp
- the heater 12 is formed in a planar shape by being arranged so that the longitudinal direction of the heater 12 intersects the transport direction D of the film F at an intersection angle ⁇ .
- the number of the lamp heaters 12 constituting the heating region H is not limited to the above four, and the heating region H can be constituted by at least one lamp heater 12.
- the lamp heater 12 is composed of, for example, a halogen lamp that emits light (electromagnetic waves) in the infrared region.
- the heating unit 11 is located immediately downstream of the partition wall 41 on the downstream side in the transport direction of the film F with respect to the partition wall 41 separating the two zones arranged in the transport direction D of the film F.
- the heating part 11 is arrange
- the position immediately after the partition wall 41 means that the film F transported to the heat setting zone Z3 through the gap t (see FIG. 7) described later of the partition wall 41 from the stretching zone Z2 enters the heat setting zone Z3. It is a position that can be heated simultaneously.
- the distance between the heating unit 11 and the partition wall 41 may be set as appropriate according to the heating capacity (wattage) and size of the lamp heater 12.
- the heating for relieving a rapid temperature change (temperature decrease) due to the air in the stretching zone Z2 being drawn into the heat setting zone Z3 is considered. Can do.
- FIG. 7 is a front view when the partition wall 41 is viewed from the downstream side in the film F conveyance direction.
- the partition wall 41 is formed by arranging two partition wall portions 41a and 41b in the vertical direction (direction perpendicular to the surface of the film F) through the gap t, and the gap t through which the film F can pass is formed. Have.
- the gap t can be changed according to the thickness of the film F by adjusting the vertical positions of the two partition walls 41a and 41b.
- the partition wall 41 can be moved according to the orientation direction of the stretched film F.
- the partition wall 41 is also 15 ° with respect to the transport direction D. It rotates so that it may incline at the angle of (refer FIG. 12).
- the partition wall 41 also rotates so as to be inclined at an angle of 45 ° with respect to the transport direction D. (See FIG. 13).
- the partition wall 41 moves so as to be substantially parallel to the orientation direction of the stretched film F.
- substantially parallel includes not only the case where the partition wall 41 and the orientation direction are completely parallel, but also the case where the partition wall 41 and the orientation direction intersect within a range of ⁇ 10 ° (preferably ⁇ 5 °).
- the partition wall 41 moves so as to be substantially parallel to the alignment direction of the film F, it does not straddle adjacent zones in the alignment direction, and thus unevenness occurs in the temperature distribution in the alignment direction in the heat setting zone Z3. Can be suppressed.
- FIG. 8 is a plan view showing a schematic configuration of the adjusting mechanism 21 provided in the extending portion 5
- FIG. 9 is a perspective view of an E portion in FIG. 10 is a cross-sectional view taken along line L-L ′ in FIG. 8, and
- FIG. 11 is a cross-sectional view taken along line M-M ′ in FIG. 8.
- the adjusting mechanism 21 is a mechanism that adjusts the above-described crossing angle ⁇ of the heating region H in accordance with the orientation direction of the film F stretched in the stretching zone Z2.
- the adjustment mechanism 21 includes a support body 22, a suspension member 23, and support members 24 and 25.
- the support body 22 supports the lamp heater 12, and is formed in a long columnar shape along the direction in which the rod-shaped lamp heater 12 extends.
- the four lamp heaters 12 are respectively attached to and supported by the bottom surfaces of the corresponding support bodies 22 via attachment members (not shown).
- Groove portions 22a into which the large-diameter portion 23b (see FIG. 10) of the suspension member 23 is slidably fitted in the longitudinal direction are provided on both sides of the longitudinal direction central portion on the upper side of the support body 22. It has been.
- the opening width of the groove portion 22a in the direction perpendicular to the longitudinal direction is formed smaller than the width of the large diameter portion 23b, thereby preventing the large diameter portion 23b from coming off from the groove portion 22a.
- the suspension member 23 is a member for suspending each support body 22 with respect to the support member 24, and is located on both sides with respect to the central portion of each support body 22 in the longitudinal direction.
- Each suspension member 23 is configured by connecting large-diameter portions 23b and 23c to both end portions of a rod-shaped member 23a.
- the rod-like member 23a is provided so as to penetrate the support member 24 in the vertical direction.
- the large-diameter portion 23b is located in a state where the large-diameter portion 23b is fitted in the groove portion 22a of the support 22 at one end portion (lower end) of the rod-shaped member 23a.
- the large diameter portion 23 c is provided at the other end (upper end) of the rod-shaped member 23 a so as to contact the upper surface of the support member 24.
- the large diameter portion 23 c has a larger diameter than the through hole 24 a of the rod-shaped member 23 a in the support member 24, thereby preventing the suspension member 23 from coming off from the support member 24.
- the support member 24 supports the suspension member 23 corresponding to each support body 22, and is long in the conveyance direction of the film F at positions on both sides with respect to the center portion of each support body 22 in the longitudinal direction. It is formed to extend in a shape.
- Each support member 24 is slidable in the transport direction by a guide member 26 extending in the transport direction. The guide member 26 is provided so as not to interfere with the suspension member 23.
- Each support member 24 is connected to a partition wall 41 through a fastener 31.
- Grooves 42 into which the large-diameter portions 31b (see FIG. 11) of the fasteners 31 are slidably fitted in the longitudinal direction are provided on both sides in the direction along each support body 22 above the partition wall 41. Yes.
- the opening width in the direction perpendicular to the longitudinal direction of the groove portion 42 is formed smaller than the width of the large diameter portion 31b of the fastener 31, thereby preventing the large diameter portion 31b from coming off from the groove portion 42.
- one end portion in the longitudinal direction of the groove portion 42 may be an open end, and the large diameter portion 31 b of the fastener 31 may be inserted into and removed from the groove portion 42.
- the above-described fastener 31 is configured by connecting large-diameter portions 31b and 31c to both ends of the rod-shaped member 31a.
- the rod-shaped member 31 a is provided so as to penetrate the support member 24.
- the large-diameter portion 31b is located in a state where the large-diameter portion 31b is fitted in the groove portion 42 of the partition wall 41 at one end portion (lower end) of the rod-shaped member 31a.
- the large diameter portion 31c is provided at the other end (upper end) of the rod-shaped member 31a so as to contact the upper surface of the support member 24.
- the large diameter portion 31 c has a larger diameter than the through hole 24 b of the rod-shaped member 31 a in the support member 24, thereby preventing the fastener 31 from coming off from the support member 24.
- the support member 25 is located between the support members 24 and 24 on both sides in parallel with each other, and connects the support bodies 22 via the rotation shaft portions 22b.
- the rotation shaft portion 22 b is a portion that becomes a shaft on which the support body 22 rotates in a plane along the film F, and penetrates the upper support member 25 in the center in the longitudinal direction of each support body 22. It is provided as follows. Note that a stopper for preventing the support shaft 25 from coming off may be provided at the end of the rotating shaft portion 22b on the support member 25 side. Further, the support member 25 is connected to the partition wall 41 via the rotation shaft portion 43.
- the rotation shaft portion 43 is a portion that becomes an axis when the partition wall 41 rotates.
- the heating section 11 heats the film F (heating process).
- the crossing angle ⁇ of the heating region H of the heating unit 11 is adjusted by the adjusting mechanism 21 in accordance with the orientation direction of the film F stretched in the stretching zone Z2 (adjusting step). This will be specifically described below.
- FIG. 12 shows the heating region H when the orientation angle ⁇ of the stretched film F is 15 °, that is, when the orientation direction of the slow axis of the film F forms an angle of 15 ° with respect to the width direction. ing.
- the partition wall 41 is moved by a drive mechanism (not shown) so as to be substantially parallel to the orientation direction of the film F as described above. That is, the partition wall 41 rotates so that the angle formed with the width direction of the film F is 15 °.
- the support member 24 located on one side in the width direction of the partition wall 41 is downstream in the transport direction of the film F via the one fastener 31. And is slid along the guide member 26 in the above direction (downstream in the transport direction). Further, the support member 24 positioned on the other side in the width direction of the partition wall 41 is pressed to the upstream side in the transport direction of the film F via the other fastener 31, and the direction (upstream side in the transport direction) along the guide member 26. ).
