WO2014156416A1 - 光学フィルムの製造方法 - Google Patents
光学フィルムの製造方法 Download PDFInfo
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- WO2014156416A1 WO2014156416A1 PCT/JP2014/054308 JP2014054308W WO2014156416A1 WO 2014156416 A1 WO2014156416 A1 WO 2014156416A1 JP 2014054308 W JP2014054308 W JP 2014054308W WO 2014156416 A1 WO2014156416 A1 WO 2014156416A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- the present invention relates to an optical film manufacturing method for manufacturing individual optical films by cutting a long optical film including a long obliquely oriented film.
- a self-luminous display device such as an organic EL (electroluminescence) display device has attracted attention.
- a reflector such as an aluminum plate is provided on the back side of the display in order to increase the light extraction efficiency. Therefore, external light incident on the display is reflected by the reflector, thereby contrasting images. Decreases.
- a circularly polarizing plate is formed by laminating a stretched film and a polarizer, and this circularly polarizing plate is disposed on the surface side of the display. At this time, the circularly polarizing plate is formed by bonding the polarizer and the stretched film so that the in-plane slow axis of the stretched film is inclined at a desired angle with respect to the transmission axis of the polarizer.
- a general polarizer (polarizing film) is obtained by stretching at a high magnification in the longitudinal direction, and its transmission axis coincides with the width direction.
- the conventional retardation film is produced by longitudinal stretching or transverse stretching, and in principle, the in-plane slow axis is in the direction of 0 ° or 90 ° with respect to the longitudinal direction of the film.
- the long polarizing film and / or the stretched film are cut out at a specific angle and the film pieces are separated from each other.
- the batch method of bonding the sheets one by one had to be adopted, and the productivity was deteriorated.
- the film is stretched in a desired angle direction (obliquely) with respect to the longitudinal direction, and the direction of the slow axis can be freely set to a direction that is neither 0 ° nor 90 ° with respect to the longitudinal direction of the film.
- Various methods for producing a long stretched film (long oblique alignment film) that can be controlled are proposed.
- the resin film is unwound from a direction different from the winding direction of the stretched film, and both ends of the resin film are gripped and transported by a pair of gripping tools. And the resin film is extended
- the long diagonally oriented film which has a slow axis in the desired angle of more than 0 degree and less than 90 degrees with respect to a longitudinal direction is manufactured.
- the long diagonally oriented film manufactured as described above is wound into a roll by a winding device after manufacturing. Moreover, when manufacturing a circularly-polarizing plate by the roll-to-roll method described above, the long diagonally oriented film is unwound from the roll again, and is bonded to the long polarizing film and wound up to form a roll. After that, the long oblique alignment film and the polarizing film are each cut at a predetermined length.
- a long circular polarizing plate is manufactured by laminating the cut oblique alignment film and the polarizing film by a roll-to-roll method, and a mirror is placed on the oblique alignment film side of the circular polarizing plate to reflect outside light.
- the long diagonally oriented film F ′ before cutting has an oblique direction when being cut in the width direction because the orientation direction is oblique to the width direction (cutting direction). It is easy to tear in (orientation direction), and this is considered to be a cause of making it easy to generate chips. Therefore, in order to reduce the bright spots, it is necessary to suppress the generation of chips due to the tearing of the film during cutting.
- the long circular polarizing plate is manufactured as a long optical film by the above roll-to-roll method, the long circular polarizing plate is cut in the width direction.
- the circular polarizing plate is torn in the orientation direction of the long obliquely oriented film, chips are generated. Therefore, even when cutting such a long circularly polarizing plate, a technique capable of suppressing generation of chips due to tearing of the film during cutting is desired.
- an object of the present invention is to cut chips by tearing in the orientation direction of a long oblique alignment film when cutting the long optical film including the long oblique alignment film in the width direction. It is providing the manufacturing method of the optical film which can suppress generation
- Q / S 1 is 5
- the long optical film is cut along a cross section including the width direction by a cutting member in a state in which a tension Q is applied to the long optical film so as to be ⁇ 100 N / m. Manufacturing method of optical film.
- the length in the width direction of the uncut region excluding the region cut by the cutting member is set to S 2 (m)
- the tension Q is decreased so that the Q / S 2 falls within the range of 5 to 100 N / m as the cutting in the width direction progresses. Manufacturing method of optical film.
- the cutting member is disposed on the upper surface side of the long optical film, a receiving portion is disposed on the lower surface side, and the cutting member is moved in the width direction while receiving the long optical film at the receiving portion.
- the long optical film is a laminated film in which a long polarizing film having a transmission axis in the width direction is attached to the long diagonally oriented film.
- the manufacturing method of the optical film in any one of.
- a tension Q such that Q / S 1 is 5 to 100 N / m is applied in the longitudinal direction, and an appropriate tension is applied to the long optical film.
- the numerical value range includes the values of the lower limit A and the upper limit B.
- the manufacturing method of the optical film which concerns on this embodiment is the length containing the elongate diagonal alignment film (henceforth a long diagonal alignment film) in which the orientation direction inclined with respect to the longitudinal direction and width direction which are orthogonal to each other.
