WO2013118172A1 - 長尺延伸フィルムの製造方法 - Google Patents
長尺延伸フィルムの製造方法 Download PDFInfo
- Publication number
- WO2013118172A1 WO2013118172A1 PCT/JP2012/000846 JP2012000846W WO2013118172A1 WO 2013118172 A1 WO2013118172 A1 WO 2013118172A1 JP 2012000846 W JP2012000846 W JP 2012000846W WO 2013118172 A1 WO2013118172 A1 WO 2013118172A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- stretched film
- long
- group
- long stretched
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- 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
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00634—Production of filters
- B29D11/00644—Production of filters polarizing
-
- 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
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/005—Oriented
- B29K2995/0051—Oriented mono-axially
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0094—Geometrical properties
- B29K2995/0097—Thickness
-
- 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
- B29L2011/00—Optical elements, e.g. lenses, prisms
- B29L2011/0066—Optical filters
-
- 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
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3475—Displays, monitors, TV-sets, computer screens
-
- 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
Definitions
- the present invention relates to a method for producing a long stretched film.
- 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 electroluminescence display device (hereinafter also referred to as an organic EL display) has attracted attention as a new display device.
- the self-luminous display device has a room for suppressing power consumption compared with a liquid crystal display device whose backlight is always lit, and further, a self-luminous display in which a light source corresponding to each color such as an organic EL display is lit.
- 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, so that external light incident on the display is reflected by this reflector, thereby contrasting the image.
- a circularly polarizing plate on the surface side of the display by bonding the stretched film and a polarizer to improve contrast of light and darkness by preventing reflection of external light.
- a circularly polarizing plate may be used also in what is called a 3D liquid crystal display device which displays a three-dimensional image.
- the above circularly polarizing plate needs to be bonded in such an arrangement that the in-plane slow axis of the stretched film is inclined at a desired angle with respect to the absorption axis of the polarizer.
- a general polarizer (polarizing film) is obtained by stretching at a high magnification in the transport direction, and its absorption axis coincides with the transport direction, and the conventional retardation film is longitudinally stretched, or Manufactured by transverse stretching, the in-plane slow axis is in principle 0 ° or 90 ° with respect to the longitudinal direction of the film.
- a long polarizing film and / or a stretched film is cut out at a specific angle to form a film.
- the resin film has a slow axis at a desired angle of more than 0 ° and less than 90 ° by obliquely stretching the resin film by changing the moving distance between the gripping portion and the other gripping portion.
- a stretched film whose slow axis is inclined with respect to the width direction a long polarizing film and a stretched film ( ⁇ / 4 retardation film) are used instead of the conventional batch-type bonding.
- ⁇ / 4 retardation film ⁇ / 4 retardation film
- each of the in-plane slow axes of the ⁇ / 2 retardation film and ⁇ / 4 retardation film has been proposed (see Patent Document 5, for example).
- the in-plane slow axis of each film needs to be inclined at an arbitrary angle with respect to the width direction. Therefore, it can be stretched in an arbitrary angle direction by changing the stretching pattern of one oblique stretching device rather than an oblique stretching device that can stretch only in a specific angular direction, and has an in-plane slow axis tilt angle.
- An oblique stretching apparatus capable of producing a long stretched film is preferably used (see, for example, Patent Document 6).
- a self-luminous display device in which a light source corresponding to each color is lit, such as an organic EL display, has few members such as a color filter that cause a reduction in contrast.
- the contrast was recognized as a problem because a very high contrast was observed, but slight variations in optical characteristics were observed as color unevenness.
- the conventional oblique stretching apparatus described above is oriented when the stretching angle is changed when manufacturing the stretched film at various stretching angles by changing the stretching direction angle. It was found that slight variations in corners occurred, and such slight variations in orientation angles were observed as color unevenness.
- the present invention has been made in view of the above-described conventional problems, and is a case where, in a long stretched film stretched in an oblique direction, the stretching angle of the long stretched film is changed by changing the travel path of the gripping tool. Even in the case where it is used for a circularly polarizing plate used in an image display device having a very high contrast such as an organic EL display, the variation in the width direction of the orientation angle of the obtained long stretched film is suppressed. It aims at providing the manufacturing method of the elongate stretched film which can suppress generation
- the tension applied not only in the width direction but also in the conveying direction is a stretched film. It was found to be an important factor in determining the orientation of the slow axis. Further, it has been found that the cause of variation in the width direction of the orientation angle depending on the stretching angle is caused by uneven tension in the width direction of the film at the grip release point. That is, when the gripped film is released from the gripper at the grip release point, uneven tension occurs in the long stretched film, and the uneven tension affects the stretching tension of the stretching zone (especially a diagonally curved zone). Thus, it has been found that the orientation angle varies in the width direction.
- the position of the grip release point changes when the stretching angle is changed. Therefore, for example, even if the tension release is reduced by adjusting the position of the grip release point so that the straight line connecting the grip release point at a certain stretching angle is parallel to the width direction of the long stretched film, When the travel route of the tool is changed (when the stretching angle is changed), the positional relationship between the straight line connecting the grip release points and the width direction of the long stretched film changes, and new uneven tension occurs. I understood.
- the manufacturing method of the elongate stretched film by one aspect of this invention for solving said subject is the process of forming the elongate film which consists of a thermoplastic resin, The film of the film after extending
- the long film is fed out from a specific direction different from the winding direction, and both ends of the long film are gripped by a holding device of an oblique stretching apparatus and conveyed, and the long film is larger than 0 ° and 90 ° with respect to the width direction.
- the oblique stretch device is a feeding direction of the long film
- the stretching direction can be arbitrarily changed so that the winding direction of the long stretched film is in a direction obliquely crossed with the grip.
- the grip release point of the holding tool can be moved independently in the winding direction of the long stretched film, and the grip release line connecting the grip release points at both ends is the width of the long stretched film. The grip release point is adjusted so as to be parallel to the direction.
- FIG. 1 is a schematic view for explaining oblique stretching used in a method for producing a long stretched film according to an embodiment of the present invention.
- FIG. 2 is a schematic view of a stretching apparatus according to an embodiment of the present invention.
- FIG. 3 is an explanatory diagram for explaining the movement of the grip release point.
- FIG. 4 is a schematic view of a stretching apparatus according to an embodiment of the present invention.
- FIG. 5 is a schematic view of a stretching apparatus according to an embodiment of the present invention.
- FIG. 6 is a schematic diagram of an organic EL display according to an embodiment of the present invention.
- FIG. 7 is a schematic view of a stretching apparatus used in the comparative example.
- FIG. 8 is a schematic view of a stretching apparatus used in the comparative example.
- FIG. 9 is a schematic view of a stretching apparatus used in the comparative example.
- the present inventors have found that in the oblique stretching apparatus, the straight line connecting the grip release points of the gripping tool for gripping both ends of the long stretched film is the film. It has been found that the above object can be achieved by adjusting the grip release point so as to be parallel to the transport direction. Then, the inventors have further studied and have completed the present invention based on these findings.
- the embodiment of the present invention includes a step of forming a long film made of a thermoplastic resin, the long film is fed out from a specific direction different from the winding direction of the stretched film, An oblique stretching step of obliquely stretching the long film in a direction larger than 0 ° and less than 90 ° with respect to the width direction while being gripped and conveyed by a gripping tool of an oblique stretching device, and after the oblique stretching step
- the oblique stretching apparatus has a winding direction of the long stretched film in a direction oblique to the feeding direction of the long film.
- the stretching direction can be arbitrarily changed, and in the oblique stretching step, the grip release points of the gripping tool for gripping both ends of the long stretched film are respectively in the winding direction of the long stretched film. It is possible to move independently, and the grip release point is adjusted so that the grip release line connecting the grip release points at both ends is parallel to the width direction of the long stretched film.
- This is a method for producing a stretched film. According to said structure, even if it is a case where the extending
- the grip open point can be adjusted to be parallel to the width direction of the long stretched film, so long stretched films having various orientation directions can be adjusted using one device. It can be manufactured. In this case, the unevenness of the orientation angle can be reduced, and as a result, the color unevenness of the display device can be suppressed.
- the present invention is characterized by the oblique stretching step among the above steps, the oblique stretching step will be described in detail.
- 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.
- the oblique stretching step is a step of stretching the formed long film in a direction oblique to the width direction.
- a film can be manufactured to desired arbitrary length by manufacturing a film continuously.
- the film after film formation may be continuously supplied to the oblique stretching process from the film forming process without winding up the film. It is preferable to perform the film forming step and the oblique stretching step continuously, because the film forming conditions can be changed by feeding back the film thickness after stretching and the optical value result, and a desired long stretched film can be obtained.
- 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. Since the slow axis is usually expressed in the stretching direction or a direction perpendicular to the stretching direction, the production method according to the present embodiment performs stretching at an angle of more than 0 ° and less than 90 ° with respect to the film extension direction. Thus, a long stretched film having such a slow axis can be produced.
- the angle formed by the extension direction of the long stretched film and the slow axis can be arbitrarily set to a desired angle in the range of more than 0 ° and less than 90 °.
- an oblique stretching apparatus In order to impart an oblique orientation to the long film subjected to stretching in this embodiment, an oblique stretching apparatus is used.
- the oblique stretching apparatus used in the present embodiment can freely set the orientation angle of the film by changing the path pattern of the gripping tool traveling support tool in various ways, and further the orientation axis of the film across the film width direction. It is preferable that the film stretching apparatus can be oriented with high precision in the left and right directions and can control the film thickness and retardation with high precision.
- FIG. 1 is a schematic diagram for explaining oblique stretching used in the method for producing a long stretched film of the present embodiment.
- this is an example, and the present invention is not limited to this.
- 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.
- the feeding angle ⁇ i can be arbitrarily set to a desired angle in the range of more than 0 ° and less than 90 °.
- the long film has a left and right gripping tool (a pair of left and right grips) at the entrance of the oblique stretching apparatus (the gripping tool is a gripping start point for gripping the long film, and a straight line connecting the gripping start points is indicated by reference symbol A). It is gripped by the gripping tool pair) and travels as the gripping tool travels.
- the gripping tool is a gripping start point for gripping the long film, and a straight line connecting the gripping start points is indicated by reference symbol A). It is gripped by the gripping tool pair) and travels as the gripping tool travels.
- the gripping tool pair is composed of left and right gripping tools Ci and Co that are opposed to a direction substantially perpendicular to the traveling direction of the long film (feeding direction D1) at the entrance of the oblique stretching apparatus.
- the left and right gripping tools Ci and Co travel along an asymmetrical path, respectively, and the position at the end of stretching (the gripping release point at which the gripping tool releases the gripping, and the straight line connecting the gripping release points is denoted by reference symbol B.
- the long stretched film gripped in (shown) is released.
- the long film is obliquely stretched in the direction of ⁇ L.
- substantially vertical indicates that the angle is in a range of 90 ⁇ 1 °.
- the production method of the present invention is performed using a stretching apparatus capable of oblique stretching.
- This stretching apparatus is an apparatus that heats a long film to an arbitrary temperature at which stretching can be performed and stretches the film in an oblique manner.
- the stretching device includes a heating zone, a plurality of gripping tools paired on both sides for traveling while gripping both sides of a long film, and a gripping tool travel support tool for supporting the travel of the gripping tool. I have. Grip both ends of the long film that is sequentially supplied to the inlet (holding start point) of the stretching device with a gripper, guide the long film into the heating zone, and grip it at the outlet (holding release point) of the stretching device. Release the long stretched film from the tool.
- the long stretched film released from the gripping tool is wound around the core.
- the gripping tool traveling support tool having the gripping tool has an endless continuous track, and the gripping tool that has released the grip of the long stretched film at the exit of the stretching device is sequentially returned to the gripping start point by the gripping tool travel support tool. It is supposed to be.
- the endless chain whose path is regulated by a guide rail or a gear may include the gripper, or the endless guide rail may be a gripper.
- the gripping tool travel support tool may be, for example, an endless guide rail provided with an endless chain, or may be an endless guide rail provided with an endless chain. There may be no endless guide rail.
- the gripper travel support tool does not include a chain, the gripper travels along the path of the gripper travel support tool itself.
- the gripper travel support tool includes the chain, the gripper travel support tool travels along the path of the gripper travel support tool. Run.
- the gripping tool travels along the path of the gripping tool travel support tool will be described as an example, but in any case, the gripping tool is connected via a chain provided on the gripping tool. You may run.
- the number of gripping tools provided in each gripping tool travel support tool is not particularly limited, but is preferably the same number.
- the path of the gripping tool travel support tool of the stretching device has an asymmetric shape on the left and right, and the path of the grip tool travel support tool depends on the orientation angle, stretch ratio, etc. given to the long stretched film to be manufactured.
- the pattern can be adjusted manually or automatically.
- the path of each gripper travel support tool can be freely set and the path pattern of the gripper travel support tool can be arbitrarily changed.