- each support body 22 has the rotation shaft portion 22 b together with the lamp heater 12. As a center, it rotates by the same angle as the partition wall 41.
- the crossing angle ⁇ of the heating region H is 15 °, which is the same as the orientation angle ⁇ .
- FIG. 13 shows the heating region H when the orientation angle ⁇ of the stretched film F is 45 °, that is, when the orientation direction of the slow axis of the film F forms an angle of 45 ° with respect to the width direction. ing.
- the partition wall 41 is moved by a drive mechanism (not shown) so as to be substantially parallel to the orientation direction of the film F. That is, the partition wall 41 rotates so that the angle formed with the width direction of the film F is 45 °.
- FIG. 14 is a plan view showing a state of the adjusting mechanism 21 when the orientation angle ⁇ of the film F is 45 °.
- the support member 24 positioned on one side in the width direction of the partition wall 41 is further pressed to the downstream side in the transport direction of the film F via the one fastener 31 and further in this direction. Slide. Further, the support member 24 located on the other side in the width direction of the partition wall 41 is further pressed to the upstream side in the transport direction of the film F via the other fastener 31 and further slides in this direction.
- each suspension member 23 slides outward in the longitudinal direction in the groove portion 22a of each support body 22, while each support body 22 is the same as the partition wall 41 with the lamp heater 12 and the rotation shaft portion 22b as the center. Rotate by an angle.
- the crossing angle ⁇ of the heating region H is 45 °, which is the same as the orientation angle ⁇ .
- the heating unit 11 is disposed in the heat fixing zone Z3 so as to face the film F to be transported, so that the film F is heated in the vicinity thereof by the heating unit 11. can do.
- the air in the upstream stretching zone Z2 is drawn into the downstream heat setting zone Z3 as the film F is transported, and temperature unevenness is caused in the vicinity of the film F. It can be suppressed from occurring. Therefore, it is possible to suppress variation in the optical value (orientation angle, retardation Ro) of the film F due to such temperature unevenness.
- the adjusting mechanism 21 adjusts the crossing angle ⁇ of the heating region H according to the orientation direction of the stretched film F, the crossing angle ⁇ is set for each film F even when the orientation direction is different for each film F. It can adjust and the film F can be uniformly heated by the heating part 11 in an orientation direction. Thereby, even when manufacturing the film F (stretched film) at high speed, the variation in the optical value of the film F can be suppressed for each film F having different orientation directions, and a film having good optical characteristics can be obtained.
- the crossing angle ⁇ of the heating region H is adjusted by the adjusting mechanism 21 to be the same angle as the orientation angle ⁇ of the film F, and the orientation direction of the stretched film F is The crossing direction of the heating region H with respect to the transport direction D of the film F is parallel.
- the film F can be reliably heated uniformly in the alignment direction by the heating region H.
- the orientation direction of the stretched film F and the intersecting direction of the heating region H with respect to the transport direction D of the film F are substantially parallel.
- “Substantially parallel” at this time includes not only the case where the alignment direction and the crossing direction are completely parallel, but also the case where one crosses the other within a range of ⁇ 10 ° (preferably 5 °). .
- the adjusting mechanism 21 adjusts the crossing angle ⁇ of the heating region H in conjunction with the movement (rotation) of the partition wall 41 according to the orientation direction of the stretched film F. It is not necessary to control the movement of 41 and the adjustment of the crossing angle ⁇ independently, and the heating control of the film F becomes easy.
- the heating unit 11 is located immediately after (in the downstream side of) the partition wall 41 in the transport direction D of the film F, the film F moves from the upstream zone (eg, the stretching zone Z2) to the downstream zone (eg, the stretching zone Z2).
- the film F can be heated immediately upon entering the heat setting zone Z3). Therefore, it is possible to reliably suppress the occurrence of temperature unevenness in the vicinity of the film F due to the air in the upstream zone being drawn into the downstream zone as the film F is conveyed. It is possible to reliably suppress variations in optical values.
- the heating region H of the heating unit 11 is formed by arranging at least one rod-shaped lamp heater 12 so that the longitudinal direction thereof is along the direction intersecting the transport direction D of the film F at the intersection angle ⁇ . ing. By disposing the lamp heater 12 in this way, it is possible to easily realize the heating region H formed to extend in a desired direction (a direction intersecting the transport direction D at the intersection angle ⁇ ).
- stretching part 5 hold
- the configuration of the present embodiment that can suppress variations in optical values due to temperature unevenness during high-speed conveyance is very effective when performing oblique stretching by the above method, and particularly when the film is conveyed in the above speed range. Becomes more effective.
- the stretching unit 5 is not limited to the configuration that performs oblique stretching by the above-described method, and is a configuration that performs simultaneous biaxial stretching as disclosed in, for example, Japanese Patent Application Laid-Open No. 2008-23775. Also good. Simultaneous biaxial stretching means that both ends in the width direction of the supplied long film are gripped by each gripping tool, and the long film is transported while moving each gripping tool. This is a method of stretching a long film in an oblique direction with respect to the width direction by making the moving speed of one gripping tool different from the moving speed of the other gripping tool while keeping it constant.
- the stretching unit 5 is configured to perform oblique stretching by such simultaneous biaxial stretching, the effect of the present embodiment can be obtained by applying the heating unit 11 and the adjusting mechanism 21 described above.
- the effect of the present embodiment can be obtained by applying the heating unit 11 and the adjustment mechanism 21 described above.
- FIG. 15 is a plan view showing another configuration of the heating unit 11.
- the heating region H of the heating unit 11 includes a plurality of (for example, five in the figure) rod-shaped lamp heaters 12 such that the longitudinal direction is along the transport direction D of the film F, and Arranged in parallel (in the width direction of the film) so that the direction connecting the end portions (upstream side) of at least two lamp heaters 12 is along the direction intersecting the transport direction D of the film F at the intersection angle ⁇ . It may be formed by doing.
- a plurality of lamp heaters 12 By arranging a plurality of lamp heaters 12 in this way, it is possible to realize a heating region H formed extending in a desired direction (a direction intersecting the transport direction at an intersection angle ⁇ ).
- FIG. 16 and 17 are plan views of the adjusting mechanism 21 that adjusts the crossing angle ⁇ of the heating region H in FIG. 15, FIG. 16 shows a case where the crossing angle ⁇ is 15 °, and FIG. The case of 45 ° is shown.
- the adjusting mechanism 21 is formed by providing a slide member 27 that slides in the transport direction while supporting the lamp heater 12 between the two supports 22 arranged in the transport direction of the film F. ing.
- Each slide member 27 is formed in a long shape in the transport direction, and each end portion is in contact with at least one of the support bodies 22.
- Each slide member 27 is guided by a guide member (not shown) and slides in the transport direction.
- the adjusting mechanism 21 in this way, the crossing angle ⁇ of the heating region H can be adjusted according to the orientation direction of the film F.
- FIG. 18 and 19 are plan views showing still another configuration of the heating unit 11.
- the heating region H is configured by arranging a plurality of lamp heaters 12 in parallel so that the longitudinal direction thereof is along the transport direction D of the film F, the direction connecting the ends of the lamp heaters 12 is the transport of the film F.
- the number of lamp heaters 12 used may be two as shown in FIG. 18 as long as the direction intersects the direction D at the intersection angle ⁇ . Further, the position of the two lamp heaters 12 at this time may be any position in the width direction of the film F. Further, as shown in FIG. 19, the direction of connecting the ends of the remaining lamp heaters 12 except for some of the lamp heaters 12 is along the direction intersecting the transport direction D of the film F at the intersection angle ⁇ .
- More than one lamp heater 12 may be arranged to form the heating region H. Even in these cases, the adjustment mechanism 21 adjusts the crossing angle ⁇ of the heating region H to be the same angle as the orientation angle ⁇ of the film F, whereby the film F is heated almost along the orientation direction by the heating region H. be able to.
- FIG. 20 is a plan view showing still another configuration of the heating unit 11.
- the heating region H of the heating unit 11 is formed by arranging the panel heater 13 so that the side 13a thereof is along a direction intersecting with the transport direction of the film F at an intersection angle ⁇ . May be.
- the panel heater 13 has a rectangular panel surface that emits electromagnetic waves, and the size of the panel surface becomes the size of the heating region H as it is.
- the side 13a may be considered as a side of the panel surface.