- This is an optical film manufacturing method for manufacturing individual optical films by cutting a long optical film (hereinafter referred to as a long optical film) in the width direction with a cutting member.
- cutting the film in the width direction means cutting the film along the film cross section including the width direction.
- the moving direction of the cutting member may be the width direction or the vertical direction perpendicular to the width direction.
- the orientation direction of the long obliquely oriented film is an angle of more than 0 ° and less than 90 ° with respect to the width direction of the film in the film plane (in the plane perpendicular to the thickness direction).
- the direction automatically forms an angle of more than 0 ° and less than 90 ° with respect to the longitudinal direction of the film). Since the slow axis usually appears in the stretching direction or a direction perpendicular to the stretching direction, the slow axis has such a slow axis by stretching at an angle of more than 0 ° and less than 90 ° with respect to the width direction of the film.
- a long diagonally oriented film can be produced.
- the angle formed by the width direction of the long obliquely oriented film and the slow axis, that is, the orientation angle can be arbitrarily set to a desired angle in the range of more than 0 ° and less than 90 °.
- the long length refers to a film having a length of at least about 5 times the width of the film, preferably a length of 10 times or more, specifically a roll shape. It is possible to consider one having a length (film roll) that is wound around and stored or transported.
- the long optical film may be composed of a long diagonally oriented film itself, or may be a laminated film in which another long film is bonded to the long diagonally oriented film.
- a long polarizing film having a transmission axis in the width direction of the film and a long protective film can be considered. That is, as the laminated film as the long optical film, a laminated body of an obliquely oriented film and a polarizing film, a laminated body of an obliquely oriented film, a polarizing film, and a protective film can be considered.
- the long optical film includes an obliquely oriented film and a polarizing film, and the two are bonded so that the orientation axis of the obliquely oriented film and the transmission axis or absorption axis of the polarizing film form a predetermined angle (for example, 45 degrees).
- the long optical film can function as a circularly polarizing plate.
- the manufacturing method of the optical film of the present embodiment can be applied to a case where a long diagonally oriented film is manufactured alone, and is also applicable to a case where a long laminated film including a long diagonally oriented film is manufactured. I can say that.
- the film When producing a long diagonally oriented film, the film can be made to have a desired length by continuously producing the film. In addition, after forming a long film into a long diagonally oriented film, it is wound around a core once to form a wound body (long film original fabric), and the long film is obliquely stretched from the wound body.
- the film may be supplied and manufactured, or may be continuously supplied from the film forming process to the oblique stretching process without winding the long film after film formation. Continuously performing the film forming step and the oblique stretching step can feed back the film thickness and optical value results of the stretched film to change the film forming conditions to obtain a desired long oblique alignment film. It is preferable because it is possible.
- a long film when it is described as a long film, it refers to a long film to be stretched in an oblique stretching process, and is a long oblique alignment film after oblique stretching, or a long film thereof. It shall be distinguished from a long optical film including an obliquely oriented film.
- the long film to be stretched in the obliquely oriented film manufacturing apparatus of the present embodiment is not particularly limited as long as it is a 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 (alicyclic olefin polymer resins), and cellulose ester resins.
- polycarbonate resins, alicyclic olefin polymer resins, and cellulose ester resins are preferable from the viewpoints of transparency and mechanical strength.
- alicyclic olefin polymer resins and cellulose ester resins which can easily adjust the phase difference when an optical film is used, are more preferable. Therefore, alicyclic olefin polymer resins, cellulose ester resins, and polycarbonate resins that are preferably used in the present embodiment will be described below.
- alicyclic olefin polymer resin examples include cyclic olefin random multi-component copolymers described in JP-A No. 05-310845, hydrogenated polymers described in JP-A No. 05-97978, and JP-A No. 11 And thermoplastic dicyclopentadiene ring-opening polymers and hydrogenated products thereof described in JP-A-124429.
- the alicyclic olefin polymer resin will be described more specifically.
- the alicyclic olefin polymer resin is a polymer having an alicyclic structure such as a saturated alicyclic hydrocarbon (cycloalkane) structure or an unsaturated alicyclic hydrocarbon (cycloalkene) structure.
- the number of carbon atoms constituting the alicyclic structure is not particularly limited, but when it is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15, the mechanical strength, The properties of heat resistance and film formability are highly balanced and suitable.
- the proportion of the repeating unit containing the alicyclic structure in the alicyclic olefin polymer-based resin may be appropriately selected, but is preferably 55% by weight or more, more preferably 70% by weight or more, and particularly preferably 90%. % By weight or more.
- the ratio of the above repeating units is within this range, it is preferable because the transparency and heat resistance of an optical material such as a retardation film obtained from the long oblique alignment film of this embodiment are improved.
- alicyclic olefin polymer resins examples include norbornene resins, monocyclic olefin resins, cyclic conjugated diene resins, vinyl alicyclic hydrocarbon resins, and hydrides thereof.
- norbornene-based resins can be suitably used because of their good transparency and moldability.