- the traveling speed of the gripping tool of the stretching apparatus can be selected as appropriate, and is preferably 1 to 150 m / min.
- the traveling speed of the gripping device of the stretching apparatus is higher than 150 m / min, the local stress applied to the end of the film is increased at the position where the conveyance of the long film is inclined, and wrinkles and There is a tendency that the effective width obtained as a non-defective product is narrowed out of the entire width of the film obtained after completion of stretching.
- the difference in travel speed between at least a gripping tool gripping the film is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less of the travel speed. It is constant speed. This is because if there is a difference in running speed between the left and right of the long stretched film at the exit of the stretching process, wrinkles and misalignment will occur at the exit of the stretching process, so the speed difference between the left and right gripping tools constituting the gripping tool pair is substantially This is because it is required to be constant speed. In general stretching devices, etc., there are speed irregularities that occur in the order of seconds or less depending on the period of the sprocket (gear) teeth that drive the chain, the frequency of the drive motor, etc. These do not correspond to the speed difference described in this embodiment.
- the length (full length) of the gripping tool travel support tool is not particularly limited, and may be the same or different.
- FIG. 2 is a schematic view of the stretching apparatus T1 of the present embodiment.
- FIG. 2A shows a stretching apparatus in which the stretching angle ⁇ 1 is set to 22.5 °
- FIG. 2B shows the stretching angle ⁇ 2. Shows a stretching apparatus in which is set to 45 °.
- 3A to 3C are explanatory views for explaining the movement of the grip release point.
- the gripping tools (the gripping tool 1i and the gripping tool 1o) grip the end in the width direction of the long film at the grip start point on the straight line A.
- the gripper releases the end of the long stretched film F that is gripped at the grip release point on the straight line B.
- the inner gripping tool travel support Ri is provided with a turning gear G1 for determining the grip release point of the gripping tool 1i traveling on the inner gripping tool travel support Ri.
- the gripping tool 1i traveling on the inner gripping tool travel support tool Ri releases the long stretched film F that has been gripped at the gripping release point whose position is determined by the turning gear G1.
- the outer gripping tool travel support tool Ro is provided with a return gear G2 for determining a grip release point of the gripping tool 1o traveling on the outer gripping tool travel support tool Ro.
- the gripping tool 1o traveling on the outer gripping tool travel support tool Ro releases the long stretched film F that has been gripped at the gripping release point whose position is determined by the turning gear G2.
- the folding gear G1 and the folding gear G2 can change the position of the grip release point by freely changing the installation position of one or both along the winding direction of the long stretched film.
- the stretching angle is changed by changing the shape of the gripping tool traveling support tool, the positional relationship of the straight line B connecting the gripping release points with respect to the long stretched film F to be conveyed is not parallel.
- the stretching device T1 changes the position of the gripping release point by changing the position of one or both of the folding gear G1 and the folding gear G2 along the winding direction of the long stretched film, It can adjust so that the positional relationship of the straight line B with respect to the width direction of the elongate stretched film F may always become parallel.
- connection angle of the gripping tool travel support tool at the connection portion 2 is adjusted to change the shape of the gripping tool travel support tool, thereby changing the stretch angle.
- the positions of the folding gear G1 and the folding gear G2 change, so the straight line B is not parallel to the width direction of the long stretched film F.
- the installation position of the folding gear G1 and the folding gear G2 or both of them can be freely changed along the winding direction of the long stretched film.
- the straight line B can be adjusted to be parallel to the width direction of the elongated stretched film F (see FIG. 2B). . That is, the angle ⁇ 3 shown in FIGS. 2A and 2B is both 90 °.
- FIGS. 3 (a) to 3 (c) the point that the folding gear G1 and the folding gear G2 can move independently in the winding direction of the long stretched film will be described more specifically.
- FIG. 3A shows the result of adjusting the stretching angle.
- the position of the folding gear G1 is located downstream of the position of the folding gear G2 in the conveyance direction (winding direction) of the long stretched film.
- a grip release line is parallel to the width direction of a elongate stretched film. So as to move from the position indicated by the two-dot chain line to the position indicated by the solid line.
- FIG. 3B illustrates a stretching apparatus in which the grip release line is no longer parallel to the width direction of the long stretched film as a result of adjusting the stretching angle.
- the folding gear G1 and the folding gear G2 can move independently of each other. That is, the folding gear G1 can move in the direction of arrow A1 (winding direction of the long stretched film), and the folding gear G2 can move in the direction of arrow A1 ′ (winding direction of the long stretched film). Can do.
- the grip release line is adjusted to be parallel to the width direction of the long stretched film.
- the angle ⁇ B formed by the direction is adjusted to be the same.
- FIG. 3C illustrates a stretching apparatus in which the grip release line is no longer parallel to the width direction of the long stretched film as a result of adjusting the stretching angle as in FIG. 3B.
- the turning gear G1 and the turning gear G2 can move independently of each other. That is, the folding gear G1 can move in the direction of arrow A1 (winding direction of the long stretched film), and the folding gear G2 can move in the direction of arrow A1 ′ (winding direction of the long stretched film). Can do.
- the grip release line is adjusted to be parallel to the width direction of the long stretched film.
- the angle ⁇ D formed by the direction is adjusted to be 90 ° in any case.
- examples of the oblique stretching apparatus include a linear motor system, a pantograph system, and a motor chain drive system.
- a motor chain system a rotatable sprocket (turnback gear) is installed on the inner periphery (or outer periphery) of an endless roller chain.
- the sprocket is driven while applying an appropriate tension to the chain to rotate the roller chain.
- the roller chain is provided with a gripping tool, and the gripping tool travels along the rail pattern of the guide rail by the rotation of the sprocket.
- the stretching device T1 of the present embodiment may include a mechanism for adjusting the tension applied to the roller chain by the folding gear G1 and the folding gear G2 so that the tension is the same even when the position of the folding gear is moved. it can.
- each gripping tool travel support tool is provided with either one or both of the folding gear G1 and the folding gear G2 so as not to cause the inconvenience.
- adjustment gears for example, adjustment gear G3 and adjustment gear G4
- the adjustment gears G3 and G4 have the tension applied to the roller chain before the movement when the folding gear G1 or the folding gear G2 moves so that the straight line B is parallel to the width direction of the long stretched film F. It can be moved to add a similar tension.
- the movement direction and the movement distance of the adjustment G3 and the adjustment gear G4 are not particularly limited as long as the tension and the distance before the folding gear G1 and the folding gear G2 move can be applied to the roller chain.
- the adjustment gear G3 and the adjustment gear G4 can move independently in the winding direction of the long stretched film, similarly to the folding gear G1 and the folding gear G2. That is, all of the folding gear G1, the folding gear G2, the adjusting gear G3, and the adjusting gear G4 of the stretching device of the present embodiment can move independently in the winding direction of the long stretched film.
- the folding gear G1 moves in parallel with the winding direction of the long film to the upstream side in the transport direction, and the stretching angle Even in the state of 45 °, the straight line B moves so as to be parallel to the width direction of the long stretched film F.
- the adjustment gear G3 moves in the direction of the arrow A2
- the adjustment gear G4 moves in the direction of the arrow A3, and the respective gripping tool travel support tools are stretched outward in the circumferential direction.
- the tension applied to the chain) can be adjusted.
- the stretching apparatus T1 of the present embodiment can be adjusted so that the straight line B and the width direction of the long stretched film are parallel regardless of the stretching angle, the gripping tool 1i that travels the inner gripping tool travel support tool Ri is long.
- the stress applied to the long stretched film F when the long stretched film F is released and the stress applied to the long stretched film F by the gripping tool 1o traveling on the outer gripping tool traveling support tool Ro when releasing the long stretched film F are mutually Be countered.
- thickness unevenness of the obtained long stretched film is reduced, and variations in the orientation angle in the width direction can be reduced.
- the gripper travels on an endless gripper travel support tool.
- the gripper grips and stretches the long film supplied at the grip start point, and then releases the long stretched film F at the grip release point on the straight line B.
- the separation distance of each gripping tool forming the gripping tool pair corresponds to the width of the supplied long film.
- the long film is transported with the traveling gripper and passes through a preheating zone, a stretching zone, a heat fixing zone, and a cooling zone (not shown).
- the angle formed by the traveling direction of the gripping tool released from gripping at the gripping release point and the transport direction of the long stretched film is equal at both ends.
- FIG. 4 is a schematic diagram of a stretching apparatus T2 having a configuration in which the traveling direction of the gripping tool released from gripping at the gripping release point is a direction orthogonal to the transport direction of the long stretched film.
- a stretching apparatus in which the stretching angle ⁇ is set to 22.5 ° is shown, and
- FIG. 4B shows a stretching apparatus in which the stretching angle ⁇ is set to 45 °.
- the stretching device T2 of the present embodiment adjusts the tension applied by the folding gear G1 and the folding gear G2 to each gripping tool travel support so that the tension is the same even when the position of the folding gear is moved.
- a mechanism can be provided.
- the stretching device T2 can be provided with an adjustment gear G3 and an adjustment gear G4 in the vicinity of the return gear G1 and the return gear G2.
- the adjustment gear G3 and the adjustment G4 each have an angle formed between the traveling direction of the gripping tool changed by the folding gear 1 and the folding gear G2 and the winding direction of the long stretched film F after the gripping is released at the gripping release point. It is a gear that can determine the travel route of the gripping tool after gripping release so as to be equal on both sides.
- the angle formed by the traveling direction of the gripping tool changed by the folding gear 1 and the folding gear G2 and the winding direction of the long stretched film F after releasing the grip at the grip release point is equal on both sides.
- the stretching device T2 includes the adjustment gear G5 and the adjustment gear in addition to the adjustment gear G3 and the adjustment gear G4 in order to correct the change in the tension of the gripping tool traveling support tool caused by the movement of the folding gear G1 and the folding gear G2.
- G6 can be provided. That is, as shown in FIG. 4A, when the tension applied to the gripping tool travel support tool changes due to the movement of the folding gear G1 and the folding gear G2, the stretching device T2 Adjustment gears (adjustment gears G3 to G6) for adding to the gripping tool travel support tool can be provided. These adjustment gears G3 to G6 can move in accordance with the movement of the turning gear G1 and the turning gear G2.
- the moving direction and moving distance of these adjusting gears G3 to G6 are not particularly limited, and the direction and distance at which the tension before the turning gear G1 or the turning gear G2 moves can be applied to each gripping tool travel support tool. I just need it.
- the stretching device T2 when changing the stretching angle from 22.5 ° (see FIG. 4 (a)) to 45 °, like the stretching device T1 shown in FIG. Moves upstream in the conveying direction in parallel with the winding direction of the long stretched film.
- the adjustment gear G3 applies appropriate tension to the inner gripping tool travel support tool Ri in accordance with the movement of the folding gear G1, and the gripping tool traveling direction and the long stretched film that are changed by the folding gear after releasing the gripping.
- the adjustment gear G4 applies an appropriate tension to the outer gripping tool travel support tool Ro in accordance with the movement of the folding gear G2, and the traveling direction and length of the gripping tool changed by the folding gear after gripping release.
- the film can be moved in the arrow A3 direction.
- the stretching device T2 uses two gears of an adjustment gear G3 and an adjustment gear G5 in order to keep the tension applied to the inner gripping tool travel support tool Ri constant.
- the stretching device T2 uses two gears, an adjustment gear G4 and an adjustment gear G6, in order to keep the tension applied to the outer gripping tool travel support tool Ro constant.
- the adjustment gear G3 stretches the inner gripping tool travel support tool Ri outward in the circumferential direction by adjusting the extension angle, and adjusts the adjustment gear.
- G5 moves in the direction of arrow A4, and the inner gripping tool travel support tool Ri is deformed and adjusted inward in the circumferential direction.
- the tension reduction (deflection) caused by the change in the stretching angle is stretched outward in the circumferential direction by the adjustment gear G4, and the adjustment gear G6 is indicated by an arrow.
- the outer gripping tool travel support tool Ro is moved in the A5 direction to be deformed and adjusted inward in the circumferential direction.
- the number of adjusting gears is not particularly limited, and may be one as in the stretching device T1, or may be a plurality of three or more.
- FIG. 5 is a schematic diagram of a stretching apparatus T3 having a configuration in which an angle formed by the traveling direction of the gripping tool changed by the folding gear after the gripping release and the winding direction of the long stretched film is a right angle.
- A shows a stretching apparatus in which the stretching angle ⁇ is set to 22.5 °
- FIG. 5 shows a stretching apparatus in which the stretching angle ⁇ is set to 45 °.
- the stretching device T3 of the present embodiment adjusts the tension applied by the folding gear G1 and the folding gear G2 to each gripping tool travel support so that the tension is the same even when the position of the folding gear is moved.
- a mechanism can be provided.
- the stretching device T3 can be provided with an adjustment gear G3 and an adjustment gear G4 in the vicinity of the return gear G1 and the return gear G2.