- the support 22 of the adjustment mechanism 21 shown in FIG. 8 is provided as one, and the back surface of the panel heater 13 is supported by the support 22 so that the heating region H It is possible to realize the adjusting mechanism 21 that adjusts the crossing angle ⁇ .
- FIG. 21 is a plan view showing still another configuration of the heating unit 11.
- the heating unit 11 may include a punch plate nozzle 14 and a wind shield plate 15.
- the punch plate nozzle 14 is a nozzle in which a plurality of blowing holes 14a for blowing hot air are two-dimensionally formed (arranged).
- the punch plate nozzle 14 is positioned below the film F to be conveyed, and heats the film F in the vicinity thereof by applying hot air to the film F from below.
- the punch plate nozzle 14 may be positioned above the film F to be transported, and hot film may be applied to the film F from above to heat the film F in the vicinity thereof.
- the wind shield 15 has an opening 15a extending in one direction, is provided on the blow hole 14a side of the punch plate nozzle 14, and a part of the hot air blown from the plurality of blow holes 14a in a region other than the opening 15a. Cut off. Therefore, only hot air blown from the blow hole 14 a of the punch plate nozzle 14 and passed through the opening 15 a of the wind shield plate 15 hits the film F and heats the film F. That is, in this configuration, the overlapping region of the formation region of the plurality of blowout holes 14 a of the punch nozzle 14 and the formation region of the opening 15 a of the wind shielding plate 15 constitutes a heating region H that heats the film F.
- the heating region H extending in the intersecting direction is realized by arranging the wind shielding plate 15 so that the one direction in which the opening 15a extends is along the direction intersecting with the transport direction of the film F at the intersecting angle ⁇ . can do.
- FIG. 21 shows a case where the crossing angle ⁇ of the heating region H is 15 °.
- the crossing angle ⁇ of the heating region H can be adjusted by rotating the wind shielding plate 15 in a plane parallel to the film F by the adjusting mechanism 21.
- the rotation of the wind shield 15 by the adjustment mechanism 21 can be realized by configuring the adjustment mechanism 21 as follows, for example.
- the wind shielding plate 15 is supported on the lower surface of at least one support 22 in a region other than the opening 15a. Then, the suspension members 23 on both sides of the support 22 are positioned on the outer side in the width direction with respect to the film F to be transported, and the support 22 and the wind shielding plate 15 are transported with the film F and the punch nozzle. 14, the support 22 is suspended from the support member 24 by the suspension member 23.
- the adjustment mechanism 21 By configuring the adjustment mechanism 21 in this way, when the support member 24 applies an external force in the rotational direction to the support body 22 via the suspension member 23 in conjunction with the movement operation of the partition wall 41, the support body 22. At the same time, the wind shielding plate 15 rotates in a plane parallel to the film F. Therefore, for example, when the orientation angle of the film F is 45 °, the wind shielding plate 15 can be rotated so that the crossing angle ⁇ is 45 ° as shown in FIG. Therefore, even if it is the structure which uses the punch plate nozzle 14 and the wind shield 15 as the heating part 11, according to the orientation direction of the film F, the wind shield 15 is rotated and the crossing angle ⁇ of the heating region H Can be adjusted.
- FIG. 23 is a plan view showing still another configuration of the heating unit 11.
- the heating unit 11 may have a slit nozzle 16 instead of the punch plate nozzle 14 described above. That is, the heating unit 11 may be configured to include the slit nozzle 16 and the wind shield plate 15 described above.
- the slit nozzle 16 has a rectangular blowing hole 16a as a single slit, and is a nozzle that blows hot air from the blowing hole 16a.
- the wind shield 15 is provided on the side of the blow hole 16a of the slit nozzle 16, and hot air blows out from the blow hole 16a in a region other than the opening 15a formed to extend in one direction. Block some of the.
- FIG. 23 shows a case where the crossing angle ⁇ of the heating region H is 15 °.
- FIG. 24 shows a state in which the wind shielding plate 15 is rotated by the adjusting mechanism 21 so that the crossing angle ⁇ of the heating region H becomes 45 °.
- FIG. 25 is a plan view showing still another configuration of the heating unit 11.
- the heating unit 11 may be composed of a single slit nozzle 17.
- the slit nozzle 17 has a rectangular slit 17a extending in one direction as a heating region H, and blows hot air from the slit 17a to heat the film F.
- the slit nozzle 17 is provided below the film F to be transported, and may blow hot air from below to heat the film F, or may be provided above the film F to be transported and Alternatively, the film F may be heated by blowing hot air downward.
- the slit nozzle 17 When the slit nozzle 17 is used as the heating unit 11, the slit nozzle 17 is disposed so that the one direction in which the slit 17 a extends extends at a crossing angle ⁇ with the transport direction of the film F. It is possible to realize a heating region H extending to Incidentally, FIG. 25 shows a case where the crossing angle ⁇ of the heating region H is 15 °.
- the crossing angle ⁇ of the heating region H can be adjusted by rotating the slit nozzle 17 in a plane parallel to the film F by the adjusting mechanism 21.
- the rotation of the slit nozzle 17 by the adjustment mechanism 21 can be realized by configuring the adjustment mechanism 21 as follows, for example.
- the slit nozzle 17 is supported on the lower surface of at least one support 22 in a region other than the slit 17a. At this time, the slit nozzle 17 is supported on the lower surface of the support 22 so that hot air is blown upward from below through the slit 17a. Then, the suspension members 23 on both sides of the support 22 are positioned on the outer side in the width direction of the film F to be transported, and the support 22 and the slit nozzle 17 are positioned below the film F to be transported. As described above, the support 22 is suspended from the support member 24 by the suspension member 23.
- the slit nozzle 17 can be rotated in a plane parallel to the film F in conjunction with the movement operation of the partition wall 41.
- the slit nozzle 17 can be rotated so that the crossing angle ⁇ is 45 ° as shown in FIG. Therefore, even if it is the structure which uses the slit nozzle 17 as the heating part 11, according to the orientation direction of the film F, the slit nozzle 17 can be rotated and the crossing angle (phi) of the heating area
- the heating part 11 should just be provided in at least 1 of the zone which includes the extending
- thermoplastic resin film After forming a thermoplastic resin film, the thermoplastic resin film was stretched by the stretching portion 5 shown in FIG. 4 to produce an obliquely stretched optical film.
- “part” or “%” is used, but unless otherwise specified, these represent “part by mass” or “% by mass”.
- Example 1-1 [Method for producing cycloolefin film] In a nitrogen atmosphere, dehydrated cyclohexane (500 parts), 1-hexene (1.2 parts), dibutyl ether (0.15 parts), and triisobutylaluminum (0.30 parts) were mixed in a reactor at room temperature.
- DCP dicyclopentadiene
- 1,4-methano-1,4,4a, 9a-tetrahydrofluorene A norbornene-based monomer comprising 140 parts of MTF (hereinafter abbreviated as MTF) and 40 parts of 8-methyl-tetracyclo [4.4.0.12, 5.17,10] -dodec-3-ene (hereinafter abbreviated as MTD).
- MTF MTF
- MTD 8-methyl-tetracyclo [4.4.0.12, 5.17,10] -dodec-3-ene
- This hydrogenated ring-opened polymer had a weight average molecular weight (Mw) of 31,000, a molecular weight distribution (Mw / Mn) of 2.5, a hydrogenation rate of 99.9%, and a Tg of 134 ° C.
- the obtained ring-opened polymer hydrogenated pellets were dried at 70 ° C. for 2 hours using a hot air dryer in which air was circulated to remove moisture.
- the pellets were melt extruded using a short shaft extruder having a coat hanger type T die (Mitsubishi Heavy Industries, Ltd .: screw diameter 90 mm, T die lip material is tungsten carbide, peel strength 44N from molten resin).
- a cycloolefin polymer film having a thickness of 75 ⁇ m was produced by molding.
- extrusion molding a long unstretched film A having a width of 1000 mm was obtained in a clean room of class 10,000 or less under molding conditions of a molten resin temperature of 240 ° C. and a T die temperature of 240 ° C. Unstretched film A was wound up on a roll.