- Examples of the norbornene-based resin include a ring-opening polymer of a monomer having a norbornene structure, a ring-opening copolymer of a monomer having a norbornene structure and another monomer, a hydride thereof, and a norbornene structure. And an addition copolymer of a monomer having a norbornene structure and an addition copolymer of another monomer or a hydride thereof.
- a ring-opening (co) polymer hydride of a monomer having a norbornene structure is particularly preferable from the viewpoints of transparency, moldability, heat resistance, low hygroscopicity, dimensional stability, and lightness. It can be used suitably.
- Examples of the monomer having a norbornene structure include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.12,5] deca-3,7-diene ( Common name: dicyclopentadiene), 7,8-benzotricyclo [4.3.12,5] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0.12, 5.17,10] dodec-3-ene (common name: tetracyclododecene), and derivatives of these compounds (for example, those having a substituent in the ring).
- examples of the substituent include an alkyl group, an alkylene group, and a polar group. Moreover, these substituents may be the same or different and a plurality may be bonded to the ring. Monomers having a norbornene structure can be used singly or in combination of two or more.
- Examples of the polar group include heteroatoms or atomic groups having heteroatoms.
- Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, and a halogen atom.
- Specific examples of the polar group include a carboxyl group, a carbonyloxycarbonyl group, an epoxy group, a hydroxyl group, an oxy group, an ester group, a silanol group, a silyl group, an amino group, a nitrile group, and a sulfone group.
- monomers capable of ring-opening copolymerization with monomers having a norbornene structure include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; and cyclic such as cyclohexadiene and cycloheptadiene. And conjugated dienes and derivatives thereof.
- a ring-opening polymer of a monomer having a norbornene structure and a ring-opening copolymer of a monomer having a norbornene structure and another monomer copolymerizable with the monomer have a known ring-opening polymerization catalyst. It can be obtained by (co) polymerization in the presence.
- monomers that can be copolymerized with a monomer having a norbornene structure include, for example, ethylene, propylene, ⁇ -olefins having 2 to 20 carbon atoms such as 1-butene and derivatives thereof; cyclobutene, cyclopentene And cycloolefins such as cyclohexene and derivatives thereof; and non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene.
- ⁇ -olefin is preferable, and ethylene is more preferable.
- An addition polymer of a monomer having a norbornene structure and an addition copolymer of a monomer having a norbornene structure with another monomer copolymerizable with a monomer having a norbornene structure are prepared in the presence of a known addition polymerization catalyst. It can be obtained by polymerization.
- X bicyclo [3.3.0] octane-2,4-diyl-ethylene structure
- Y tricyclo [4.3.0.12,5] decane-7, Having a 9-diyl-ethylene structure
- the content of these repeating units is 90% by weight or more based on the total repeating units of the norbornene resin
- the X content ratio and the Y content ratio The ratio is preferably 100: 0 to 40:60 by weight ratio of X: Y.
- the molecular weight used for the norbornene-based resin is appropriately selected according to the purpose of use, but is converted to polyisoprene measured by gel permeation chromatography using cyclohexane (toluene if the thermoplastic resin does not dissolve) as the solvent (the solvent is In the case of toluene, the weight average molecular weight (Mw) in terms of polystyrene is usually 10,000 to 100,000, preferably 15,000 to 80,000, more preferably 20,000 to 50,000. When the weight average molecular weight is in such a range, the mechanical strength and molding processability of the optical material obtained by the obliquely oriented film of the present embodiment are highly balanced and suitable.
- the glass transition temperature of the norbornene-based resin may be appropriately selected depending on the purpose of use, but is preferably 80 ° C. or higher, more preferably in the range of 100 to 250 ° C.
- the optical material obtained by the obliquely oriented film of the present embodiment can be excellent in durability without causing deformation or stress in use at high temperatures. .
- the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the norbornene resin is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 4.0, more preferably 1 The range is from 2 to 3.5.
- the absolute value of the photoelastic coefficient C of norbornene-based resin is preferably 10 ⁇ 10 -12 Pa -1 or less, more preferably 7 ⁇ 10 -12 Pa -1 or less, 4 ⁇ 10 -12 Pa Particularly preferably, it is ⁇ 1 or less.
- thermoplastic resin used in this embodiment is a colorant such as a pigment or dye, a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent, an antioxidant, a lubricant, and a solvent.
- the compounding agent such as may be appropriately blended.
- the content of the residual volatile component in the obliquely oriented film made of a norbornene resin is not particularly limited, but is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and further preferably 0.02% by weight. It is as follows. By setting the content of the volatile component in such a range, the dimensional stability is improved, and the temporal change of the retardation Ro in the in-plane direction and the retardation Rt in the thickness direction of the film can be reduced.
- the residual volatile component is a substance having a molecular weight of 200 or less contained in a trace amount in the film, and examples thereof include a residual monomer and a solvent.
- the content of residual volatile components can be quantified by analyzing the film by gas chromatography as the sum of the substances having a molecular weight of 200 or less contained in the film.