- the adjustment gear G3 and the adjustment G4 determine the travel route so that the travel direction of the gripping tool changed by the return gear after the grip release is orthogonal to the angle formed by the winding direction of the long stretched film.
- the turning gear G1, the turning gear G2, the adjusting gear G3, and the adjusting gear G4 are all arranged on the straight line B.
- the travel direction of the gripping tool changed by the folding gear after the grip release is configured to travel in the direction perpendicular to the winding direction of the long stretched film.
- the gripper can relieve the stress applied to the long stretched film, suppress uneven tension in the resulting long stretched film, and further reduce the variation in the width direction of the orientation angle. Since the waviness at the time can be suppressed, the density of the wound body wound up in the subsequent winding process can be increased, and deterioration of the shape of the wound body can be suppressed even after the durability test.
- the stretching device T3 includes the adjustment gear G5 and the adjustment gear in addition to the adjustment gear G3 and the adjustment gear G4 in order to correct the change in the tension of the gripping tool traveling support tool caused by the movement of the folding gear G1 and the folding gear G2.
- G6 can be provided. That is, as shown in FIG. 5 (a), when the tension applied to the gripping tool travel support tool is changed by the movement of the folding gear G1 and the folding gear G2, the stretching device T3 changes the tension before the movement to the respective tension.
- Adjustment gears (adjustment gears G3 to G6) for adding to the gripping tool travel support tool can be provided. These adjustment gears G3 to G6 can move in accordance with the movement of the turning gear G1 and the turning gear G2.
- the moving direction and moving distance of these adjusting gears G3 to G6 are not particularly limited, and the direction and distance at which the tension before the turning gear G1 or the turning gear G2 moves can be applied to each gripping tool travel support tool. I just need it.
- the stretching device T3 when the stretching angle is changed from 22.5 ° (see FIG. 5A) to 45 °, is similar to the stretching device T1 shown in FIG. Moves upstream in the conveying direction in parallel with the winding direction of the long stretched film.
- the adjustment gear G3 applies an appropriate tension to the inner gripping tool travel support tool Ri, and maintains the travel direction of the gripping tool in a direction orthogonal to the long stretched film being conveyed. Therefore, it moves in the direction of arrow A2.
- the adjustment gear G4 applies an appropriate tension to the outer gripping tool travel support tool Ro in accordance with the movement of the folding gear G2, and the traveling direction and length of the gripping tool changed by the folding gear after gripping release.
- the film can be moved in the arrow A3 direction.
- the stretching device T3 uses two gears, an adjustment gear G3 and an adjustment gear G5, to keep the tension applied to the inner gripping tool travel support tool Ri constant.
- the stretching device T3 uses two gears, an adjustment gear G4 and an adjustment gear G6, in order to keep the tension applied to the outer gripping tool travel support tool Ro constant.
- the adjustment gear G3 stretches the inner gripping tool travel support tool Ri outward in the circumferential direction by adjusting the extension angle, and adjusts the adjustment gear.
- G5 moves in the direction of arrow A4, and the inner gripping tool travel support tool Ri is deformed and adjusted inward in the circumferential direction.
- the tension reduction (deflection) caused by the change in the stretching angle is stretched outward in the circumferential direction by the adjustment gear G4, and the adjustment gear G6 is indicated by an arrow.
- the outer gripping tool travel support tool Ro is moved in the A5 direction to be deformed and adjusted inward in the circumferential direction.
- the number of adjusting gears is not particularly limited, and may be one as in the stretching device T1, or may be a plurality of three or more.
- a high bending rate is often required for the gripping tool traveling support that regulates the locus of the gripping tool, particularly in a portion where the conveyance of the long film is oblique.
- the long film is sequentially gripped by the left and right gripping tools (a pair of gripping tools) at the entrance of the oblique stretching apparatus (position of the straight line A in FIG. 1), and the gripping tool travels. Drive with it.
- a pair of gripping tools facing the direction substantially perpendicular to the long film traveling direction D1 at the entrance of the oblique stretching apparatus travels on a rail that is asymmetrical and has a preheating zone, a stretching zone, and a heat fixing zone. Pass through the zone.
- the preheating zone refers to a section where the distance between the gripping tools gripping both ends is kept constant at the heating zone entrance.
- the stretching zone refers to the interval until the gap between the gripping tools that grips both ends starts to reach a predetermined interval.
- the film can be stretched in an oblique direction in the stretching zone, but is not limited to the stretching in the oblique direction. You may extend
- the heat setting zone refers to the section in which the gripping tools at both ends run parallel to each other during the period when the spacing between the gripping tools after the stretching zone becomes constant again. You may pass through the area (cooling zone) by which the temperature in a zone is set to below the glass transition temperature Tg degreeC of the thermoplastic resin which comprises a elongate film, after passing through a heat setting zone. At this time, in consideration of the shrinkage of the long stretched film due to cooling, a rail pattern that narrows the gap between the opposing grippers in advance may be used.
- transverse stretching and longitudinal stretching may be carried out as necessary in the steps before and after introducing the long film into the oblique stretching apparatus for the purpose of adjusting the mechanical properties and optical properties of the film.
- the temperature of each zone is set to Tg to Tg + 30 ° C in the preheating zone, Tg to Tg + 30 ° C in the preheating zone, and Tg-30 to Tg ° C in the cooling zone with respect to the glass transition temperature Tg of the thermoplastic resin. It is preferable to do.
- a temperature difference in the width direction may be applied in the stretching zone in order to control thickness unevenness in the width direction.
- 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 is known. Can be used.
- the length of the preheating zone, the stretching zone and the cooling zone can be appropriately selected. The length of the preheating zone is usually 100 to 150% and the length of the fixed zone is usually 50 to 100% with respect to the length of the stretching zone. . Further, a cooling zone may be provided after the heat setting zone.
- the draw ratio R (W / W0) in the drawing step is preferably 1.3 to 3.0, more preferably 1.5 to 2.8. If the draw ratio is in this range, thickness unevenness in the width direction is reduced, which is preferable. In the stretching zone of the oblique stretching tenter, if the stretching temperature is differentiated in the width direction, the thickness unevenness in the width direction can be further improved.
- W0 represents the width of the long film before stretching
- W represents the width of the long film after stretching.
- the film forming step is a step of forming a long film made of a thermoplastic resin.
- the long film formed in this embodiment is not particularly limited as long as it is a long film made 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, and cellulose ester resins.
- polycarbonate resins, olefin polymer resins having an alicyclic structure, and cellulose ester resins are preferable from the viewpoints of transparency and mechanical strength.
- an olefin polymer resin having an alicyclic structure and a cellulose ester resin which are easy to adjust a phase difference when an optical film is used, are more preferable, and among them, an olefin polymer resin having an alicyclic structure is stretched. Since stress is low, it is particularly preferable from the viewpoint that wrinkles and shifts are less likely to occur at the end of the film even when obliquely stretched by high-speed conveyance.
- alicyclic olefin polymer-based 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
- the thermoplastic dicyclopentadiene ring-opening polymer and hydrogenated product thereof described in JP-A-124429 can be employed.
- the olefin polymer resin having an alicyclic structure 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 formability of the long film are highly balanced and suitable.
- the proportion of the repeating unit containing the alicyclic structure in the alicyclic olefin polymer 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. That's it.
- the ratio of the repeating unit having an alicyclic structure in the alicyclic polyolefin resin is within this range, the transparency and heat resistance of an optical material such as a retardation film obtained from the long stretched film of the present invention are improved. Therefore, it is preferable.
- olefin polymer resin having an alicyclic structure 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 suitable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability and lightness. Can be used.
- 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 hydroxy group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfo 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 conjugated dienes such as cyclohexadiene and cycloheptadiene. 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.
- ⁇ -olefins having 2 to 20 carbon atoms such as ethylene, propylene and 1-butene, and derivatives thereof
- cyclobutene, cyclopentene and And cycloolefins such as cyclohexene and derivatives thereof
- 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 long stretched film of the present invention 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 long stretched film of the present invention 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 the norbornene resin is preferably 10 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less, more preferably 7 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less, and 4 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less. It is particularly preferred that The photoelastic coefficient C is a value expressed by ⁇ n / ⁇ where birefringence is ⁇ n and stress is ⁇ . When the photoelastic coefficient of the thermoplastic resin is within such a range, variation in retardation (Re) in the in-plane direction, which will be described later, can be reduced.
- thermoplastic resin used in the present invention includes colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants and solvents.
- colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, antioxidants, lubricants and solvents.
- the compounding agent may be appropriately blended.
- the content of the residual volatile component in the long stretched film of norbornene-based resin is not particularly limited, but is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and further preferably 0.02% by mass. It is as follows. By setting the content of the volatile component in such a range, the dimensional stability can be improved, the temporal change of Re and Rth can be reduced, and further obtained from the long stretched film of the present invention. Deterioration of an image display device such as a retardation film, a polarizing plate or an organic EL display can be suppressed, and the display of the image display device such as an organic EL display can be kept stable and favorable for a long period.
- a residual volatile component is a substance having a molecular weight of 200 or less contained in a trace amount in a long film, and examples thereof include a residual monomer and a solvent.
- the content of the residual volatile component can be quantified by analyzing the long film by gas chromatography as the total of substances having a molecular weight of 200 or less contained in the long film.
- the saturated water absorption of the long stretched film of norbornene-based resin is preferably 0.03% by mass or less, more preferably 0.02% by mass or less, and particularly preferably 0.01% by mass or less.
- an image display device such as a retardation film, a polarizing plate or an organic EL display obtained from the long stretched film of the present invention Degradation can be suppressed, and the display of an image display device such as an organic EL display can be stably and satisfactorily maintained over a long period of time.
- Saturated water absorption is a value expressed as a percentage of the mass of a test piece of a long film immersed in water at a constant temperature for a fixed time and the increased mass before the immersion. Usually, it is measured by immersing in 23 ° C. water for 24 hours.
- the saturated water absorption rate in the long stretched film of the present invention can be adjusted to the above value by, for example, reducing the amount of polar groups in the thermoplastic resin, but preferably a resin having no polar groups. It is desirable to be.
- melt extrusion method As a method for forming a long film using the above preferred norbornene-based resin, a solution casting method or a melt extrusion method is preferred.
- 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.
- the extrusion molding method using a T-die is a method for maintaining retardation and orientation by a method of keeping a molten thermoplastic resin in a stable state when closely contacting a cooling drum as described in JP-A-2004-233604. It is possible to produce a long film with favorable optical characteristics such as corners.
- 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 to a specific temperature from the sheet-like thermoplastic resin extruded from the die opening when producing a long film by the melt extrusion method; A sheet-like thermoplastic resin extruded from a die so as to satisfy the above condition is taken into close contact with a cooling drum under a pressure of 50 kPa or less; A method in which a wind having a speed difference of 0.2 m / s or less from the cooling speed of the cooling drum that is first brought into close contact with the sheet-like thermoplastic resin extruded from the die opening is produced. It is done.
- This long film 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.
- cellulose ester-based resin examples include those characterized by containing a cellulose acylate satisfying the following formulas (i) and (ii) and containing a compound represented by the following general formula (A). .
- Formula (i) 2.0 ⁇ Z1 ⁇ 3.0
- Formula (ii) 0.5 ⁇ X
- Z1 represents the total acyl substitution degree of cellulose acylate
- X represents the sum of the propionyl substitution degree and butyryl substitution degree of cellulose acylate
- L1 and L2 each independently represent a single bond or a divalent linking group.
- L1 and L2 include the following structures. (The following R represents a hydrogen atom or a substituent.)
- L1 and L2 are preferably —O—, —COO—, and —OCO—.
- R1, R2 and R3 each independently represent a substituent.
- substituent represented by R1, R2 and R3 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 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,
- R1 and R2 are preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted cyclohexyl group. More preferred are a phenyl group having a substituent and a cyclohexyl group having a substituent, and further preferred are a phenyl group having a substituent at the 4-position and a cyclohexyl group having a substituent at the 4-position.
- R3 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, and 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.),
- Wa and Wb are bonded to each other to form a ring, it is preferably a nitrogen-containing 5-membered ring or a sulfur-containing 5-membered ring, particularly preferably represented by the following general formula (1) or general formula (2). It is a compound.
- A1 and A2 each independently represent —O—, —S—, —NRx— (Rx represents a hydrogen atom or a substituent) or CO—.
- Rx represents 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.
- L1, L2, R1, R2, R3, and n are synonymous with L1, L2, R1, R2, R3, and n in the general formula (A).
- Q1 is —O—, —S—, —NRy— (Ry represents a hydrogen atom or a substituent), —CRaRb— (Ra and Rb represent a hydrogen atom or a substituent) or CO -Represents.
- 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.