- the norbornene-based unstretched film A obtained above is stretched by the stretching section 5 (see FIG. 4 and the like) of the production system 1 of the present embodiment by the method shown below to obtain a stretched film A ′. It was. In addition, in the extending
- both ends of the unstretched film A sent from the film feeding section 2 are connected to the first clip as the preceding holding tool Ci and the first clip as the delaying holding tool Co. Grip with 2 clips.
- the unstretched film A is gripped, the unstretched film A is gripped by moving the clip levers of the first and second clips with the clip closer.
- both ends of the unstretched film A are simultaneously gripped by the first and second clips, and the line connecting the grip positions at both ends is parallel to the axis parallel to the width direction of the film.
- the gripped unstretched film A is conveyed while being gripped by the first and second clips, and heated by passing through the preheating zone Z1, the stretching zone Z2 and the heat fixing zone Z3 in the heating zone Z, and the width A stretched film A ′ stretched in an oblique direction with respect to the hand direction (a direction of 45 ° with respect to the width direction) is obtained.
- the film moving speed during heating and stretching was 30 m / min. Further, the temperature of the preheating zone Z1 was 140 ° C., the temperature of the stretching zone Z2 was 140 ° C., and the temperature of the heat setting zone Z3 was 137 ° C. Further, the stretching ratio of the film before and after stretching was 2.0 times, and the thickness of the film after stretching was 52 ⁇ m and the width was 2000 mm.
- the slit nozzle 17 of FIG. 25 and FIG. 26 was arrange
- the partition wall 41 is rotated so as to be substantially parallel to the orientation direction (orientation angle 45 °) of the stretched film A ′, and in conjunction with the rotation operation of the partition wall 41, the orientation direction of the stretched film A ′.
- the adjustment mechanism 21 adjusts the crossing angle ⁇ of the heating region H of the heating unit 11 so that the crossing direction of the heating region H with respect to the transport direction D is substantially parallel.
- trimming treatment was applied to both ends of the obtained stretched film A 'to obtain a final film width of 1500 mm.
- the average value of in-plane retardation Ro of the obtained film was 140 nm, and the average value of the orientation angle ⁇ was 45 °.
- the cycloolefin polymer film described above is also referred to as a COP film.
- the stretched film ( ⁇ / 4 retardation film) produced by the above-described method was bonded to one side of the above polarizer using a 5% polyvinyl alcohol aqueous solution as an adhesive.
- the lamination was performed such that the transmission axis of the polarizer and the slow axis of the ⁇ / 4 retardation film were oriented at 45 °.
- a Konica Minolta-tack film KC6UA manufactured by Konica Minolta Opto Co., Ltd.
- alkali saponification treatment was similarly bonded to the other surface of the polarizer to produce a circularly polarizing plate.
- a reflective electrode made of chromium having a thickness of 80 nm was formed on a glass substrate by sputtering.
- ITO indium tin oxide
- PEDOT poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate
- PEDOT poly(3,4-ethylenedioxythiophene) -polystyrene sulfonate
- PEDOT poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate
- each of the RGB light emitting layers was formed to a thickness of 100 nm on the hole transport layer using a shadow mask.
- red light emitting layer tris (8-hydroxyquinolinate) aluminum (Alq 3 ) as a host and a light emitting compound [4- (dicyanomethylene) -2-methyl-6 (p-dimethylaminostyryl) -4H-pyran] (DCM ) Were co-evaporated (mass ratio 99: 1) to form a thickness of 100 nm.
- the green light-emitting layer was formed with a thickness of 100 nm by co-evaporating Alq 3 as a host and the light-emitting compound coumarin 6 (mass ratio 99: 1).
- the blue light emitting layer was formed as a host by co-evaporating BAlq represented by the following structural formula and a light emitting compound Perylene (mass ratio 90:10) to a thickness of 100 nm.
- calcium was deposited to a thickness of 4 nm by vacuum deposition as a first cathode having a low work function so that electrons can be efficiently injected onto the light emitting layer.
- aluminum was formed to a thickness of 2 nm as a second cathode on the first cathode.
- the aluminum used as the second cathode has a role of preventing the calcium as the first cathode from being chemically altered when the transparent electrode formed thereon is formed by sputtering. .
- an organic light emitting layer was obtained.
- a transparent conductive film having a thickness of 80 nm was formed on the cathode by sputtering.
- ITO was used as the transparent conductive film.
- 200 nm of silicon nitride was formed on the transparent conductive film by a CVD method (chemical vapor deposition method) to obtain an insulating film. This produced the organic EL element.
- the size of the produced organic EL element was 1296 mm ⁇ 784 mm.
- the circularly polarizing plate prepared as described above is fixed on the insulating film of the organic EL element prepared above with an adhesive so that the surface of the ⁇ / 4 retardation film faces the insulating film of the organic EL element. Turn into. Thereby, an organic EL image display device was produced.
- Example 1-2 In Example 1-2, the angle ⁇ i formed by the film feeding direction D1 and the winding direction D2 was changed, and the film stretching direction was set to 15 ° (orientation angle 15 °) with respect to the width direction. This is the same as Example 1-1.
- Example 2-1 In Example 2-1, the halogen lamp 12 shown in FIG. 6 was used as the heating unit 11 disposed in the heat setting zone Z3, and the stretched film A ′ (orientation angle 45 °) was heated in the vicinity thereof. Except for this, this is the same as Example 1-1.
- Example 2-2 In Example 2-2, the angle ⁇ i formed by the film feeding direction D1 and the winding direction D2 was changed, and the film stretching direction was set to 15 ° (orientation angle 15 °) with respect to the width direction. This is the same as Example 2-1.
- Comparative Example 1-1 was the same as Example 1-1 except that the heating unit 11 was not disposed in the heat setting zone Z3, and the stretched film A ′ (orientation angle 45 °) was not heated by the heating unit 11. It is.
- ⁇ Evaluation method for variation in orientation angle> A long stretched film (COP film) produced by the same method as in Examples 1-1 to 2-2 and Comparative Examples 1-1 to 1-2 described above, with the width direction being the width of the film as produced. After making it a strip-like film with a longitudinal direction of 10 cm and leaving it in a room at 23 ° C. and 55% RH for 24 hours, the width of the long stretched film was measured using a phase difference measuring device (manufactured by Oji Scientific Co., Ltd., KOBRA-WXK). The orientation angle was measured at intervals of 50 mm in the hand direction, and the difference between the maximum value and the minimum value was defined as the variation (°) in the orientation angle ⁇ .
- a phase difference measuring device manufactured by Oji Scientific Co., Ltd., KOBRA-WXK
- standard at the time of evaluating a reflected light amount nonuniformity visually is as follows.
- Double-circle In the produced organic electroluminescent image display apparatus, the ratio of the person who feels a difference in the reflected light quantity for every location is 10% or less.
- A In the produced organic EL image display device, the percentage of people who feel a difference in the amount of reflected light at each location is more than 10% and 20% or less.
- X In the produced organic electroluminescent image display apparatus, the ratio of the person who feels a difference in the reflected light quantity for every location is more than 50%.
- the film conveyance speed in the oblique stretching step is 30 m / min, but when the film conveyance speed is relatively high, 15 m / min to 150 m / min, the upstream zone The air is drawn into the downstream zone as the film is transported, and temperature unevenness is likely to occur in the vicinity of the film. Therefore, the configuration of the present embodiment that can suppress variations in the optical value of the film due to temperature unevenness is very effective when the film is conveyed in the above speed range.
- a cellulose film is prepared by the following method, and Examples 1-1 to 2-2 and Comparative Examples 1-1 to 1-2 are prepared.
- a stretched film, a circularly polarizing plate, and an organic EL image display device were produced under the same conditions as in Example 1, and the reflected light amount unevenness was evaluated.
- the result was the same as the result of Table 1 performed using the COP film. .
- ⁇ Fine particle additive solution Based on the following composition, the fine particle dispersion was slowly added to a dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution. 99 parts by mass of methylene chloride 5 parts by mass of fine particle dispersion 1
- a main dope solution having the following composition was prepared. That is, first, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose acetate was added to a pressurized dissolution tank containing a solvent while stirring. This was heated and stirred to dissolve completely, and this was dissolved in Azumi Filter Paper No.
- the main dope solution was prepared by filtration using 244.
- combined by the following synthesis examples was used for the sugar ester compound and the ester compound.
- the inside of the Kolben was depressurized to 4 ⁇ 10 2 Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 ⁇ 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off.