- the saturated water absorption of the obliquely oriented film made of norbornene resin is preferably 0.03% by weight or less, more preferably 0.02% by weight or less, and particularly preferably 0.01% by weight or less.
- the saturated water absorption is within the above range, the change in retardation Ro ⁇ Rt with time can be reduced. Furthermore, it is possible to suppress the deterioration of the retardation film obtained from the obliquely oriented film of the present embodiment, and when this is applied to a polarizing plate of a liquid crystal display device or a circularly polarizing plate of an organic EL display device, a long-term display The display can be kept stable and good.
- the saturated water absorption is a value expressed as a percentage of the mass of the test piece before immersion, after the film specimen is immersed in water at a constant temperature for a certain period of time. Usually, it is measured by immersing in 23 ° C. water for 24 hours.
- the saturated water absorption in the obliquely oriented film of the present embodiment can be adjusted to the above value by, for example, reducing the amount of polar groups in the thermoplastic resin, but is preferably a resin having no polar groups. It is desirable to be.
- a production method such as a solution casting method (solution casting method) or a melt casting method (for example, melt extrusion method) described later is preferred.
- the melt extrusion method include an inflation method using a die, but a method using a T die is preferable in terms of excellent productivity and thickness accuracy.
- a sheet-like thermoplastic resin extruded from a die is brought into close contact with a cooling drum under a pressure of 50 kPa or less; 2) melting When producing a long film by extrusion, the enclosure member covers from the die opening to the first cooling drum that is in close contact, and the distance from the enclosure member to the die opening or the first contact cooling drum is 100 mm or less.
- Method 3) Method of heating the temperature of the atmosphere within 10 mm from the sheet-like thermoplastic resin extruded from the die opening to a specific temperature when producing a long film by the melt extrusion method; 4) Melting When producing a long film by the extrusion method, the speed difference from the take-up speed of the cooling drum that first adheres to the sheet-like thermoplastic resin extruded from the die opening is 0.2 m. s method of spraying the following wind; and the like.
- cellulose ester resin films include cellulose acylates that satisfy the following formulas (1) and (2). Moreover, what contains the compound represented with the following general formula (A) is still more preferable.
- Formula (1) 2.0 ⁇ Z1 ⁇ 3.0
- Formula (2) 0 ⁇ X ⁇ 3.0 In formulas (1) and (2), Z1 represents the total acyl substitution degree of cellulose acylate, and X represents the sum of the propionyl substitution degree and butyryl substitution degree of cellulose acylate.
- L 1 and L 2 each independently represent a single bond or a divalent linking group.
- L 1 and L 2 include the following structures. (The following R represents a hydrogen atom or a substituent.)
- L 1 and L 2 are preferably —O—, —COO—, and —OCO—.
- R 1 , R 2 and R 3 each independently represents a substituent.
- substituent represented by R 1 , R 2 and R 3 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 groups (2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl groups (ethynyl group, propargyl group, etc.), ary
- R 1 and R 2 are preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted cyclohexyl group, more preferably a substituted phenyl group or a substituted cyclohexyl group, Preferred are a phenyl group having a substituent at the 4-position and a cyclohexyl group having a substituent at the 4-position.
- R 3 is preferably a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, cyano group, amino group, More preferably, they are a hydrogen atom, a halogen atom, an alkyl group, a cyano group, and an alkoxy group.
- Wa and Wb represent a hydrogen atom or a substituent, (I) Wa and Wb may be bonded to each other to form a ring; (II) At least one of Wa and Wb may have a ring structure, or (III) At least one of Wa and Wb may be an alkenyl group or an alkynyl group.
- substituent represented by Wa and Wb include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl groups (methyl group, ethyl group, n-propyl group, isopropyl group, tert- Butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), alkenyl group (vinyl group, allyl group, etc.), cycloalkenyl group ( 2-cyclopenten-1-yl, 2-cyclohexen-1-yl group, etc.), alkynyl group (ethynyl group, propargyl group etc.), aryl group (phenyl group, p-tolyl group, naphthyl group etc.),
- the ring is preferably a nitrogen-containing 5-membered ring or a sulfur-containing 5-membered ring.
- the general formula (A) is particularly preferably a compound represented by the following general formula (1) or general formula (2).
- a 1 and A 2 each independently represent —O—, —S—, —NRx— (Rx represents a hydrogen atom or a substituent) or —CO—.
- Rx represents a hydrogen atom or a substituent
- the example of the substituent represented by Rx is synonymous with the specific example of the substituent represented by said Wa and Wb.
- Rx is preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
- X represents a nonmetallic atom belonging to Groups 14-16.
- X is preferably ⁇ O, ⁇ S, ⁇ NRc, ⁇ C (Rd) Re.
- Rc, Rd, and Re represent substituents, and examples thereof are synonymous with specific examples of the substituents represented by Wa and Wb.
- L 1, L 2, R 1 , R 2, R 3, n is L 1, L 2, R 1 , same meanings as R 2, R 3, n in the general formula (A).