- 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, and 1 to 6 alkylsulfinyl groups, alkylsulfonyl groups having 1 to 6 carbon atoms, carboxyl groups, fluoroalkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, alkylthio groups having 1 to 6 carbon atoms, 1 carbon atom N-alkylamino group having 6 to 6, N, N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 6 carbon atoms, N, N-dialkylsulfur group having 2 to 12 carbon atoms
- substituent include a moyl group.
- L1, L2, R1, R2, R3, and n are synonymous with L1, L2, R1, R2, R3, and n in the general formula (A).
- Q3 represents ⁇ N— or ⁇ CRz— (Rz represents a hydrogen atom or a substituent), and Q4 represents a nonmetallic atom belonging to Groups 14-16.
- Z represents a nonmetallic atom group that forms a ring with Q3 and Q4.
- the ring formed from Q3, Q4 and Z may be condensed with another ring.
- the ring formed from Q3, Q4 and Z is preferably a nitrogen-containing 5-membered ring or 6-membered ring condensed with a benzene ring.
- L1, L2, R1, R2, R3, and n are synonymous with L1, L2, R1, R2, R3, and n in the general formula (A).
- Wa and Wb is an alkenyl group or an alkynyl group
- a vinyl group having a substituent and an ethynyl group are preferable.
- 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) of the present invention 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 anti-bleeding property can be imparted to the cellulose derivative of the present invention.
- general formula (A), general formula (1), general formula (2), and general formula (3) can be performed with reference to a known method. Specifically, it can be synthesized with reference to Journal of Chemical Crystallography (1997); 27 (9); 512-526, JP 2010-31223 A, JP 2008-107767 A, and the like.
- the cellulose acylate film that can be used in the present invention contains cellulose acylate as a main component.
- the cellulose acylate film that can be used in the present invention preferably contains cellulose acylate in the range of 60 to 100% by mass with respect to 100% by mass of the total mass of the film. Further, 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 0.5 or more.
- 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 according to the present invention preferably satisfies the following mathematical formulas (iii) and (iv).
- Formula (iii) 2.0 ⁇ X + Y ⁇ 3.0
- Formula (iv) 0.5 ⁇ X
- 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.
- cellulose acetate propionate 0 ⁇ Y ⁇ 2.5 and 0.5 ⁇ X ⁇ 3.0 (where 2.0 ⁇ X + Y ⁇ 3.0) are preferable, and 0 More preferably, 0.5 ⁇ Y ⁇ 2.0 and 1.0 ⁇ X ⁇ 2.0 (where 2.0 ⁇ X + Y ⁇ 3.0).
- the substitution degree of the acyl group can be measured according to ASTM-D817-96.
- the number average molecular weight of the cellulose acylate is preferably in the range of 60000 to 300000, since the mechanical strength of the obtained long stretched 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 invention.
- 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 can be preferable.
- a cellulose acylate is a thing with few bright spot foreign materials when it is set as a elongate stretched 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. 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 thought to be related to the water used in the production process, but it is preferable that there are few components that can become insoluble nuclei, in particular, metal ions such as iron, calcium, magnesium,
- An insoluble matter may be formed by salt formation with a polymer degradation product or the like that may contain an organic acidic group, and it is preferable that the amount 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.
- Fe iron
- Ca calcium
- Mg magnesium
- analysis can be performed using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer).
- the long stretched film obtained by the present invention 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 long stretched film is 80% or more, more preferably 90% or more, and further preferably 92% or more. preferable.
- Additives that can be added include plasticizers, UV absorbers, retardation modifiers, antioxidants, deterioration inhibitors, peeling aids, surfactants, dyes, and fine particles.
- 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 a polarizing plate used in an image display device such as an organic EL display.
- 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.
- 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 the compound to be added for adjusting the retardation, an aromatic compound having two or more aromatic rings as described in EP 911,656 A2 can be used.
- the aromatic ring of the aromatic compound includes an aromatic heterocyclic ring in addition to the aromatic hydrocarbon ring. Particularly preferred is an aromatic heterocycle, and 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 sulfo group, and has a weight average molecular weight in the range of 500 to 200,000. It is preferable to contain a polymer or oligomer of a certain vinyl compound.
- 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 long stretched film as a matting agent, whereby when the stretched film is long, conveyance and winding can be facilitated.
- 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.
- 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.
- polymer fine particles include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. Examples include Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.). Can do.
- 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 primary particles is more preferably 5 to 16 nm, 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 is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and still more preferably 0.08 to 0.16 g per 1 m2 of the stretched film.
- 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 that can be used in the present invention can be formed by a known method, and among them, the solution casting method and the melt casting method are preferable.
- polycarbonate resin various resins can be used without particular limitation, and an aromatic polycarbonate resin is preferable from the viewpoint of chemical properties and physical properties, and a bisphenol A polycarbonate resin is particularly preferable.
- an aromatic polycarbonate resin is preferable from the viewpoint of chemical properties and physical properties
- a bisphenol A polycarbonate resin is particularly preferable.
- those using a bisphenol A derivative in which a benzene ring, a cyclohexane ring, an aliphatic hydrocarbon group and the like are introduced into bisphenol A are more preferable.
- a polycarbonate resin having a structure in which the anisotropy in the unit molecule is reduced, obtained by using a derivative in which the functional group is introduced asymmetrically with respect to the central carbon of bisphenol A is particularly preferable.
- a polycarbonate resin for example, two methyl groups in the center carbon of bisphenol A are replaced by benzene rings, and one hydrogen of each benzene ring of bisphenol A is centered by a methyl group or a phenyl group.
- a polycarbonate resin obtained by using an asymmetrically substituted carbon is particularly preferable.
- 4,4′-dihydroxydiphenylalkane or a halogen-substituted product thereof can be obtained by a phosgene method or a transesterification method.
- 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl Examples include ethane and 4,4'-dihydroxydiphenylbutane.
- polycarbonate resins described in JP-A-2006-215465, JP-A-2006-91836, JP-A-2005-121813, JP-A-2003-167121 and the like can be mentioned. It is done.
- the polycarbonate resin may be used by mixing with a transparent resin such as polystyrene resin, methyl methacrylate resin, and cellulose acetate resin. Moreover, you may laminate
- the polycarbonate resin preferably has a glass transition point (Tg) of 110 ° C. or higher and a water absorption rate (measured under conditions of 23 ° C. water and 24 hours) of 0.3% or less. Yes. Moreover, Tg is 120 degreeC or more, and a water absorption rate is 0.2% or less more preferable.
- the polycarbonate resin film that can be used in the present invention can be formed by a known method, and among them, the solution casting method and the melt casting method are preferable.
- thermoplastic resin film Next, a method for forming a thermoplastic resin film will be described. In the following description, a method of forming a long film of cellulose ester resin will be described as an example.
- the solution casting method is preferable from the viewpoints of suppression of film coloring, suppression of foreign matter defects, suppression of optical defects such as die lines, excellent film flatness, and transparency.
- Organic solvent useful for forming the dope when the cellulose ester resin film according to the present invention is produced by the solution casting method is used without limitation as long as it dissolves cellulose acetate and other additives at the same time. Can do.
- 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. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.
- the concentration of cellulose acetate in the dope is preferably higher because the drying load after casting on a metal support can be reduced. However, if the concentration of cellulose acetate is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse.
- 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 temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness 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 warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.
- 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 60 to 130%. % By mass, particularly preferably 20 to 30% by mass or 70 to 120% by mass.
- the amount of residual solvent is defined by the following formula.
- Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100 Note that M is the mass of a sample collected at any time during or after the production of the web or long film, and N is the mass after heating M at 115 ° C. for 1 hour.
- the web is preferably peeled off from the metal support and further dried to make the residual solvent amount 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 in which the web is dried while being conveyed by a tenter method are employed.
- the melt casting method is a preferable film forming method from the viewpoint that it is easy to reduce the retardation Rt in the thickness direction after oblique stretching, the amount of residual volatile components is small, and the dimensional stability of the film is excellent.
- the melt casting method refers to heating and melting a composition containing an additive such as a resin and a plasticizer to a temperature exhibiting fluidity, and then casting a melt containing fluid cellulose acetate. 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 is preferable, in which a long film having excellent mechanical strength and surface accuracy can be obtained.
- a plurality of raw materials used for melt extrusion are usually kneaded and pelletized in advance.
- Pelletization may be performed by a known method. For example, dry cellulose acetate, a plasticizer, and other additives are fed to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder, and formed into a strand form from a die. It can be done by extrusion, water cooling or air cooling and cutting.
- Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.
- a small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.
- 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.
- the film is nipped by a cooling roll and an 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 by the cooling roll and the elastic touch roll is preferably Tg or more and Tg + 110 ° C. or less of the film.
- a well-known roll can be used for the roll which has the elastic body 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 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 long film formed by the above method is conveyed to the above stretching apparatus and stretched in an oblique direction.
- the thickness of the long film is preferably 20 to 400 ⁇ m, more preferably 30 to 200 ⁇ m.
- the thickness unevenness ⁇ m in the flow direction of the long film supplied for stretching keeps the take-up tension of the long film at the above-described oblique stretching tenter entrance constant, and stabilizes optical characteristics such as orientation angle and retardation. From the viewpoint, it is preferably less than 0.30 ⁇ m, preferably less than 0.25 ⁇ m, 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 long film having a thickness gradient in the width direction may be supplied as the long film.
- the gradient of the thickness of the long film was experienced by stretching a long film with various thickness gradients experimentally so that the film thickness at the position where the stretching of the subsequent process was completed could be the most uniform. Can be obtained.
- 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 modulus of elasticity is too low, the shrinkage rate during stretching and after stretching will be low, and wrinkles will be difficult to disappear. If it is too high, the tension applied during stretching will increase, and the part that holds both side edges of the long film will be It is necessary to increase the strength, and the load on the tenter in the subsequent process increases.
- a non-oriented film may be used, or a long film having an orientation in advance may be supplied. Further, if necessary, the width distribution of the orientation of the long film may be bowed, so-called bowing. In short, the orientation state of the long film can be adjusted so that the orientation of the long stretched film at the position where stretching in the subsequent step is completed can be made desirable.
- the oblique stretching process has already been described above.
- the long stretched film that has undergone the oblique stretching step is stretched obliquely in a direction greater than 0 ° and less than 90 ° with respect to the width direction of the long film.
- the stretched long stretched film is wound up by a subsequent winding process.
- the winding device is provided at the outlet of the oblique stretching device.
- the take-up position and angle of the long stretched film can be finely controlled. It becomes possible to wind up a long stretched film with small variations. Therefore, the occurrence of wrinkles in the long stretched film can be effectively prevented, and the windability of the long stretched film is improved, so that the stretched film can be wound up in a long length.
- the take-up tension T (N / m) of the stretched long film is adjusted to 100 N / m ⁇ T ⁇ 300 N / m, preferably 150 N / m ⁇ T ⁇ 250 N / m. Is preferred.
- the take-up tension When the take-up tension is 100 N / m or less, slack and wrinkles of the long stretched film are likely to occur, and the retardation and the profile in the width direction of the orientation axis tend to deteriorate. On the other hand, when the take-up tension is 300 N / m or more, the variation in the orientation angle in the width direction is deteriorated, and the width yield (taking efficiency in the width direction) tends to be 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 fluctuation of the take-up tension T is ⁇ 5% or more, the variation in the optical characteristics in the width direction and the flow direction becomes large.
- Examples of the method for measuring the load include a method in which a load cell is attached to a bearing portion of a roll and a load applied to the roll, that is, a tension of a long stretched film is measured.
- a load cell a known tensile type or compression type can be used.
- the stretched long film is released from the tenter exit after being held by the gripper, and is wound around a winding core (winding roll) to form a wound body of the long stretched film.
- a winding core winding roll
- both ends (both sides) of the long stretched film may be trimmed for the purpose of excising grip marks on both sides of the long stretched film held by the tenter gripping tool or obtaining a desired width. desirable.
- the above trimming may be performed at once or may be performed in a plurality of times.
- the long stretched film is fed out again as necessary, trimming both ends of the long stretched film, and winding up again as a wound body of the long stretched film. Good.
- the masking film may be overlapped and wound up at the same time, or at least one of the long stretched films, preferably tapes or the like at both ends. You may wind up while bonding.
- a masking film if the said elongate stretched film can be protected, it will not restrict
- the long stretched film obtained by the production method of the present embodiment has an orientation angle inclined in a range of greater than 0 ° and less than 90 ° with respect to the winding direction. Specific values can be appropriately selected depending on the application, and examples thereof include 15 °, 22.5 °, 45 °, 67.5 °, and 75 °.
- the value of the in-plane retardation of the long stretched film obtained by the production method of the present embodiment is preferably 120 nm or more and 160 nm or less, and more preferably 130 nm or more and 150 nm.
- the variation in the orientation angle in the width direction of the long stretched film obtained by the production method of the present embodiment is preferably 0.6 ° or less, more preferably 0.4 ° or less, in a width of at least 1300 mm.