- the ester compound had an ester of benzoic acid at the end of the polyester chain formed by condensation of 1,2-propylene glycol, phthalic anhydride and adipic acid.
- the acid value of the ester compound was 0.10, and the number average molecular weight was 450.
- the composition was put into a closed container and dissolved with stirring to prepare a dope solution.
- the dope solution was uniformly cast on a stainless steel belt support with a width of 1000 mm.
- the solvent was evaporated until the residual solvent amount in the cast (cast) film was 75%, and the film was peeled off from the stainless steel belt support.
- the peeled cellulose ester film was stretched 1.1 times in the width direction by a transverse stretching tenter.
- the temperature conditions of the transverse stretching tenter oven at that time were adjusted to 160 ° C. in the preheating zone, 165 ° C. in the stretching zone, 172 ° C. in the holding zone, and 110 ° C. in the cooling zone.
- the tenter clip marks at both ends of the film are trimmed, the drying temperature is 130 ° C., and the drying is finished while the long film is conveyed in the drying zone using a number of rolls, and then wound in the winding process. It was wound up as a circular body. As described above, a roll-shaped long film (long film original fabric) having a dry film thickness of 75 ⁇ m was obtained.
- the long film of the cellulose-based resin obtained above was obliquely stretched using the stretched portion 5 shown in FIG. 4 to obtain a long stretched film.
- the film moving speed is 30 m / min
- the temperature of the preheating zone Z1 is 187 ° C.
- the temperature of the stretching zone Z2 is 185 ° C.
- the temperature of the heat setting zone Z3 is 170 ° C.
- the stretching ratio is 2.0 times.
- a final stretched film was produced under the same conditions as in the above-described cycloolefin film production method except that the final film width after trimming was 1500 mm.
- the present invention can be used for the production of a long obliquely stretched film applied to a circularly polarizing plate for preventing external light reflection of an organic EL image display device.
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Abstract
Description
前記延伸ゾーンを含んでこれよりも搬送方向下流側に位置するゾーンのうち、少なくとも1つのゾーン内に、搬送される前記フィルムと対向するように位置し、かつ、前記フィルムの面内で搬送方向と交差角φで交差する方向に沿って位置する加熱領域を有する加熱部によって、前記フィルムを加熱する加熱工程と、
前記延伸ゾーンにて延伸されたフィルムの配向方向に応じて、前記加熱領域の前記交差角φを調整する調整工程とを有していることを特徴とする延伸フィルムの製造方法。
前記延伸ゾーンを含んでこれよりも搬送方向下流側に位置するゾーンのうち、少なくとも1つのゾーン内に、搬送される前記フィルムと対向するように位置し、かつ、前記フィルムの面内で搬送方向と交差角φで交差する方向に沿って位置する加熱領域によって、前記フィルムを加熱する加熱部と、
前記延伸ゾーンにて延伸されたフィルムの配向方向に応じて、前記加熱領域の前記交差角φを調整する調整機構とを備えていることを特徴とする延伸フィルムの製造装置。
熱風を吹き出す複数の吹出孔が2次元的に形成されたパンチ板ノズルと、
一方向に伸びる開口部を有し、前記パンチ板ノズルの前記吹出孔側に設けられて、前記開口部以外の領域で前記複数の吹出孔から吹き出す熱風の一部を遮断する遮風板とを備え、
前記加熱領域は、前記開口部が伸びる前記一方向が、前記フィルムの搬送方向と交差角φで交差する方向に沿うように、前記遮風板を配置することによって形成されていることを特徴とする前記7から11のいずれかに記載の延伸フィルムの製造装置。
熱風を吹き出す単一の吹出孔が形成されたスリットノズルと、
一方向に伸びる開口部を有し、前記スリットノズルの前記吹出孔側に設けられて、前記開口部以外の領域で前記吹出孔から吹き出す熱風の一部を遮断する遮風板とを備え、
前記加熱領域は、前記開口部が伸びる前記一方向が、前記フィルムの搬送方向と交差角φで交差する方向に沿うように、前記遮風板を配置することによって形成されていることを特徴とする前記7から11のいずれかに記載の延伸フィルムの製造装置。
前記スリットノズルは、前記スリットが伸びる前記一方向が、前記フィルムの搬送方向と交差角φで交差する方向に沿うように設けられていることを特徴とする前記7から11のいずれかに記載の延伸フィルムの製造装置。
前記延伸フィルムの製造装置に対して、延伸対象となるフィルムを繰り出すフィルム繰り出し部とを備えていることを特徴とする延伸フィルムの製造システム。
まず、本実施形態で延伸対象となる長尺フィルムについて説明する。
脂環式オレフィンポリマー系樹脂としては、特開平05-310845号公報に記載されている環状オレフィンランダム多元共重合体、特開平05-97978号公報に記載されている水素添加重合体、特開平11-124429号公報に記載されている熱可塑性ジシクロペンタジエン系開環重合体およびその水素添加物等を挙げることができる。
好ましいセルロースエステル系樹脂フィルムとしては、下記式(1)および(2)を満たすセルロースアシレートを含有し、かつ、下記一般式(A)で表される化合物を含有するものが挙げられる。
式(1) 2.0≦Z1<3.0
式(2) 0≦X<3.0
(式(1)および(2)において、Z1はセルロースアシレートの総アシル置換度を表し、Xはセルロースアシレートのプロピオニル置換度およびブチリル置換度の総和を表す。)
(I)WaおよびWbが互いに結合して環を形成してもよく、
(II)WaおよびWbの少なくとも一つが環構造を有してもよく、または
(III)WaおよびWbの少なくとも一つがアルケニル基またはアルキニル基であってもよい。