- Q 1 is —O—, —S—, —NRy— (Ry represents a hydrogen atom or a substituent), —CRaRb— (Ra and Rb represent a hydrogen atom or a substituent) or Represents —CO—.
- Ry, Ra, and Rb represent substituents, and examples thereof are synonymous with the specific examples of the substituents represented by Wa and Wb.
- Y represents a substituent.
- substituent represented by Y it is synonymous with the specific example of the substituent represented by said Wa and Wb.
- Y is preferably an aryl group, a heterocyclic group, an alkenyl group, or an alkynyl group.
- Examples of the aryl group represented by Y include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group.
- a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
- heterocyclic group examples include heterocyclic groups containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group.
- a heterocyclic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group.
- Group, pyrrolyl group, thienyl group, pyridinyl group and thiazolyl group are preferred.
- aryl groups or heterocyclic groups may have at least one substituent.
- substituents include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, and 1 carbon atom.
- 1 to 6 fluoroalkyl groups 1 to 6 carbon atoms alkoxy groups, 1 to 6 carbon atoms alkylthio groups, 1 to 6 carbon atoms N-alkylamino groups, 2 to 12 carbon atoms N, N-dialkylamino groups And an N-alkylsulfamoyl group having 1 to 6 carbon atoms and an N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms.
- L 1, L 2, R 1 , R 2, R 3, n is L 1, L 2, R 1 , same meanings as R 2, R 3, n in the general formula (A).
- Q 3 represents ⁇ N— or ⁇ CRz— (Rz represents a hydrogen atom or a substituent), and Q 4 represents a nonmetallic atom in Groups 14 to 16.
- Z represents a nonmetallic atom group that forms a ring with Q 3 and Q 4 .
- the ring formed from Q 3 , Q 4 and Z may be condensed with another ring.
- the ring formed from Q 3 , Q 4 and Z is preferably a nitrogen-containing 5-membered ring or 6-membered ring condensed with a benzene ring.
- L 1, L 2, R 1 , R 2, R 3, n is L 1, L 2, R 1 , same meanings as R 2, R 3, n in the general formula (A).
- Wa and Wb are preferably a vinyl group having a substituent or an ethynyl group.
- the compound represented by general formula (3) is particularly preferable.
- the compound represented by the general formula (3) is superior in heat resistance and light resistance to the compound represented by the general formula (1), and is an organic solvent compared to the compound represented by the general formula (2).
- the solubility with respect to and the compatibility with a polymer are favorable.
- the compound represented by the general formula (A) can be contained by appropriately adjusting the amount for imparting desired wavelength dispersibility and anti-bleeding property.
- the content is preferably 1 to 15% by mass, and particularly preferably 2 to 10% by mass. If it is in this range, sufficient wavelength dispersibility and bleeding prevention property can be imparted to the cellulose derivative.
- general formula (A), general formula (1), general formula (2), and general formula (3) can be obtained by referring to known methods. Specifically, it can be synthesized with reference to Journal of Chemical Crystallography (1997); 27 (9); 512-526), JP2010-31223, JP2008-107767, and the like.
- the cellulose acylate film according to this embodiment contains cellulose acylate as a main component.
- the cellulose acylate film according to this embodiment preferably contains cellulose acylate in the range of 60 to 100% by mass with respect to the total mass (100% by mass) of the film.
- the total acyl group substitution degree of cellulose acylate is 2.0 or more and less than 3.0, and more preferably 2.2 to 2.7.
- cellulose acylate examples include esters of cellulose and aliphatic carboxylic acids and / or aromatic carboxylic acids having about 2 to 22 carbon atoms, and in particular, esters of cellulose and lower fatty acids having 6 or less carbon atoms. Preferably there is.
- the acyl group bonded to the hydroxyl group of cellulose may be linear or branched, and may form a ring. Furthermore, another substituent may be substituted.
- the degree of substitution is the same, birefringence decreases when the number of carbon atoms described above is large. Therefore, the number of carbon atoms is preferably selected from acyl groups having 2 to 6 carbon atoms.
- the degree of propionyl substitution and the degree of butyryl substitution are preferred. Is a sum of 0 or more and less than 3.0.
- the cellulose acylate preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
- cellulose acylate includes propionate group, butyrate group or phthalyl group in addition to acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate propionate butyrate or cellulose acetate phthalate.
- Bound cellulose mixed fatty acid esters can be used.
- the butyryl group forming butyrate may be linear or branched.
- cellulose acetate, cellulose acetate butyrate, or cellulose acetate propionate is particularly preferably used as the cellulose acylate.
- the 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, which is one of the standards established and issued by ASTM (American Society for Testing and Materials).
- the number average molecular weight of cellulose acylate is preferably in the range of 60,000 to 300,000, since the mechanical strength of the resulting film becomes strong. More preferably, cellulose acylate having a number average molecular weight of 70,000 to 200,000 is used.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of cellulose acylate are measured using gel permeation chromatography (GPC).
- the measurement conditions are as follows.
- this measuring method can be used also as a measuring method of the other polymer in this embodiment.