- a long stretched film with an orientation angle variation exceeding 0.6 ° is bonded to a polarizer to obtain a circularly polarizing plate.
- a self-luminous image display device such as an organic EL display device
- a black image is displayed. Sometimes color unevenness occurs.
- the value of the in-plane retardation of the long stretched film obtained by the production method of the present embodiment is preferably 120 nm or more and 160 nm or less, and more preferably 130 nm or more and 150 nm.
- the dispersion of the in-plane retardation of the long stretched film obtained by the production method of the present embodiment is preferably 3 nm or less, more preferably 1 nm or less, at least 1300 mm in the width direction.
- the optimum value of the in-plane retardation of the long stretched film obtained by the production method of the present embodiment is selected according to the design of the display device used.
- the in-plane retardation of the film is obtained by multiplying the difference between the refractive index nx in the in-plane slow axis direction and the refractive index ny in the direction orthogonal to the slow axis by the average thickness d of the long stretched film. Value ((nx ⁇ ny) ⁇ d).
- the film thickness of the long stretched film obtained by the production method of the present embodiment is, for example, preferably 10 to 200 ⁇ m, and more preferably The thickness is 10 to 60 ⁇ m, more preferably 10 to 35 ⁇ m.
- the thickness unevenness in the width direction is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less, because it affects the availability of winding.
- the circularly polarizing plate of the present invention has a polarizing plate protective film, a polarizer, a ⁇ / 4 retardation film (long stretched film obtained in the present invention), and an adhesive layer laminated in this order.
- the angle formed by the slow axis of the retardation film and the absorption axis of the polarizer is 45 °.
- a long polarizing plate protective film, a long polarizer, and a long ⁇ / 4 retardation film are preferably laminated in this order.
- the circularly polarizing plate according to the present invention 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. Can do.
- the film thickness of the polarizer is 5 to 40 ⁇ m, preferably 5 to 30 ⁇ m, and 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 prepared 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.
- the ⁇ / 4 plate using the long stretched film of the embodiment of the present invention is particularly preferably used as a circularly polarizing plate used for antireflection of a self-luminous display device such as an organic EL display.
- the long stretched film according to the embodiment of the present invention is excellent in uniformity in the direction of the slow axis (orientation angle) in the width direction. Therefore, when used in an organic EL display, it is particularly uniform in color.
- the display device can be made excellent.
- FIG. 6 shows an example of the configuration of the organic EL display D of the present invention, but the present invention is not limited to this.
- the organic EL display D includes an organic EL display having a metal electrode F2, a light emitting layer F3, a transparent electrode (ITO etc.) F4, and a sealing layer F5 on a substrate F1 made of glass, polyimide, or the like.
- an organic EL display is configured by providing a circularly polarizing plate with a polarizer F8 sandwiched between a ⁇ / 4 retardation film F7 and a protective film F9 via an adhesive tank F6. It is preferable that a cured layer is laminated on the protective film F8. The cured layer not only prevents scratches on the surface of the organic EL display but also has an effect of preventing warpage due to the circularly polarizing plate. Further, an antireflection layer may be provided on the cured layer.
- the thickness of the organic EL element 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, or Structures with various combinations such as a laminate of such a light-emitting layer and an electron injection layer composed of a perylene derivative, and / or a laminate of these hole injection layer, light-emitting layer, and electron injection layer are known. ing.
- holes and electrons are injected into the light emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the fluorescent material, It emits light based on the principle that it emits light when the excited fluorescent material returns 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 display 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. ing.
- 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 display looks like a mirror surface.
- the circularly polarizing plate made of a long stretched film manufactured using the present invention is suitable for an organic EL display in which such external light reflection is particularly problematic.
- the method for producing a long stretched film includes a step of forming a long film made of a thermoplastic resin, and the long film is fed out from a specific direction different from the winding direction of the stretched film.
- An oblique stretching step of obliquely stretching the long film in a direction greater than 0 ° and less than 90 ° with respect to the width direction while transporting the both ends of the long film with a gripping device of an oblique stretching device;
- the oblique stretching device is configured so that the long stretched film extends in a direction oblique to the feeding direction of the long film.
- the stretching direction can be arbitrarily changed so that the winding direction comes, and in the oblique stretching process, the grip release points of the gripping tool that grips both ends of the long stretched film are the long stretched film.
- the grip release point is adjusted so that the grip release lines connecting the grip release points at both ends are parallel to the width direction of the long stretched film. It is characterized by that.
- the present invention is a long stretched film stretched in an oblique direction, even when the stretching angle of the long stretched film is changed by changing the shape of the path of the gripping tool travel support tool, It is possible to provide a long stretched film having a small variation in the width direction of the orientation angle of the obtained long stretched film.
- the oblique stretching device in the oblique stretching step, includes a folding gear for changing the traveling direction of the gripping tool, and the folding immediately after the grip release point.
- the gear preferably includes a mechanism for adjusting the position along the winding direction of the long stretched film.
- the present invention can relieve the stress applied to the long stretched film by the gripper at the grip release point, suppress uneven tension in the obtained long stretched film, and further increase the width of the orientation angle.
- the variation in hand direction can be further reduced.
- the traveling direction of each gripping tool that grips both ends of the long stretched film is the traveling direction of the gripping tool changed by the folding gear immediately after the gripping release point, It is preferable that the angle formed by the winding direction of the long stretched film is adjusted to be equal for each gripping tool that grips both ends of the long stretched film.
- the present invention can particularly alleviate the stress applied to the long stretched film by the gripper at the grip release point, particularly suppress the uneven tension of the obtained long stretched film, and further increase the orientation angle.
- the variation in the width direction can be further reduced.
- the traveling direction of each gripping tool that grips both ends of the long stretched film is the traveling direction of the gripping tool changed by the folding gear immediately after the gripping release point, It is preferable to adjust so that the winding direction of the long stretched film is orthogonal.
- the present invention can relieve the stress applied to the long stretched film by the gripper at the grip release point, suppress uneven tension in the obtained long stretched film, and further increase the width of the orientation angle.
- the in-plane retardation of the long stretched film is preferably 120 to 160 nm.
- thermoplastic resin is preferably a norbornene resin.
- the film thickness of the long stretched film is preferably 10 to 35 ⁇ m.
- the film thickness of the obtained long stretched film is within the above range, the sensitivity of the width variation of the orientation angle becomes low, and the width variation of the long stretch film orientation angle can be suppressed.
- a long stretched film according to another aspect of the present invention is characterized by being produced by the above-described method for producing a long stretched film.
- long films A to C were prepared by the following method.
- the long film A1 is a cycloolefin resin film, and was produced by the following production method.
- DCP dicyclopentadiene
- MTF 9a-tetrahydrofluorene
- MTD 8-methyl-tetracyclo [4.4.0.12, 5.17,10] -dodec-3-ene
- a norbornene-based monomer mixture composed of parts and 40 parts by mass of tungsten hexachloride (0.7% toluene solution) were continuously added over 2 hours for polymerization.
- 1.06 parts by mass of butyl glycidyl ether and 0.52 parts by mass of isopropyl alcohol were added to deactivate the polymerization catalyst and stop the polymerization reaction.
- a soft polymer manufactured by Kuraray Co., Ltd .; Septon 2002
- an antioxidant manufactured by Ciba Specialty Chemicals Co., Ltd .; Irganox 1010
- cyclohexane and other volatile components which are solvents, are removed from the solution using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.), and the hydrogenated polymer is extruded in a strand form from an extruder in a molten state. After cooling, it was pelletized and collected.
- 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 melted by using a short-shaft extruder having a coat hanger type T die (manufactured by Mitsubishi Heavy Industries, Ltd .: screw diameter 90 mm, T die lip member quality is tungsten carbide, peel strength 44N from molten resin).
- a cycloolefin polymer film having a thickness of 75 ⁇ m was produced by extrusion molding. In extrusion molding, a long film A1 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.
- the long film B1 is a cellulose ester resin film and was produced by the following production method.
- Fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by mass Ethanol 89 parts by mass The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.
- ⁇ 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.
- a main dope solution having the following composition was prepared. 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 is completely dissolved with heating and stirring. This was designated as 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. Moreover, the following were used for the compound (B).
- Composition of main dope solution Methylene chloride 340 parts by mass Ethanol 64 parts by mass Cellulose acetate propionate (acetyl group substitution degree 1.39, propionyl group substitution degree 0.50, total substitution degree 1.89) 100 parts by mass Compound (B) 5.0 parts by mass Sugar ester compound 5.0 parts by mass Ester compound 2.5 parts by mass Fine particle additive 1 1 part by mass
- the inside of the Kolben is reduced to 4 ⁇ 102 Pa or less, and after excess pyridine is distilled off at 60 ° C., the inside of the Kolben is reduced to 1.3 ⁇ 10 Pa or less, the temperature is raised to 120 ° C., benzoic anhydride, Most of the produced benzoic acid was distilled off.
- LC section Equipment Column oven (JASCO CO-965) manufactured by JASCO Corporation, detector (JASCO UV-970-240 nm), pump (JASCO PU-980), degasser (JASCO DG-980-50) Column: Inertsil ODS-3 Particle size 5 ⁇ m 4.6 ⁇ 250 mm (manufactured by GL Sciences Inc.) Column temperature: 40 ° C Flow rate: 1 ml / min Mobile phase: THF (1% acetic acid): H2O (50:50) Injection volume: 3 ⁇ l 2) MS unit Device: LCQ DECA (manufactured by Thermo Quest Co., Ltd.) Ionization method: Electrospray ionization (ESI) method Spray Voltage: 5 kV Capillary temperature: 180 ° C Vaporizer temperature: 450 ° C
- 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 main dope solution was cast uniformly on a stainless steel belt support.
- the solvent is evaporated until the residual solvent amount in the cast (cast) long film reaches 75%, peeled off from the stainless steel belt support, and transported by many rolls. Drying was terminated, and a long film B1 having a width of 1000 mm was obtained. At this time, the film thickness of the long film B1 was 100 ⁇ m.
- the long film C is a polycarbonate film and was produced by the following production method.
- ⁇ Dope composition Polycarbonate resin (viscosity average molecular weight 40,000, bisphenol A type) 100 parts by mass 2- (2′hydroxy-3 ′, 5′-di-t-butylphenyl) -benzotriazole 1.0 part by mass Methylene chloride 430 parts by mass Methanol 90 parts by mass
- the above composition was put into a sealed container, kept at 80 ° C. under pressure, and completely dissolved with stirring to obtain a dope composition.
- this dope composition was filtered, cooled and kept at 33 ° C., cast uniformly on a stainless steel band, and dried at 33 ° C. for 5 minutes. Thereafter, the drying time was adjusted so that the retardation was 5 nm at 65 ° C., and after peeling from the stainless steel band, drying was terminated while being conveyed by a large number of rolls to obtain a long film C1 having a film thickness of 85 ⁇ m and a width of 1000 mm.
- the stretching device T1 is shown in FIGS. 2 (a) and 2 (b).
- 2A shows the stretching apparatus T1 in which the stretching angle ⁇ is set to 22.5 °
- FIG. 2B shows the stretching apparatus T1 in which the stretching angle ⁇ is set to 45 °.
- the stretching device T1 includes the same number of grippers (a total of 800) in each gripper travel support tool.
- the inner gripping tool travel support tool Ri has a length from the grip start point to the grip release point of 20 m and a total length of 46 m.
- the outer gripping tool travel support tool Ro has a length from the grip start point to the grip release point of 22 m and a total length of 46 m.
- the stretching device T1 can independently change the installation positions of the folding gear G1 and the folding gear G2 along the winding direction of the long stretched film, and is a straight line B (hereinafter referred to as a grip release line) that connects the grip release points. And the long stretched film width direction can be adjusted in parallel.
- the end trimming process of the long stretched film discharged from the stretching apparatus T1 was performed, and the final long stretched film was adjusted to have a film width of 1600 mm. Then, it wound up in roll shape with the take-up tension
- FIG. 1 Drawing apparatus T2 is shown in Drawing 4 (a) and Drawing 4 (b).
- the stretching device T2 includes adjustment gears G3 to G6, and the gripping tool released from gripping at the gripping release point is changed in traveling direction by the turning gear immediately after the gripping release point. Except that the traveling path of the gripping tool can be adjusted so that the angle formed by the winding direction of the stretched film is equal between the gripping tools on both sides, the configuration is the same as that of the stretching device T1.
- Drawing apparatus T3 is shown in Drawing 5 (a) and Drawing 5 (b).
- the stretching device T3 includes adjusting gears G3 to G6, and the gripping tool released from gripping at the gripping release point is changed in traveling direction by the turning gear immediately after the gripping release point. Except that the travel path of the gripper can be adjusted so that the angle formed by the winding direction of the stretched film is orthogonal, the configuration is the same as that of the stretching apparatus T2.
- FIG. 7 is a schematic diagram of the stretching apparatus T4.