本実施形態に係るセルロースアシレートフィルムは、セルロールアシレートを主成分として含有する。例えば、本実施形態に係るセルロースアシレートフィルムは、フィルムの全質量(100質量%)に対して、セルロースアシレートを好ましくは60~100質量%の範囲で含む。また、セルロースアシレートの総アシル基置換度は、2.0以上3.0未満であり、2.2~2.7であることがより好ましい。
式(i) 2.0≦X+Y<3.0
式(ii) 0≦X<3.0
式中、Yはアセチル基の置換度を表し、Xはプロピオニル基もしくはブチリル基またはその混合物の置換度を表す。
カラム:Shodex K806、K805、K803G(昭和電工株式会社製)を3本接続して使用する;
カラム温度:25℃;
試料濃度:0.1質量%;
検出器:RI Model 504(GLサイエンス社製);
ポンプ:L6000(日立製作所株式会社製);
流量:1.0ml/min
校正曲線:標準ポリスチレンSTK standard ポリスチレン(東ソー株式会社製)Mw=1000000~500の13サンプルによる校正曲線を使用する。13サンプルは、ほぼ等間隔に用いる。
本実施形態に係る製造方法により得られた長尺延伸フィルムは、後述するセルロースエステル以外の高分子成分を適宜混合したものでもよい。混合される高分子成分はセルロースエステルと相溶性に優れるものが好ましく、フィルムにした時の透過率が80%以上、更に好ましくは90%以上、更に好ましくは92%以上であることが好ましい。
リタデーションを調整するために添加する化合物としては、欧州特許911,656A2号明細書に記載されているような、二つ以上の芳香族環を有する芳香族化合物を使用することができる。
本実施形態におけるセルロースエステルフィルムは、セルロースエステルと、カルボキシル基、ヒドロキシル基、アミノ基、アミド基、およびスルホン酸基から選ばれる置換基を有し、かつ、重量平均分子量が500~200,000の範囲内であるビニル系化合物のポリマーまたはオリゴマーとを含有することが好ましい。当該セルロースエステルと、当該ポリマーまたはオリゴマーとの含有量の質量比が、95:5~50:50の範囲内であることが好ましい。
本実施形態では、マット剤として微粒子を延伸フィルム中に含有させることができ、これによって、延伸フィルムが長尺フィルムの場合、搬送や巻き取りをしやすくすることができる。
その他、カオリン、タルク、ケイソウ土、石英、炭酸カルシウム、硫酸バリウム、酸化チタン、アルミナ等の無機微粒子、カルシウム、マグネシウム等のアルカリ土類金属の塩等の熱安定剤を加えてもよい。更に界面活性剤、剥離促進剤、帯電防止剤、難燃剤、滑剤、油剤等も加えてもよい。
本実施形態におけるセルロースエステル系樹脂フィルムには、より高温の環境下での使用に耐えられることが求められている。このため、セルロースエステル系樹脂フィルムの張力軟化点は、105℃~145℃であれば十分な耐熱性を示すため好ましく、特に110℃~130℃であることが好ましい。
本実施形態におけるセルロースエステル系樹脂フィルムを有機EL画像表示装置に用いた場合、吸湿による寸法変化により、厚みムラや位相差値の変化、およびコントラストの低下や色ムラといった問題を発生させないために、該セルロースエステル系樹脂フィルムの寸法変化率(%)は0.5%未満が好ましく、更に、0.3%未満であることが好ましい。
本実施形態におけるセルロースエステル系樹脂フィルムは、フィルム中の欠点が少ないことが好ましい。ここで、欠点とは、溶液製膜の乾燥工程において溶媒の急激な蒸発に起因して発生するフィルム中の空洞(発泡欠点)や、製膜原液中の異物や製膜中に混入する異物に起因するフィルム中の異物(異物欠点)を言う。
また、本実施形態に係るセルロースエステル系樹脂フィルムは、JIS(Japanese Industrial Standards Committee;日本工業標準調査会)の規格の一つである、JIS-K7127-1999に準拠した測定において、少なくとも一方向の破断伸度が、10%以上であることが好ましく、より好ましくは20%以上である。
本実施形態に係るセルロースエステル系樹脂フィルムは、その全光線透過率が90%以上であることが好ましく、より好ましくは93%以上である。また、全光線透過率の現実的な上限としては、99%程度である。かかる全光線透過率にて表される優れた透明性を達成するには、可視光を吸収する添加剤や共重合成分を導入しないようにすることや、ポリマー中の異物を高精度濾過により除去し、フィルム内部の光の拡散や吸収を低減させることが有効である。また、製膜時のフィルム接触部(冷却ロール、カレンダーロール、ドラム、ベルト、溶液製膜における塗布基材、搬送ロールなど)の表面粗さを小さくしてフィルム表面の表面粗さを小さくすることによりフィルム表面の光の拡散や反射を低減させることが有効である。
上述した樹脂からなる本実施形態の長尺フィルムは、以下に示す溶液流延法、溶融流延法のどちらでも製膜することができる。以下、各製膜法について説明する。なお、以下では、長尺フィルムとして、例えばセルロースエステル系樹脂フィルムを製膜する場合について説明するが、他の樹脂フィルムの製膜についても勿論適用することができる。
フィルムの着色抑制、異物欠点の抑制、ダイラインなどの光学欠点の抑制、フィルムの平面性、透明度に優れるなどの観点からは、長尺フィルムを溶液流延法で製膜することが好ましい。
本実施形態に係るセルロースエステル系樹脂フィルムを溶液流延法で製造する場合のドープを形成するのに有用な有機溶媒は、セルロースアセテート、その他の添加剤を同時に溶解するものであれば制限なく用いることができる。
本実施形態に係るセルロースエステル系樹脂フィルムは、溶液流延法によって製造することができる。溶液流延法では、樹脂および添加剤を溶剤に溶解させてドープを調製する工程、ドープをベルト状もしくはドラム状の金属支持体上に流延する工程、流延したドープをウェブとして乾燥する工程、金属支持体から剥離する工程、延伸または幅保持する工程、更に乾燥する工程、仕上がったフィルムを巻き取る工程により行われる。
残留溶媒量(質量%)={(M-N)/N}×100
なお、Mはウェブまたはフィルムを製造中または製造後の任意の時点で採取した試料の質量(g)であり、NはMを115℃で1時間の加熱した後の質量(g)である。
溶融流延法は、後述する斜め延伸後のフィルムの厚み方向のリタデーションRtを小さくすることが容易となり、残留揮発性成分量が少なくフィルムの寸法安定性にも優れる等の観点から、好ましい製膜法である。溶融流延法は、樹脂および可塑剤などの添加剤を含む組成物を、流動性を示す温度まで加熱溶融し、その後、流動性のセルロースアセテートを含む溶融物を流延してフィルムを製膜する方法をいう。溶融流延によって形成される方法は、溶融押出(成形)法、プレス成形法、インフレーション法、射出成形法、ブロー成形法、延伸成形法などに分類できる。これらの中で、機械的強度および表面精度などに優れるフィルムが得られる溶融押出法が好ましい。また、溶融押出法で用いる複数の原材料は、通常、予め混錬してペレット化しておくことが好ましい。
本実施形態における長尺フィルムの厚さは、好ましくは30~200μm、より好ましくは40~150μmである。また、本実施形態では、後述する延伸ゾーンに供給される長尺フィルムの流れ方向(搬送方向)の厚みムラσmは、後述する斜め延伸テンター入口でのフィルムの引取張力を一定に保ち、配向角やリタデーションといった光学特性を安定させる観点から、0.30μm未満、好ましくは0.25μm未満、さらに好ましくは0.20μm未満である必要がある。長尺フィルムの流れ方向の厚みムラσmが0.30μm以上となると、長尺延伸フィルムのリタデーションや配向角といった光学特性のバラツキが顕著に悪化する。
次に、上述した長尺フィルムを幅手方向に対して斜め方向に延伸する長尺斜め延伸フィルムの製造装置について説明する前に、その製造装置を備えた長尺斜め延伸フィルムの製造システム全体について説明する。
図1は、延伸フィルムの製造システム1の概略の構成を模式的に示す平面図である。また、図2は、製造システム1の他の構成を模式的に示す平面図であり、図3は、製造システム1のさらに他の構成を模式的に示す平面図である。図1に示すように、本実施形態の製造システム1は、長尺フィルムの搬送方向上流側から順に、フィルム繰り出し部2と、搬送方向変更部3と、ガイドロール4と、延伸部5と、ガイドロール6と、搬送方向変更部7と、フィルム巻き取り部8とを備えている。なお、延伸部5は、本実施形態の延伸フィルムの製造装置であるが、その詳細については後述する。
次に、上述した延伸部5の詳細について説明する。図4は、延伸部5のレールパターンの一例を模式的に示す平面図である。但し、これは一例であって、本発明はこれに限定されるものではない。
本発明の実施形態に係る製造方法により得られた長尺延伸フィルムにおいては、配向角θが巻取方向に対して、例えば0°より大きく90°未満の範囲に傾斜しており、少なくとも1300mmの幅において、幅方向の、面内リタデーションRoのバラツキが2nm以下、配向角θのバラツキが0.5°以下であることが好ましい。