- the residual sulfuric acid content in the cellulose acylate is preferably in the range of 0.1 to 45 mass ppm in terms of elemental sulfur. These are considered to be contained in the form of salts. If the residual sulfuric acid content exceeds 45 ppm by mass, there is a tendency to break during hot stretching or slitting after hot stretching.
- the residual sulfuric acid content is more preferably in the range of 1 to 30 ppm by mass.
- the residual sulfuric acid content can be measured by the method prescribed in ASTM-D817-96.
- the free acid content in the cellulose acylate is preferably 1 to 500 ppm by mass.
- the above range is preferable because it is difficult to break as described above.
- the free acid content is preferably in the range of 1 to 100 ppm by mass, and is more difficult to break.
- the range of 1 to 70 mass ppm is particularly preferable.
- the free acid content can be measured by the method prescribed in ASTM-D817-96.
- the residual alkaline earth metal content, residual sulfuric acid content, and residual acid content are within the above ranges. And is preferable.
- 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.
- the long diagonally oriented film obtained by the production method of the present embodiment may be one obtained by appropriately mixing polymer components other than the cellulose ester described later.
- the polymer component to be mixed is preferably one having excellent compatibility with the cellulose ester, and the transmittance when formed into a film is preferably 80% or more, more preferably 90% or more, and further preferably 92% or more.
- Additives added to the dope include plasticizers, ultraviolet absorbers, retardation adjusting agents, antioxidants, deterioration inhibitors, peeling aids, surfactants, dyes, fine particles, and the like.
- additives other than the fine particles may be added during the preparation of the cellulose ester solution, or may be added during the preparation of the fine particle dispersion. It is preferable to add a plasticizer, an antioxidant, an ultraviolet absorber, or the like that imparts heat and moisture resistance to the polarizing plate used in the liquid crystal image display device.
- These compounds are preferably contained in an amount of 1 to 30% by mass, preferably 1 to 20% by mass, based on the cellulose ester. Further, in order to suppress bleeding out during stretching and drying, a compound having a vapor pressure at 200 ° C. of 1400 Pa or less is preferable.
- These compounds may be added together with the cellulose ester and the solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.
- Retardation adjuster As a compound to be added for adjusting the retardation, an aromatic compound having two or more aromatic rings as described in the specification of European Patent 911,656A2 can be used.
- the aromatic ring of the aromatic compound particularly preferably contains an aromatic hetero ring in addition to the aromatic hydrocarbon ring.
- the aromatic heterocycle is generally an unsaturated heterocycle. Of these, a 1,3,5-triazine ring is particularly preferred.
- the cellulose ester film in the present embodiment has a cellulose ester and a substituent selected from a carboxyl group, a hydroxyl group, an amino group, an amide group, and a sulfonic acid group, and has a weight average molecular weight of 500 to 200,000. It is preferable to contain a polymer or oligomer of a vinyl compound within the range.
- the mass ratio of the content of the cellulose ester and the polymer or oligomer is preferably in the range of 95: 5 to 50:50.
- fine particles can be contained in the obliquely oriented film as a matting agent, whereby when the obliquely oriented film is a long film, it can be easily conveyed and wound.
- the particle size of the matting agent is preferably primary particles or secondary particles of 10 nm to 0.1 ⁇ m.
- a substantially spherical matting agent having a primary particle acicular ratio of 1.1 or less is preferably used.
- the fine particles those containing silicon are preferable, and silicon dioxide is particularly preferable.
- silicon dioxide is particularly preferable.
- silicon dioxide for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) manufactured by Nippon Aerosil Co., Ltd.
- commercially available products such as Aerosil 200V, R972, R972V, R974, R202, and R812 can be preferably used.
- the polymer fine particles include silicone resin, fluorine resin, and acrylic resin. Silicone resins are preferred, and those having a three-dimensional network structure are particularly preferred. Examples of such resins include Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.).
- the fine silicon dioxide particles preferably have a primary average particle diameter of 20 nm or less and an apparent specific gravity of 70 g / L or more.
- the average diameter of the primary particles is more preferably 5 to 16 nm, and further preferably 5 to 12 nm. A smaller primary particle average diameter is preferred because haze is low.
- the apparent specific gravity is preferably 90 to 200 g / L or more, and more preferably 100 to 200 g / L or more. Higher apparent specific gravity makes it possible to produce a high-concentration fine particle dispersion, which is preferable because no haze or aggregates are generated.
- the addition amount of the matting agent in this embodiment is preferably 0.01 to 1.0 g, more preferably 0.03 to 0.3 g, and further preferably 0.08 to 0.16 g per 1 m 2 of the long obliquely oriented film. .
- heat stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, and alumina, and alkaline earth metal salts 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.
- Polycarbonate resin As the polycarbonate-based resin according to the present embodiment, various resins can be used without particular limitation, and aromatic polycarbonate resin is preferable from the viewpoint of chemical properties and physical properties, and in particular, polycarbonate having a fluorene skeleton and bisphenol A-based polycarbonate. Resins are preferred. Among these, 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. Furthermore, 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 bonded to the central carbon of bisphenol A are replaced with benzene rings, and one hydrogen of each benzene ring of bisphenol A is replaced with a methyl group or a phenyl group.