- FIG. 7A shows a stretching apparatus in which the stretching angle ⁇ is set to 22.5 °
- FIG. 7B shows the stretching angle ⁇ set to 45 °.
- the set drawing apparatus is shown.
- the stretching device T4 has the same configuration as the stretching device T1 except that it does not have an adjustment gear.
- FIG. 7 (a) the stretching device T4 is folded so that the positional relationship between the grip release line and the width direction of the long stretched film is parallel when the stretching angle is 22.5 °.
- a gear G3 and a turn-back G4 are arranged. Since the stretching device T4 does not have an adjustment gear, as shown in FIG. 7B, when the stretching angle is changed to 45 °, the positional relationship between the grip release line and the width direction of the long stretched film Changes, and the angle ⁇ 4 becomes 22.5 °.
- FIG. 8 is a schematic diagram of the stretching apparatus T5.
- FIG. 8A shows a stretching apparatus in which the stretching angle ⁇ is set to 22.5 °
- FIG. 8B shows the stretching angle ⁇ set to 45 °.
- the set drawing apparatus is shown.
- the stretching device T5 has the same configuration as the stretching device T1 except that it does not have an adjustment gear.
- FIG. 8 (b) when the stretching angle is 45 °, the stretching device T5 has a folding gear G3 so that the positional relationship between the grip release line and the width direction of the long stretched film is parallel.
- a turn-back G4 is arranged.
- the stretching device T5 does not have an adjustment gear, when the stretching angle is changed to 22.5 ° as shown in FIG. 8A, the grip release line and the width direction of the long stretched film are changed. The positional relationship changes, and the angle ⁇ 5 becomes 22.5 °.
- FIG. 9 is a schematic diagram of a stretching apparatus T6 (stretching apparatus T5).
- FIG. 9 (a) shows a stretching apparatus in which the stretching angle ⁇ is set to 22.5 °
- FIG. 9 (b) shows a stretching angle.
- a stretching apparatus in which ⁇ is set to 45 ° is shown.
- the stretching device T6 has the same configuration as the stretching device T1 except that it does not have an adjustment gear. As shown in FIG. 9 (a), when the stretching angle is 22.5 °, the stretching device T6 is not parallel in the positional relationship between the grip release line and the width direction of the long stretched film, and has an angle ⁇ 6.
- the return gear G3 and the return gear G4 are arranged so that the angle is 13 °. As shown in FIG. 9B, in the stretching device T6, even when the stretching angle is changed to 45 °, the positional relationship between the grip release line and the width direction of the long stretched film does not become parallel.
- the folding gear G3 and the folding gear G4 are arranged so that the angle ⁇ 7 is 12.5 °.
- the temperature conditions of the tenter oven when using the long film B were adjusted to 180 ° C. for the preheating zone, 180 ° C. for the stretching zone, 177 ° C. for the heat setting zone, and 90 ° C. for the cooling zone.
- the temperature conditions of the tenter oven when using the long film C were adjusted to 160 ° C. for the preheating zone, 160 ° C. for the stretching zone, 157 ° C. for the heat setting zone, and 80 ° C. for the cooling zone.
- Examples 10 to 15 and Comparative Examples 10 to 15> Except for the combinations shown in Table 2 with the traveling speed of the gripper set to 100 m / min, the long films A to C were stretched by the stretching devices T1 to T6 in the same manner as in Examples 1 to 9, and the long Stretched films 19-1 to 30-1 and 19-2 to 30-2 were produced.
- Example 22 A 120 ⁇ m-thick polyvinyl alcohol film was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times).
- the produced long stretched film 1-2 was bonded to one side of the polarizer using a 5% aqueous solution of polyvinyl alcohol as an adhesive. At that time, the lamination was performed so that the absorption axis of the polarizer and the slow axis of the ⁇ / 4 retardation film were oriented at 45 °.
- Konica Minolta Tack Film KC6UA manufactured by Konica Minolta Opto Co., Ltd. was similarly subjected to alkali saponification treatment and bonded to produce a circularly polarizing plate 1.
- a reflective electrode made of chromium having a thickness of 80 nm is formed on a glass substrate by sputtering, ITO (indium tin oxide) is formed as a positive electrode on the reflective electrode to a thickness of 40 nm by sputtering, and a polyelectrolyte is formed on the anode as a hole transport layer.
- ITO indium tin oxide
- PEDOT polystyrene sulfonate
- red light emitting layer tris (8-hydroxyquinolinate) aluminum (Alq3) 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.
- Alq3 as a host and the light emitting compound coumarin 6 were co-evaporated (mass ratio 99: 1) to form a thickness of 100 nm.
- the blue light-emitting layer was formed as a host by co-evaporating BAlq shown below and a light-emitting compound Perylene (mass ratio 90:10) with a thickness of 100 nm.
- first cathode having a low work function so that electrons can be efficiently injected onto the light-emitting layer calcium is deposited to a thickness of 4 nm by a vacuum deposition method, and a second cathode is formed on the first cathode.
- Aluminum was formed to a thickness of 2 nm.
- the aluminum used as the second cathode has a role to prevent 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 with 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.
- the circularly polarizing plate 1 was fixed with an adhesive so that the surface of the ⁇ / 4 retardation film was directed to the surface of the insulating film, and the organic EL display 1 was manufactured.
- Liquid crystal display devices 302 to 303 were produced in the same manner as in the production of the liquid crystal display device 301 except that the circularly polarizing plate 13 was changed to the circularly polarizing plates 14 to 15, respectively. It shows in Table 7 about the used elongate stretched film and the obtained liquid crystal display device.
- the orientation angles of the produced long stretched films 1-1 to 42-1 and 1-2 to 42-2 were measured using a phase difference measuring device (manufactured by Oji Scientific Co., Ltd., KOBRA-WXK). As an evaluation method, measurement was performed at an interval of 50 mm of the long stretched film in the film width direction of the long stretched film, and an average of all data was taken. Further, the difference between the maximum value and the minimum value of all measured values was evaluated as variation.
- In-plane retardation and lateral distribution of in-plane retardation In-plane retardation of the produced long stretched films 1-1 to 42-1 and 1-2 to 42-2 was measured using a phase difference measuring device (manufactured by Oji Scientific Co., Ltd., KOBRA-WXK). As an evaluation method, measurement was performed at an interval of 50 mm of the long stretched film in the film width direction of the long stretched film and evaluated.
- the obtained organic EL display and liquid crystal display device were evaluated as follows.
- ⁇ No difference is seen in the color of each place in the prepared organic EL display and liquid crystal display device.
- ⁇ In the prepared organic EL display and the liquid crystal display device, a difference in color is seen in each place.
- ⁇ There is no problem. In the prepared organic EL display and liquid crystal display device, there is a difference in color for each part, and the product cannot be used as a product.
- ⁇ In the created organic EL display and liquid crystal display device, there are large differences in color for each part, and it cannot be used as a product.
- Tables 1 to 7 summarize the various elongated stretched films, organic EL displays, and liquid crystal display devices, and the results of various evaluations.
- long stretched films 1-1 to 9-1 and 1-2 to 9-2 corresponding to Examples 1 to 9 are long stretched films 10 corresponding to Comparative Examples 1 to 9.
- the variation in the width direction of the orientation angle was less than ⁇ 0.6 ° regardless of the stretching angle, which was good.
- the travel direction of the gripping tool is changed by the turning gear immediately after the grip release point.
- the variation in the width direction of the orientation angle is ⁇ 0. It was less than 4 ° and was particularly good.
- the shape of the gripping tool travel support tool was changed so that the angle formed by the traveling direction of the gripping tool on each side and the winding direction of the long stretched film are orthogonal to each other, the travel direction being changed by the turning gear immediately after the grip release point.
- the long stretched films 7-1 to 9-1 and 7-2 to 9-2 obtained by using the stretching apparatus T3 have a variation in the width direction of the orientation angle of less than ⁇ 0.4 °. Besides being good, the winding shape after the durability test was also good.