本実施形態の円偏光板は、偏光板保護フィルム、偏光子、λ/4位相差フィルムがこの順で積層されており、前記λ/4位相差フィルムの遅相軸と偏光子の吸収軸(または透過軸)とのなす角度が45°である。なお、上記の偏光板保護フィルム、偏光子、λ/4位相差フィルムは、それぞれ、図5の保護フィルム313、偏光子312、λ/4位相差フィルム311にそれぞれ対応している。本実施形態においては、長尺状偏光板保護フィルム、長尺状偏光子、長尺状λ/4位相差フィルム(長尺延伸フィルム)がこの順で積層して形成されることが好ましい。
図5は、本実施形態の有機EL画像表示装置100の概略の構成を示す断面図である。なお、有機EL画像表示装置100の構成は、これに限定されるものではない。
次に、上述した延伸部5の加熱ゾーンZに設けられる加熱部および調整機構の詳細について説明する。なお、以下では、加熱ゾーンZを仕切る隔壁の移動動作と連動して、調整機構が加熱領域の後述する交差角φを調整する例について説明するが、調整機構は、隔壁の移動動作とは連動せずに(別個独立に)、上記交差角φを調整するようにしてもよい。
図15は、加熱部11の他の構成を示す平面図である。同図に示すように、加熱部11の加熱領域Hは、複数本(同図では例えば5本)の棒状のランプヒータ12を、長手方向がフィルムFの搬送方向Dに沿うように、かつ、少なくとも2本のランプヒータ12の(上流側の)端部同士を結ぶ方向がフィルムFの搬送方向Dと交差角φで交差する方向に沿うように、(フィルムの幅手方向に)並列に配置することによって形成されていてもよい。このように複数本のランプヒータ12を配置することによっても、所望の方向(搬送方向と交差角φで交差する方向)に伸びて形成される加熱領域Hを実現することができる。
以下、本実施形態における延伸フィルムの製造に関する具体例な実施例について、比較例も挙げながら説明する。なお、本発明は、以下の実施例に限定されるものではない。以下の実施例では、熱可塑性樹脂フィルムを成膜後、図4で示した延伸部5で熱可塑性樹脂フィルムを延伸し、斜め延伸光学フィルムを作製した。なお、以下では、「部」あるいは「%」の表記を用いるが、特に断らない限り、これらは「質量部」あるいは「質量%」を表すものとする。
[シクロオレフィン系フィルムの製造方法]
窒素雰囲気下、脱水したシクロヘキサン500部に、1-ヘキセン1.2部、ジブチルエーテル0.15部、トリイソブチルアルミニウム0.30部を室温で反応器に入れ混合した後、45℃に保ちながら、トリシクロ[4.3.0.12,5]デカ-3,7-ジエン(ジシクロペンタジエン、以下、DCPと略記)20部、1,4-メタノ-1,4,4a,9a-テトラヒドロフルオレン(以下、MTFと略記)140部、および8-メチル-テトラシクロ[4.4.0.12,5.17,10]-ドデカ-3-エン(以下、MTDと略記)40部からなるノルボルネン系モノマー混合物と、六塩化タングステン(0.7%トルエン溶液)40部とを、2時間かけて連続的に添加し重合した。重合溶液にブチルグリシジルエーテル1.06部とイソプロピルアルコール0.52部を加えて重合触媒を不活性化し重合反応を停止させた。
厚さ120μmのポリビニルアルコールフィルムを、一軸延伸し(温度110℃、延伸倍率5倍)、ヨウ素0.075g、ヨウ化カリウム5g、水100gからなる水溶液に60秒間浸漬し、次いでヨウ化カリウム6g、ホウ酸7.5g、水100gからなる68℃の水溶液に浸漬した。浸漬後のフィルムを水洗、乾燥し、偏光子を得た。
ガラス基板上にスパッタリング法によって厚さ80nmのクロムからなる反射電極を製膜した。次に、反射電極上に陽極としてITO(酸化インジウムスズ)をスパッタリング法で厚さ40nmで製膜した。続いて、陽極上に正孔輸送層としてポリ(3,4-エチレンジオキシチオフェン)-ポリスチレンスルホネート(PEDOT:PSS)をスパッタリング法で厚さ80nmで製膜した。その後、正孔輸送層上にシャドーマスクを用いて、RGBそれぞれの発光層を100nmの膜厚で形成した。
実施例1-2では、フィルムの繰出方向D1と巻取方向D2とがなす角度θiを変更して、フィルムの延伸方向を幅手方向に対して15°(配向角15°)とした以外は、実施例1-1と同様である。
実施例2-1では、熱固定ゾーンZ3に配置される加熱部11として、図6で示したハロゲンランプ12を用い、延伸フィルムA’(配向角45°)をその近傍で加熱するようにした以外は、実施例1-1と同様である。
実施例2-2では、フィルムの繰出方向D1と巻取方向D2とがなす角度θiを変更して、フィルムの延伸方向を幅手方向に対して15°(配向角15°)とした以外は、実施例2-1と同様である。
比較例1-1では、熱固定ゾーンZ3に加熱部11を配置せず、加熱部11による延伸フィルムA’(配向角45°)の加熱を行わなかった以外は、実施例1-1と同様である。
比較例1-2では、フィルムの繰出方向D1と巻取方向D2とがなす角度θiを変更して、フィルムの延伸方向を幅手方向に対して15°(配向角15°)とした以外は、比較例1-1と同様である。
上記の実施例1-1~2-2および比較例1-1~1-2と同じ手法で作製した長尺延伸フィルム(COPフィルム)を、幅手方向は作製時のフィルムの幅のままで、長手方向が10cmの短冊状のフィルムとし、23℃55%RHの部屋に24h放置した後、位相差測定装置(王子計測(株)製、KOBRA-WXK)を用い、長尺延伸フィルムの幅手方向に50mmの間隔で配向角を測定し、その最大値と最小値との差を配向角θのバラツキ(°)とした。
上記の実施例1-1~2-2および比較例1-1~1-2と同じ手法で作製した長尺延伸フィルム(COPフィルム)を、幅手方向は作製時のフィルムの幅のままで、長手方向が10cmの短冊状のフィルムとし、23℃55%RHの部屋に24h放置した後、位相差測定装置(王子計測(株)製、KOBRA-WXK)を用い、長尺延伸フィルムの幅手方向に50mmの間隔で面内リタデーションRoを測定し、その最大値と最小値との差を面内リタデーションRoのバラツキ(nm)とした。
上記作製した有機EL画像表示装置を、太陽光の下で、黒表示した際のディスプレイ全面における反射光量ムラを目視で評価した。表1は、実施例1-1、2-1および比較例1-1について反射光量ムラを評価した結果と、実施例1-1~2-2および比較例1-1~1-2についての各光学値(配向角、面内リタデーション)とを併せて示している。なお、実施例1-2、2-2および比較例1-2については、ロールtoロール方式で偏光板を作製した場合、単独では円偏光板として機能しないため(配向角が幅手方向に対して15°であるため)、反射光量ムラの評価は行っていない。
◎:作製した有機EL画像表示装置において、箇所ごとの反射光量に違いを感じる人の割合が10%以下である。
○:作製した有機EL画像表示装置において、箇所ごとの反射光量に違いを感じる人の割合が10%よりも多く、20%以下である。
△:作製した有機EL画像表示装置において、箇所ごとの反射光量に違いを感じる人の割合が20%よりも多く、50%以下である。
×:作製した有機EL画像表示装置において、箇所ごとの反射光量に違いを感じる人の割合が50%よりも多い。
<微粒子分散液>
微粒子(アエロジル R972V 日本アエロジル(株)製)
11質量部
エタノール 89質量部
以上をディゾルバーで50分間攪拌混合した後、マントンゴーリンで分散を行った。
以下の組成に基づいて、メチレンクロライドを入れた溶解タンクに充分攪拌しながら、上記微粒子分散液をゆっくりと添加した。さらに二次粒子の粒径が所定の大きさとなるようにアトライターにて分散を行った。これを日本精線(株)製のファインメットNFで濾過し、微粒子添加液を調製した。
メチレンクロライド 99質量部
微粒子分散液1 5質量部
下記組成の主ドープ液を調製した。すなわち、まず、加圧溶解タンクにメチレンクロライドとエタノールを添加した。溶剤の入った加圧溶解タンクにセルロースアセテートを攪拌しながら投入した。これを加熱し、攪拌しながら、完全に溶解し、これを安積濾紙(株)製の安積濾紙No.244を使用して濾過し、主ドープ液を調製した。なお、糖エステル化合物およびエステル化合物は、以下の合成例により合成した化合物を用いた。また、化合物(B)は、以下のものを用いた。
メチレンクロライド 340質量部
エタノール 64質量部
セルロースアセテートプロピオネート(アセチル基置換度1.39、プロピオニル基置換度0.50、総置換度1.89) 100質量部
化合物(B) 5.0質量部
糖エステル化合物 5.0質量部
エステル化合物 2.5質量部
微粒子添加液1 1質量部
以下の工程により、糖エステル化合物を合成した。
1)LC部
装置:日本分光(株)製カラムオーブン(JASCO CO-965)、ディテクター(JASCO UV-970-240nm)、ポンプ(JASCO PU-980)、デガッサ-(JASCO DG-980-50)