- a polycarbonate resin obtained by using an asymmetric substitution with respect to the central carbon is particularly preferred.
- 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.
- specific examples of polycarbonate resins include, for example, JP-A-2006-215465, JP-A-2006-91836, JP-A-2005-121813, JP-A-2003-167121. And polycarbonate resins described in JP-A No. 2009-126128, JP-A 2012-67300, and International Publication No. 2000/026705.
- 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. Moreover, Tg is 120 degreeC or more, and a water absorption rate is 0.2% or less more preferable.
- Tg glass transition point
- water absorption rate measured under conditions of 23 ° C. water and 24 hours
- the polycarbonate-based resin film that can be used in the present embodiment can be formed by a known method, and among them, it is preferable to form a film using a solution casting method or a melt casting method described later.
- the long film of this embodiment made of the above-described resin can be formed by either the solution casting method or the melt casting method described below. Hereinafter, each film forming method will be described. In addition, below, although the case where a cellulose ester-type resin film is formed into a film as a long film is demonstrated, for example, it is applicable also to film forming of another resin film.
- Organic solvent An organic solvent useful for forming a dope when the cellulose ester resin film according to this embodiment is produced by a solution casting method is used without limitation as long as it dissolves cellulose acetate and other additives simultaneously. be able to.
- methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
- Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.
- the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
- a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
- the proportion of alcohol in the dope increases, the web gels and becomes easy to peel off from the metal support.
- the proportion of alcohol is small, the role of promoting cellulose acetate dissolution in non-chlorine organic solvent systems There is also.
- the dope composition is dissolved in%.
- linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Of these, ethanol is preferable because the stability of the dope can be ensured, the boiling point is relatively low, and the drying property is good.
- the cellulose ester resin film according to this embodiment can be produced by a solution casting method.
- a step of preparing a dope by dissolving a resin and an additive in a solvent a step of casting the dope on a belt-like or drum-like metal support, and a step of drying the cast dope as a web , A step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.
- the concentration of cellulose acetate in the dope is high because the drying load after casting on the metal support can be reduced. However, if the concentration is too high, the load during filtration increases and the filtration accuracy deteriorates.
- the concentration that achieves both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.
- the metal support in the casting (casting) step preferably has a mirror-finished surface, and a stainless steel belt or a drum whose surface is plated with a casting is preferably used as the metal support.
- the surface temperature of the metal support in the casting process is set to ⁇ 50 ° C. to a temperature at which the solvent boils and does not foam.
- a higher support temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or the planarity may deteriorate.
- a preferable support temperature is appropriately determined at 0 to 100 ° C., and more preferably 5 to 30 ° C.
- the method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use hot water because heat is efficiently transmitted and the time until the temperature of the metal support becomes constant is shortened.
- the amount of residual solvent when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or It is 60 to 130% by mass, and particularly preferably 20 to 30% by mass or 70 to 120% by mass.
- M is the mass (g) of the sample collected at any time during or after the production of the web or film
- N is the mass (g) after heating M at 115 ° C. for 1 hour.
- the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less. Particularly preferably, it is 0 to 0.01% by mass or less.
- a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method of drying while transporting the web by a tenter method are employed.
- melt casting method The melt casting method is preferable from the viewpoint that it becomes easy to reduce the retardation Rt in the thickness direction of the film after oblique stretching, which will be described later, and that the amount of residual volatile components is small and the dimensional stability of the film is excellent. Is the law.
- a composition containing an additive such as a resin and a plasticizer is heated and melted to a temperature showing fluidity, and then a melt containing fluid cellulose acetate is cast to form a film. How to do.
- Methods formed by melt casting can be classified into melt extrusion (molding) methods, press molding methods, inflation methods, injection molding methods, blow molding methods, stretch molding methods, and the like. Among these, the melt extrusion method that can obtain a film having excellent mechanical strength and surface accuracy is preferable.
- the plurality of raw materials used in the melt extrusion method are usually kneaded and pelletized in advance.
- the pelletization may be performed by a known method. For example, dry cellulose acetate, plasticizer, and other additives are fed to the extruder with a feeder, kneaded using a single or twin screw extruder, extruded into a strand from a die, water-cooled or air-cooled, and cut. Can be pelletized.
- Additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders. Moreover, in order to mix a small amount of additives, such as particle
- the extruder is preferably processed at as low a temperature as possible so that it can be pelletized so as to suppress the shearing force and prevent the resin from deteriorating (molecular weight reduction, coloring, gel formation, etc.).
- a twin screw extruder it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.
- Film formation is performed using the pellets obtained as described above.
- the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.
- the melting temperature at the time of extrusion is about 200 to 300 ° C, filtered through a leaf disk type filter, etc. to remove foreign matter, and then formed into a film from the T die. Then, the film is nipped between the cooling roll and the elastic touch roll and solidified on the cooling roll.
- the extrusion flow rate is preferably carried out stably by introducing a gear pump.