- the long stretched films 19-1 to 24-1 and 19-2 to 24-2 corresponding to Examples 10 to 15 which were conveyed at high speed are long in length corresponding to Comparative Examples 10 to 15.
- the variation in the width direction of the orientation angle was less than ⁇ 0.6 ° regardless of the stretching angle, which was good.
- the long stretched films 19-1, 22-1 and 19-2, 22-2 made by using a long film made of a thermoplastic resin containing a norbornene resin are used in the width direction of the orientation angle. The variation was less than ⁇ 0.4 °, which was particularly good.
- long stretched films 31-1 to 36-1 and 31-2 to 36-2 corresponding to Examples 16 to 21 prepared as thin films correspond to Comparative Examples 16 to 21.
- the variation in the width direction of the orientation angle was less than ⁇ 0.6 ° regardless of the stretch angle, which was good. It was.
- the long stretched films 31-1, 34-1 and 31-2, 34-2 made by using a long film made of a thermoplastic resin containing a norbornene resin are used in the width direction of the orientation angle. The variation was less than ⁇ 0.4 °, which was particularly good.
- the liquid crystal display devices 301 to 303 corresponding to Reference Examples 1 to 3 have no difference in color compared to the organic EL displays 13 to 15 corresponding to Comparative Examples 25 to 27. It was found that the problem was observed when a long stretched film was applied to the organic EL display.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ophthalmology & Optometry (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Polarising Elements (AREA)
Abstract
Description
(斜め延伸工程)
斜め延伸工程は、製膜された長尺フィルムを幅手方向に対して斜めの方向に延伸する工程である。長尺フィルムの製造方法では、フィルムを連続的に製造することにより、所望の任意の長さにフィルムを製造しうる。なお、長尺延伸フィルムの製造方法は、長尺フィルムを製膜した後に一度巻芯に巻き取り、巻回体(原反ともいう)にしてから斜め延伸工程に供給するようにしてもよいし、製膜後のフィルムを巻き取ることなく、製膜工程から連続して斜め延伸工程に供給してもよい。製膜工程と斜め延伸工程を連続して行うことは、延伸後の膜厚や光学値の結果をフィードバックして製膜条件を変更し、所望の長尺延伸フィルムを得ることができるので好ましい。
本実施形態における延伸に供される長尺フィルムに斜め方向の配向を付与するために、斜め延伸装置を用いる。本実施形態で用いられる斜め延伸装置は、把持具走行支持具の経路パターンを多様に変化させることにより、フィルムの配向角を自在に設定でき、さらに、フィルムの配向軸をフィルム幅方向に渡って左右均等に高精度に配向させることができ、かつ、高精度でフィルム厚みやリタデーションを制御できるフィルム延伸装置であることが好ましい。
製膜工程は、熱可塑性樹脂からなる長尺フィルムを製膜する工程である。
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採用することができる。
セルロースエステル系樹脂としては、下記式(i)および(ii)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ことを特徴とするものが挙げられる。
式(ii) 0.5≦X
(式(i)および式(ii)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)
以下、一般式(A)について詳細に説明する。
(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。
本発明で用いることができ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。
式(iv) 0.5≦X
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。
本発明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、長尺延伸フィルムにした時の透過率が80%以上、さらに好ましくは90%以上、さらに好ましくは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長尺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。さらに界面活性剤、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。
次に、ポリカーボネート系樹脂について説明する。
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溶液流延法が好ましい。
本発明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。
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、さらに乾燥する工程、仕上がった長尺延伸フィルムを巻き取る工程により行われる。
なお、Mはウェブまたは長尺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で、NはMを115℃で1時間の加熱後の質量である。
溶融流延法は、斜め延伸後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することをいう。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長尺フィルムが得られる、溶融押出し法が好ましい。
斜め延伸工程は、すでに上記したとおりである。斜め延伸工程を経た長尺延伸フィルムは、長尺フィルムの幅手方向に対して0°より大きく90°未満の方向に斜め延伸されている。延伸された長尺延伸フィルムは、後続する巻取り工程により巻き取られる。
巻き取り装置は、斜め延伸装置の出口に設けられている。巻取り装置は、延伸装置に対して所定角度で長尺延伸フィルムを引き取れるように配置することにより、長尺延伸フィルムの引き取り位置および角度を細かく制御することが可能となり、膜厚、光学値のばらつきが小さい長尺延伸フィルムを巻き取ることが可能となる。そのため、長尺延伸フィルムのシワの発生を有効に防止することができるとともに、長尺延伸フィルムの巻き取り性が向上するため、延伸フィルムを長尺で巻き取ることが可能となる。本実施形態において、延伸後の長尺フィルムの引取り張力T(N/m)は、100N/m<T<300N/m、好ましくは150N/m<T<250N/mの間で調整することが好ましい。
本実施形態の製造方法により得られた長尺延伸フィルムは、配向角が巻取方向に対して、0°より大きく90°未満の範囲に傾斜している。具体的な値は用途によって適宜選択することができるが、例えば15°、22.5°、45°、67.5°、75°などの値があげられる。
本発明の円偏光板は、偏光板保護フィルム、偏光子、λ/4位相差フィルム(本発明で得られた長尺延伸フィルム)、粘着層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とのなす角度が45°である。
また、本発明の実施形態の長尺延伸フィルムを用いたλ/4板は、有機ELディスプレイのような自発光型表示装置の反射防止の用途に用いられる円偏光板として特に好ましく用いられる。本発明の実施形態に係る長尺延伸フィルムは、幅手方向における遅相軸の方向(配向角)の均一性に優れる為、有機ELディスプレイに用いられた場合には、特に色味の均一性に優れた表示装置とすることができる。
製膜工程では、以下の方法により、長尺フィルムA~Cを作製した。
長尺フィルムA1は、シクロオレフィン系樹脂フィルムであり、以下の製造方法により作製した。
上記長尺フィルムA1の作成方法のうち、溶融押出成形後の厚みが35μmとなるようにTダイリップのダイスギャップを適宜調整した他は長尺フィルムA1と同様にして、長尺フィルムA2を得た。
長尺フィルムB1は、セルロースエステル系樹脂フィルムであり、以下の製造方法により作製した。
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。
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。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。
上記長尺フィルムB1の作成方法のうち、乾燥工程後の厚みが50μmとなるように流延時の膜厚を適宜調整した他は長尺フィルムB1と同様にして、長尺フィルムB2を得た。
長尺フィルムCは、ポリカーボネート系フィルムであり、以下の製造方法により作製した。
ポリカーボネート樹脂(粘度平均分子量4万、ビスフェノールA型)
100質量部
2-(2′ヒドロキシ-3′,5′-ジ-t-ブチルフェニル)-ベンゾトリアゾール
1.0質量部
メチレンクロライド 430質量部
メタノール 90質量部
上記長尺フィルムC1の作成方法のうち、溶融後の厚みが40μmとなるように流延時の膜厚を適宜調整した他は長尺フィルムC1と同様にして、長尺フィルムC2を得た。
斜め延伸工程および巻取り工程では、以下の条件に調整された斜め延伸装置(T1~6)により、長尺フィルムA~Cを延伸し、ロール状に巻き取った。
延伸装置T1は図2(a)および図2(b)に示される。図2(a)は延伸角度θを22.5°に設定した延伸装置T1を示しており、図2(b)は延伸角度θを45°に設定した延伸装置T1を示している。延伸装置T1は、それぞれの把持具走行支持具に同数の把持具(計800個)を備える。内回り把持具走行支持具Riは、把持開始点から把持解放点までの長さが20mであり、全長が46mである。外回り把持具走行支持具Roは、把持開始点から把持解放点までの長さが22mであり、全長が46mである。延伸装置T1は、折返しギアG1および折返しギアG2の設置位置を長尺延伸フィルムの巻取方向に沿ってそれぞれ独立して変更することができ、把持解放点を結ぶ直線B(以下、把持解放線という)と長尺延伸フィルム幅方向とを平行に調整することができる。
延伸装置T2は、図4(a)および図4(b)に示される。延伸装置T2は、調整ギアG3~G6を備え、把持解放点において把持を解放した把持具が、把持解放点直後の折返しギアによって走行方向が変更される各々両側の把持具の走行方向と長尺延伸フィルムの巻取方向がなす角度が、各々両側の把持具で等しくなるように把持具の走行経路を調整可能である以外は、延伸装置T1と同様の構成である。
延伸装置T3は、図5(a)および図5(b)に示される。延伸装置T3は、調整ギアG3~G6を備え、把持解放点において把持を解放した把持具が、前記把持解放点直後の折返しギアによって走行方向が変更される各々両側の把持具の走行方向と長尺延伸フィルムの巻取方向がなす角度が直交するように把持具の走行経路を調整可能である以外は、延伸装置T2と同様の構成である。
延伸装置T4は、図7に示される。図7は、延伸装置T4の概略図であり、図7(a)は延伸角度θを22.5°に設定した延伸装置を示しており、図7(b)は延伸角度θを45°に設定した延伸装置を示している。延伸装置T4は、調整ギアを有していない以外は、延伸装置T1と同様の構成である。図7(a)に示されるように、延伸装置T4は、延伸角度が22.5°の場合に、把持解放線と長尺延伸フィルムの幅手方向との位置関係が平行になるように折返しギアG3および折返しG4が配置されている。延伸装置T4は、調整ギアを有していないため、図7(b)に示されるように、延伸角度を45°に変更すると、把持解放線と長尺延伸フィルムの幅手方向との位置関係が変化し、角度θ4が22.5°となる。
延伸装置T5は、図8に示される。図8は、延伸装置T5の概略図であり、図8(a)は延伸角度θを22.5°に設定した延伸装置を示しており、図8(b)は延伸角度θを45°に設定した延伸装置を示している。延伸装置T5は、調整ギアを有していない以外は、延伸装置T1と同様の構成である。図8(b)に示されるように、延伸装置T5は、延伸角度が45°の場合に、把持解放線と長尺延伸フィルムの幅手方向との位置関係が平行になるように折返しギアG3および折返しG4が配置されている。延伸装置T5は、調整ギアを有していないため、図8(a)に示されるように、延伸角度を22.5°に変更すると、把持解放線と長尺延伸フィルムの幅手方向との位置関係が変化し、角度θ5が22.5°となる。
延伸装置T6は、図9に示される。図9は、延伸装置T6(延伸装置T5)の概略図であり、図9(a)は延伸角度θを22.5°に設定した延伸装置を示しており、図9(b)は延伸角度θを45°に設定した延伸装置を示している。延伸装置T6は、調整ギアを有していない以外は、延伸装置T1と同様の構成である。図9(a)に示されるように、延伸装置T6は、延伸角度が22.5°の場合に、把持解放線と長尺延伸フィルムの幅手方向との位置関係が平行ではなく、角度θ6が13°となるよう折返しギアG3および折返しギアG4が配置されている。図9(b)に示されるように、延伸装置T6は、延伸角度を45°に変更した場合においても、把持解放線と長尺延伸フィルムの幅手方向との位置関係が平行にはならず、角度θ7が12.5°となるよう折返しギアG3および折返しギアG4が配置されている。
表1に示す組み合わせに基づいて、長尺フィルムA1~C1を、延伸装置T1~6により延伸した。このときの延伸角度は22.5°および45°とし、それぞれの延伸角度で得られた長尺延伸フィルムを、長尺延伸フィルム1-1~18-1および長尺延伸フィルム1-2~18-2として作成した。このときの把持具の走行速度は20m/分とした。また、長尺フィルムAを用いる際のテンターオーブンの温度条件としては、予熱ゾーンは140℃、延伸ゾーンは140℃、熱固定ゾーンは137℃、冷却ゾーンは80℃に調整した。また、長尺フィルムBを用いる際のテンターオーブンの温度条件としては、予熱ゾーンは180℃、延伸ゾーンは180℃、熱固定ゾーンは177℃、冷却ゾーンは90℃に調整した。また、長尺フィルムCを用いる際のテンターオーブンの温度条件としては、予熱ゾーンは160℃、延伸ゾーンは160℃、熱固定ゾーンは157℃、冷却ゾーンは80℃に調整した。
把持具の走行速度を100m/分として、表2に示す組み合わせに基づいたほかは、実施例1~9と同様にして長尺フィルムA~Cを、延伸装置T1~T6により延伸し、長尺延伸フィルム19-1~30-1および19-2~30-2を作製した。
把持具の走行速度を20m/分として、表3に示す組み合わせに基づいたほかは、実施例1~9と同様にして長尺フィルムA~Cを、延伸装置T1~T6により延伸し、長尺延伸フィルム31-1~42-1および31-2~42-2を作製した。
厚さ120μmのポリビニルアルコールフィルムを、一軸延伸(温度110℃、延伸倍率5倍)した。
作成した円偏光板13を用いて、市販の液晶表示パネル(ソニー製:型名BRAVIA KDL-26J5)の視認側の偏光板を剥がし、上記作製した円偏光板13~15とを貼合して、液晶パネル201を作製した。次に液晶パネル201を液晶テレビにセットし、液晶表示装置301を作製した。
上記液晶表示装置301の作製において、円偏光板13を円偏光板14~15に、それぞれ変更した以外は同様にして液晶表示装置302~303を作製した。使用した長尺延伸フィルムおよび得られた液晶表示装置について表7に示す。
得られた長尺延伸フィルムについて、以下の評価を行った。
作成した長尺延伸フィルム1-1~42-1および1-2~42-2の配向角を位相差測定装置(王子計測(株)製、KOBRA-WXK)を用いて測定した。評価方法としては、長尺延伸フィルムのフィルム幅方向に長尺延伸フィルムの50mmの間隔で測定を行い、全データの平均をとった。また、全測定値の最大値と最小値との差をばらつきとして評価した。
(配向角の幅手ばらつきの評価基準)
◎:配向角の幅手ばらつきが0.4°未満
○:配向角の幅手ばらつきが0.4°以上0.6°未満
△:配向角の幅手ばらつきが0.6°以上1.0°未満
×:配向角の幅手ばらつきが1.0°以上
作成した長尺延伸フィルム1-1~42-1および1-2~42-2の面内リタデーションを位相差測定装置(王子計測(株)製、KOBRA-WXK)を用いて測定した。評価方法としては、長尺延伸フィルムのフィルム幅方向に長尺延伸フィルムの50mmの間隔で測定を行い、評価した。
上記作成した有機ELディスプレイおよび液晶表示装置において、黒表示した際のディスプレイ全面における色ムラを、以下の基準で目視評価した。
◎:作成した有機ELディスプレイおよび液晶表示装置において、箇所ごとの色味に違いは見られない
○:作成した有機ELディスプレイおよび液晶表示装置において、箇所ごとに色味に違いが見られるが使用に際して問題がない程度である
△:作成した有機ELディスプレイおよび液晶表示装置において、箇所ごとに色味に違いが見られ、製品として使用できない程度である。
×:作成した有機ELディスプレイおよび液晶表示装置において、箇所ごとに色味違いが大きく、製品として使用できない程度である
Claims (7)
- 熱可塑性樹脂からなる長尺フィルムを製膜する工程、前記長尺フィルムを延伸後のフィルムの巻取方向とは異なる特定の方向から繰り出し、該長尺フィルムの両端部を斜め延伸装置の把持具によって把持して搬送しつつ前記長尺フィルムを幅手方向に対して0°より大きく90°未満の方向に斜め延伸する斜め延伸工程、及び、斜め延伸工程後の長尺延伸フィルムを巻き取る工程を少なくとも有する長尺延伸フィルムの製造方法において、
前記斜め延伸装置は、長尺フィルムの繰出方向と斜交する方向に長尺延伸フィルムの巻取方向がくるように、延伸方向を任意に変更でき、
前記斜め延伸工程において、長尺延伸フィルムの両端部を把持する把持具の把持解放点が、長尺延伸フィルムの巻取方向にそれぞれ独立に移動することが可能であり、各々両端部の把持解放点を結んだ把持解放線が、長尺延伸フィルムの幅手方向と平行となるよう把持解放点を調整することを特徴とする、長尺延伸フィルムの製造方法。 - 前記斜め延伸工程において、