カラム:Inertsil ODS-3 粒子径5μm 4.6×250mm(ジーエルサイエンス(株)製)
カラム温度:40℃
流速:1ml/min
移動相:THF(1%酢酸):H2O(50:50)
注入量:3μl
2)MS部
装置:LCQ DECA(Thermo Quest(株)製)
イオン化法:エレクトロスプレーイオン化(ESI)法
Spray Voltage:5kV
Capillary温度:180℃
Vaporizer温度:450℃
以下の工程により、エステル化合物を合成した。
上記組成物を密閉容器に投入し、攪拌しながら溶解してドープ液を調製した。次いで、無端ベルト流延装置を用い、上記ドープ液を、1000mm幅でステンレススティールベルト支持体上に均一に流延した。ステンレススティールベルト支持体上で、流延(キャスト)したフィルム中の残留溶媒量が75%になるまで溶媒を蒸発させ、ステンレススティールベルト支持体上から剥離した。
2 フィルム繰り出し部
5 延伸部
11 加熱部
12 ランプヒータ
13 パネルヒータ
13a 側辺
14 パンチ板ノズル
14a 吹出孔
15 遮風板
15a 開口部
16 スリットノズル
16a 吹出孔
17 スリットノズル
17a スリット
21 調整機構
41 隔壁
Ci 把持具
Co 把持具
H 加熱領域
Z 加熱ゾーン
Z2 延伸ゾーン
Z3 熱固定ゾーン
φ 交差角
Claims (19)
- フィルムの搬送方向に沿って並び、前記フィルムに対して加熱または冷却のための温度制御を行う複数のゾーンに含まれる延伸ゾーンにて、前記フィルムを幅手方向に対して斜め方向に延伸する延伸フィルムの製造方法であって、
前記延伸ゾーンを含んでこれよりも搬送方向下流側に位置するゾーンのうち、少なくとも1つのゾーン内に、搬送される前記フィルムと対向するように位置し、かつ、前記フィルムの面内で搬送方向と交差角φで交差する方向に沿って位置する加熱領域を有する加熱部によって、前記フィルムを加熱する加熱工程と、
前記延伸ゾーンにて延伸されたフィルムの配向方向に応じて、前記加熱領域の前記交差角φを調整する調整工程とを有していることを特徴とする延伸フィルムの製造方法。 - 前記調整工程では、延伸されたフィルムの配向方向と、前記フィルムの搬送方向に対する前記加熱領域の交差方向とが略平行となるように、前記加熱領域の前記交差角φを調整することを特徴とする請求項1に記載の延伸フィルムの製造方法。
- 前記調整工程では、前記フィルムが通過可能な隙間を有して、前記加熱部が配置されるゾーンとその上流側のゾーンとの間に設けられる隔壁が、延伸されたフィルムの配向方向に応じて移動する動作と連動して、前記加熱領域の前記交差角φを調整することを特徴とする請求項1または2に記載の延伸フィルムの製造方法。
- 前記隔壁は、延伸されたフィルムの配向方向と略平行となるように移動することを特徴とする請求項3に記載の延伸フィルムの製造方法。
- 前記延伸ゾーンでは、前記フィルムの幅手方向の両端部を各把持具によって把持し、各把持具を移動させながら前記フィルムを搬送するとともに、前記フィルムの搬送方向を途中で変えることにより、前記フィルムを幅手方向に対して斜め方向に延伸することを特徴とする請求項1から4のいずれかに記載の延伸フィルムの製造方法。
- 前記延伸ゾーンでは、前記フィルムを、15m/min~150m/minの速度で搬送しながら斜め延伸することを特徴とする請求項5に記載の延伸フィルムの製造方法。
- フィルムの搬送方向に沿って並び、前記フィルムに対して加熱または冷却のための温度制御を行う複数のゾーンを備え、前記複数のゾーンに含まれる延伸ゾーンにて、前記フィルムを幅手方向に対して斜め方向に延伸する延伸フィルムの製造装置であって、
前記延伸ゾーンを含んでこれよりも搬送方向下流側に位置するゾーンのうち、少なくとも1つのゾーン内に、搬送される前記フィルムと対向するように位置し、かつ、前記フィルムの面内で搬送方向と交差角φで交差する方向に沿って位置する加熱領域によって、前記フィルムを加熱する加熱部と、
前記延伸ゾーンにて延伸されたフィルムの配向方向に応じて、前記加熱領域の前記交差角φを調整する調整機構とを備えていることを特徴とする延伸フィルムの製造装置。 - 前記調整機構は、延伸されたフィルムの配向方向と、前記フィルムの搬送方向に対する前記加熱領域の交差方向とが略平行となるように、前記加熱領域の前記交差角φを調整することを特徴とする請求項7に記載の延伸フィルムの製造装置。
- 前記調整機構は、前記フィルムが通過可能な隙間を有して、前記加熱部が配置されるゾーンとその上流側のゾーンとの間に設けられる隔壁が、延伸されたフィルムの配向方向に応じて移動する動作と連動して、前記加熱領域の前記交差角φを調整することを特徴とする請求項7または8に記載の延伸フィルムの製造装置。
- 前記隔壁は、延伸されたフィルムの配向方向と略平行となるように移動することを特徴とする請求項9に記載の延伸フィルムの製造装置。
- 前記加熱部は、前記隔壁に対して前記フィルムの搬送方向下流側であって、前記隔壁の直後に位置していることを特徴とする請求項9または10に記載の延伸フィルムの製造装置。
- 前記加熱部の前記加熱領域は、少なくとも1本の棒状のランプヒータを、その長手方向が前記フィルムの搬送方向と交差角φで交差する方向に沿うように配置することによって形成されていることを特徴とする請求項7から11のいずれかに記載の延伸フィルムの製造装置。
- 前記加熱部の前記加熱領域は、複数本の棒状のランプヒータを、長手方向が前記フィルムの搬送方向に沿うように、かつ、少なくとも2本のランプヒータの端部同士を結ぶ方向が前記フィルムの搬送方向と交差角φで交差する方向に沿うように、並列に配置することによって形成されていることを特徴とする請求項7から11のいずれかに記載の延伸フィルムの製造装置。
- 前記加熱部の前記加熱領域は、パネルヒータを、その側辺が前記フィルムの搬送方向と交差角φで交差する方向に沿うように配置することによって形成されていることを特徴とする請求項7から11のいずれかに記載の延伸フィルムの製造装置。
- 前記加熱部は、
熱風を吹き出す複数の吹出孔が2次元的に形成されたパンチ板ノズルと、
一方向に伸びる開口部を有し、前記パンチ板ノズルの前記吹出孔側に設けられて、前記開口部以外の領域で前記複数の吹出孔から吹き出す熱風の一部を遮断する遮風板とを備え、
前記加熱領域は、前記開口部が伸びる前記一方向が、前記フィルムの搬送方向と交差角φで交差する方向に沿うように、前記遮風板を配置することによって形成されていることを特徴とする請求項7から11のいずれかに記載の延伸フィルムの製造装置。 - 前記加熱部は、
熱風を吹き出す単一の吹出孔が形成されたスリットノズルと、
一方向に伸びる開口部を有し、前記スリットノズルの前記吹出孔側に設けられて、前記開口部以外の領域で前記吹出孔から吹き出す熱風の一部を遮断する遮風板とを備え、
前記加熱領域は、前記開口部が伸びる前記一方向が、前記フィルムの搬送方向と交差角φで交差する方向に沿うように、前記遮風板を配置することによって形成されていることを特徴とする請求項7から11のいずれかに記載の延伸フィルムの製造装置。 - 前記加熱部は、一方向に伸びるスリットを前記加熱領域として有し、前記スリットから熱風を吹き出して前記フィルムを加熱するスリットノズルを備え、
前記スリットノズルは、前記スリットが伸びる前記一方向が、前記フィルムの搬送方向と交差角φで交差する方向に沿うように設けられていることを特徴とする請求項7から11のいずれかに記載の延伸フィルムの製造装置。 - 前記延伸ゾーンでは、前記フィルムの幅手方向の両端部を各把持具によって把持し、各把持具を移動させながら前記フィルムを搬送するとともに、前記フィルムの搬送方向を途中で変えることにより、前記フィルムを幅手方向に対して斜め方向に延伸することを特徴とする請求項7から17のいずれかに記載の延伸フィルムの製造装置。
- 請求項7から18のいずれかに記載の延伸フィルムの製造装置と、
前記延伸フィルムの製造装置に対して、延伸対象となるフィルムを繰り出すフィルム繰り出し部とを備えていることを特徴とする延伸フィルムの製造システム。
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JP2016060184A (ja) * | 2014-09-22 | 2016-04-25 | 富士フイルム株式会社 | 延伸装置、フィルム製造設備及び方法 |
WO2022215407A1 (ja) * | 2021-04-06 | 2022-10-13 | コニカミノルタ株式会社 | 偏光板保護フィルムの製造方法 |
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US20150048548A1 (en) | 2015-02-19 |
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