前記斜め延伸装置は、前記把持具の走行方向を変更するための折返しギアを備えており、
前記把持解放点直後の折返しギアは、前記長尺延伸フィルムの巻取方向に沿って位置を調整する機構を備える、請求項1記載の長尺延伸フィルムの製造方法。 - 前記斜め延伸工程において、
長尺延伸フィルムの両端部を把持するそれぞれの前記把持具の走行方向は、前記把持解放点直後の折返しギアによって変更された把持具の走行方向と、長尺延伸フィルムの巻取方向とがなす角度が、長尺延伸フィルムの両端部を把持するそれぞれの前記把持具で等しくなるよう調整されている、請求項1または2記載の長尺延伸フィルムの製造方法。 - 前記斜め延伸工程において、長尺延伸フィルムの両端部を把持するそれぞれの前記把持具の走行方向は、前記把持解放点直後の折返しギアによって変更された把持具の走行方向と、長尺延伸フィルムの巻取方向とが直交するよう調整されている、請求項1~3のいずれかに記載の長尺延伸フィルムの製造方法。
- 前記長尺延伸フィルムの面内リタデーションが120~160nmである、請求項1~4のいずれか1項に記載の長尺延伸フィルムの製造方法。
- 前記熱可塑性樹脂がノルボルネン系樹脂である、請求項1~5のいずれか1項に記載の長尺延伸フィルムの製造方法。
- 前記長尺延伸フィルムの膜厚が10~35μmである、請求項1~6のいずれか1項に記載の長尺延伸フィルムの製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/376,693 US9186837B2 (en) | 2012-02-08 | 2012-02-08 | Method for producing long stretched film |
PCT/JP2012/000846 WO2013118172A1 (ja) | 2012-02-08 | 2012-02-08 | 長尺延伸フィルムの製造方法 |
JP2012528979A JP5083483B1 (ja) | 2012-02-08 | 2012-02-08 | 長尺延伸フィルムの製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2012/000846 WO2013118172A1 (ja) | 2012-02-08 | 2012-02-08 | 長尺延伸フィルムの製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013118172A1 true WO2013118172A1 (ja) | 2013-08-15 |
Family
ID=47435561
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/000846 WO2013118172A1 (ja) | 2012-02-08 | 2012-02-08 | 長尺延伸フィルムの製造方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US9186837B2 (ja) |
JP (1) | JP5083483B1 (ja) |
WO (1) | WO2013118172A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015199209A1 (ja) * | 2014-06-27 | 2015-12-30 | 富士フイルム株式会社 | 輝度向上フィルムの転写材料、転写材料の作製方法、輝度向上フィルム、転写材料を用いた光学シート部材の製造方法、および光学シート部材 |
JP2019174847A (ja) * | 2019-07-09 | 2019-10-10 | 日本ゼオン株式会社 | 円偏光板の製造方法及び光学積層体の製造方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013125196A1 (ja) * | 2012-02-22 | 2013-08-29 | コニカミノルタ株式会社 | 長尺延伸フィルムの製造方法 |
JP5983418B2 (ja) * | 2013-01-18 | 2016-08-31 | コニカミノルタ株式会社 | 光学フィルム、円偏光板および画像表示装置 |
CN105658410B (zh) | 2013-10-30 | 2017-11-24 | 日本瑞翁株式会社 | 长条拉伸膜及其制造方法 |
KR101662912B1 (ko) * | 2014-12-30 | 2016-10-06 | 주식회사 효성 | 노보넨계 광학 필름, 및 이의 제조방법 |
TWI783132B (zh) * | 2018-03-27 | 2022-11-11 | 日商日本瑞翁股份有限公司 | 長條狀之延伸薄膜及長條狀之偏光薄膜的製造方法 |
CN116533552B (zh) * | 2023-06-12 | 2024-04-02 | 青岛金福鑫塑料机械有限公司 | 一种pet打包带生产成形装置及生产方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005169856A (ja) * | 2003-12-11 | 2005-06-30 | Fuji Photo Film Co Ltd | テンター装置 |
JP2007175974A (ja) * | 2005-12-27 | 2007-07-12 | Nippon Zeon Co Ltd | フィルム延伸装置およびフィルム延伸方法 |
JP2010221624A (ja) * | 2009-03-25 | 2010-10-07 | Nippon Zeon Co Ltd | 光学フィルムの製造装置 |
Family Cites Families (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3063311B2 (ja) | 1991-10-09 | 2000-07-12 | ジェイエスアール株式会社 | 水素添加重合体 |
JP3237072B2 (ja) | 1992-05-11 | 2001-12-10 | 三井化学株式会社 | 環状オレフィン系ランダム多元共重合体およびその製造方法 |
JP4035182B2 (ja) | 1996-07-30 | 2008-01-16 | ダイセル化学工業株式会社 | セルロースの混合脂肪酸エステルの製造方法 |
EP0911656B1 (en) | 1997-10-20 | 2005-01-26 | Fuji Photo Film Co., Ltd. | Optical compensatory sheet and liquid crystal display |
US6778242B1 (en) | 1997-10-20 | 2004-08-17 | Fuji Photo Film Co., Ltd. | Optical compensatory sheet comprising cellulose acetate support and optically anisotropic layer, an ellipsoidal polarizing plate, and a liquid crystal display |
US6511756B1 (en) | 1997-10-23 | 2003-01-28 | Nippon Zeon Co., Ltd. | Thermoplastic dicyclopentadiene-base open-ring polymers, hydrogenated derivatives thereof, and processes for the preparation of both |
JP4707779B2 (ja) | 1997-10-23 | 2011-06-22 | 日本ゼオン株式会社 | 熱可塑性ジシクロペンタジエン系開環重合体、及びその製造方法 |
JP2002086554A (ja) * | 2000-07-10 | 2002-03-26 | Fuji Photo Film Co Ltd | ポリマーフィルムの延伸方法、偏光膜、偏光板および位相差膜の製造方法、および液晶表示装置 |
JP2002372622A (ja) | 2001-06-14 | 2002-12-26 | Nitto Denko Corp | 複合位相差板、円偏光板及び液晶表示装置、有機el表示装置 |
US7099082B2 (en) * | 2001-08-29 | 2006-08-29 | Fuji Photo Film Co., Ltd. | Method for producing optical compensating film, optical compensating film, circularly polarizing plate, and liquid crystal display |
JP2003167121A (ja) | 2001-11-30 | 2003-06-13 | Fuji Photo Film Co Ltd | ポリカーボネート系位相差フィルムおよびその製造方法 |
CN1287972C (zh) * | 2002-01-16 | 2006-12-06 | 富士胶片株式会社 | 拉幅机装置 |
JP2004009543A (ja) * | 2002-06-06 | 2004-01-15 | Fuji Photo Film Co Ltd | テンター装置 |
US7138185B2 (en) * | 2002-07-05 | 2006-11-21 | Fuji Photo Film Co., Ltd. | Anti-reflection film, polarizing plate and display device |
TW200428268A (en) * | 2002-07-15 | 2004-12-16 | Fuji Photo Film Co Ltd | Internal touch panel, and process for producing it and display device |
KR100977427B1 (ko) * | 2002-08-07 | 2010-08-24 | 후지필름 가부시키가이샤 | 위상차판 및 원편광판 |
US20040056380A1 (en) * | 2002-09-19 | 2004-03-25 | Fuji Photo Film Co., Ltd. | Method and apparatus for orienting an optical polymer film, and tenter apparatus for the same |
JP2004106423A (ja) * | 2002-09-19 | 2004-04-08 | Fuji Photo Film Co Ltd | テンター装置 |
JP2004160665A (ja) * | 2002-11-08 | 2004-06-10 | Fuji Photo Film Co Ltd | 光学用フィルムの製造方法 |
JP4277531B2 (ja) | 2003-01-30 | 2009-06-10 | 日本ゼオン株式会社 | 光学用フィルムおよびその製造方法 |
JP2005121813A (ja) | 2003-10-15 | 2005-05-12 | Sekisui Chem Co Ltd | 光学フィルム及び偏光板 |
TWI388876B (zh) * | 2003-12-26 | 2013-03-11 | Fujifilm Corp | 抗反射膜、偏光板,其製造方法,液晶顯示元件,液晶顯示裝置,及影像顯示裝置 |
JP2006091836A (ja) | 2004-08-26 | 2006-04-06 | Nitto Denko Corp | 位相差フィルムおよびその製造方法、ならびに、該位相差フィルムを用いた光学フィルム、液晶パネルおよび液晶表示装置 |
JP4525326B2 (ja) | 2004-12-09 | 2010-08-18 | 日本ゼオン株式会社 | フィルム延伸装置およびフィルム延伸方法 |
JP2006215465A (ja) | 2005-02-07 | 2006-08-17 | Nitto Denko Corp | 偏光子保護フィルム、偏光板、および画像表示装置 |
CN101341016B (zh) * | 2005-11-28 | 2013-02-06 | 日本瑞翁株式会社 | 长的斜向延伸膜的制造方法 |
JP5084293B2 (ja) | 2006-02-07 | 2012-11-28 | 富士フイルム株式会社 | 光学フィルムおよび位相差板、並びに液晶化合物 |
US8293146B2 (en) | 2006-02-07 | 2012-10-23 | Fujifilm Corporation | Optical film and phase difference plate, and liquid crystal compound |
CN101410239B (zh) * | 2006-03-24 | 2011-01-26 | 日本瑞翁株式会社 | 长形状的延伸膜及其制造方法和用途 |
JP2008080674A (ja) | 2006-09-28 | 2008-04-10 | Nippon Zeon Co Ltd | 延伸フィルムの製造方法、位相差フィルム、円偏光板、及び液晶表示装置 |
JP5151356B2 (ja) | 2007-09-26 | 2013-02-27 | 日本ゼオン株式会社 | 延伸フィルムの製造方法、延伸フィルム、偏光板、及び液晶表示装置 |
KR100989962B1 (ko) * | 2007-09-26 | 2010-10-26 | 니폰 제온 가부시키가이샤 | 연신 필름의 제조 방법, 연신 필름, 편광판 및 액정 표시 장치 |
JP5463666B2 (ja) | 2007-12-28 | 2014-04-09 | 住友化学株式会社 | 化合物、光学フィルム及び光学フィルムの製造方法 |
JP2010173261A (ja) | 2009-01-30 | 2010-08-12 | Nippon Zeon Co Ltd | 延伸光学フィルムの製造方法 |
JP5233746B2 (ja) | 2009-02-27 | 2013-07-10 | 日本ゼオン株式会社 | 斜め延伸フィルムの製造方法、斜め延伸フィルム、偏光板、および液晶表示装置 |
-
2012
- 2012-02-08 JP JP2012528979A patent/JP5083483B1/ja active Active
- 2012-02-08 US US14/376,693 patent/US9186837B2/en not_active Expired - Fee Related
- 2012-02-08 WO PCT/JP2012/000846 patent/WO2013118172A1/ja active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005169856A (ja) * | 2003-12-11 | 2005-06-30 | Fuji Photo Film Co Ltd | テンター装置 |
JP2007175974A (ja) * | 2005-12-27 | 2007-07-12 | Nippon Zeon Co Ltd | フィルム延伸装置およびフィルム延伸方法 |
JP2010221624A (ja) * | 2009-03-25 | 2010-10-07 | Nippon Zeon Co Ltd | 光学フィルムの製造装置 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015199209A1 (ja) * | 2014-06-27 | 2015-12-30 | 富士フイルム株式会社 | 輝度向上フィルムの転写材料、転写材料の作製方法、輝度向上フィルム、転写材料を用いた光学シート部材の製造方法、および光学シート部材 |
KR20170013909A (ko) * | 2014-06-27 | 2017-02-07 | 후지필름 가부시키가이샤 | 휘도 향상 필름의 전사 재료, 전사 재료의 제작 방법, 휘도 향상 필름, 전사 재료를 이용한 광학 시트 부재의 제조 방법, 및 광학 시트 부재 |
JPWO2015199209A1 (ja) * | 2014-06-27 | 2017-04-27 | 富士フイルム株式会社 | 輝度向上フィルムの転写材料、転写材料の作製方法、輝度向上フィルム、転写材料を用いた光学シート部材の製造方法、および光学シート部材 |
KR101912159B1 (ko) * | 2014-06-27 | 2018-10-26 | 후지필름 가부시키가이샤 | 휘도 향상 필름의 전사 재료의 제조 방법 |
JP2019174847A (ja) * | 2019-07-09 | 2019-10-10 | 日本ゼオン株式会社 | 円偏光板の製造方法及び光学積層体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2013118172A1 (ja) | 2015-05-11 |
US20140361456A1 (en) | 2014-12-11 |
US9186837B2 (en) | 2015-11-17 |
JP5083483B1 (ja) | 2012-11-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5083483B1 (ja) | 長尺延伸フィルムの製造方法 | |
JP5177332B1 (ja) | 長尺延伸フィルムの製造方法及び製造装置 | |
WO2014073020A1 (ja) | 長尺斜め延伸フィルム、該長尺斜め延伸フィルムを用いた円偏光板および有機elディスプレイ | |
WO2013161581A1 (ja) | 斜め延伸フィルムの製造方法 | |
JP5088718B1 (ja) | 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 | |
JP2013202979A (ja) | 斜め延伸フィルムの製造方法および製造装置 | |
JP5126456B1 (ja) | 長尺斜め延伸フィルムの製造方法および製造装置 | |
JP6903001B2 (ja) | 斜め延伸フィルムの製造方法 | |
JP5979224B2 (ja) | 長尺延伸フィルムの製造方法及び製造装置 | |
JP5083482B1 (ja) | 長尺延伸フィルムの製造方法 | |
JP5105034B1 (ja) | 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 | |
JP5862686B2 (ja) | 長尺延伸フィルムの製造方法 | |
JP5862687B2 (ja) | 長尺延伸フィルムの製造方法 | |
WO2014156416A1 (ja) | 光学フィルムの製造方法 | |
JP5983732B2 (ja) | 長尺延伸フィルムの製造方法 | |
JP5979217B2 (ja) | 長尺延伸フィルムの製造方法および斜め延伸装置 | |
JP5987896B2 (ja) | 長尺延伸フィルムの製造方法、及び斜め延伸装置 | |
JP5110234B1 (ja) | 長尺斜め延伸フィルムの製造方法および製造装置 | |
JP2013193226A (ja) | 長尺延伸フィルムの製造方法 | |
JP5971327B2 (ja) | 長尺延伸フィルムの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2012528979 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12868011 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14376693 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12868011 Country of ref document: EP Kind code of ref document: A1 |