- a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances.
- the stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated. The density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.
- Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.
- the film temperature on the touch roll side when the film is nipped between the cooling roll and the elastic touch roll is preferably Tg (glass transition temperature) or higher and Tg + 110 ° C. or lower.
- Tg glass transition temperature
- a known roll can be used as the roll having an elastic surface used for such a purpose.
- the elastic touch roll is also called a pinching rotator.
- As the elastic touch roll a commercially available one can be used.
- the long film formed by each film forming method described above may be a single layer or a laminated film of two or more layers.
- the laminated film can be obtained by a known method such as a coextrusion molding method, a co-casting molding method, a film lamination method, or a coating method. Of these, the coextrusion molding method and the co-casting molding method are preferable.
- the thickness of the long film in this embodiment is 20 to 400 ⁇ m, more preferably 30 to 200 ⁇ m.
- the thickness unevenness ⁇ m in the flow direction (conveying direction) of the long film supplied to the stretching zone described later maintains the film take-up tension at the oblique stretching tenter inlet described later, and the orientation angle.
- 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 oblique alignment film are remarkably deteriorated.
- a film having a thickness gradient in the width direction may be supplied as the long film.
- the thickness gradient of the long film is empirically determined by stretching a film with various thickness gradients experimentally so that the film thickness at the position where the stretching in the subsequent process is completed can be made the most uniform. Can be sought.
- the gradient of the thickness of the long film can be adjusted, for example, so that the end portion on the thick side is thicker by about 0.5 to 3% than the end portion on the thin side.
- the preferable elastic modulus at the stretching temperature at the time of oblique stretching of the long film is 0.01 MPa or more and 5000 MPa or less, more preferably 0.1 MPa or more and 500 MPa or less, expressed as Young's modulus. If the elastic modulus is too low, the shrinkage rate during and after stretching becomes low and wrinkles are difficult to disappear. On the other hand, if the elastic modulus is too high, the tension applied during stretching increases, and it is necessary to increase the strength of the portions that hold the side edges of the film, which increases the load on the tenter in the subsequent step.
- a non-oriented film may be used, or a film having an orientation in advance may be supplied. Further, if necessary, the distribution in the width direction of the orientation of the long film may be bow-shaped, so-called bowing. In short, the orientation state of the long film can be adjusted so that the orientation of the film at the position where the subsequent stretching has been completed can be made desirable.
- FIG. 1 is a plan view schematically showing a schematic configuration of a manufacturing apparatus 1 for an obliquely oriented film.
- the manufacturing apparatus 1 includes, in order from the upstream side in the transport direction of the long film, a film feeding unit 2, a transport direction changing unit 3, a guide roll 4, a stretching unit 5, a guide roll 6, and a transport direction changing unit 7.
- the film cutting device 8 and the film winding unit 9 are provided. The details of the extending portion 5 will be described later.
- the film feeding unit 2 feeds the above-described long film and supplies it to the stretching unit 5.
- This film supply part 2 may be comprised separately from the film-forming apparatus of a long film, and may be comprised integrally.
- a long film is wound around a core after film formation, and a wound body (long film original fabric) is loaded into the film unwinding section 2 so that the film unwinds from the film unwinding section 2. The film is paid out.
- the film feeding unit 2 feeds the long film to the stretching unit 5 without winding the long film after the long film is formed.
- the conveyance direction changing unit 3 changes the conveyance direction of the long film fed from the film feeding unit 2 to a direction toward the entrance of the stretching unit 5 as an oblique stretching tenter.
- a conveyance direction change part 3 is comprised including the turntable which rotates the turn bar which changes the conveyance direction by, for example, returning while conveying a film, and the turn bar in the surface parallel to a film.
- the width of the entire manufacturing apparatus 1 can be made narrower, and the film feed position and angle are finely controlled. This makes it possible to obtain a long diagonally oriented film with small variations in film thickness and optical value. Further, if the film feeding unit 2 and the conveyance direction changing unit 3 can be moved (slidable and turnable), the left and right clips (gripping tools) sandwiching both ends of the long film in the width direction in the stretching unit 5 can be used. It is possible to effectively prevent the biting into the film.
- the above-described film feeding unit 2 may be slidable and turnable so that a long film can be fed out at a predetermined angle with respect to the entrance of the stretching unit 5.
- a configuration in which the installation of the conveyance direction changing unit 3 is omitted may be employed.
- At least one guide roll 4 is provided on the upstream side of the stretching portion 5 in order to stabilize the track during running of the long film.
- the guide roll 4 may be comprised by a pair of upper and lower rolls which pinch
- the guide roll 4 closest to the entrance of the extending portion 5 is a driven roll that guides the travel of the film, and is rotatably supported via a bearing portion (not shown).
- a known material can be used as the material of the guide roll 4.
- one of the rolls upstream of the guide roll 4 closest to the entrance of the extending portion 5 is nipped by pressing the rubber roll.
- a pair of bearing portions at both ends (left and right) of the guide roll 4 closest to the entrance of the extending portion 5 includes a first tension detecting device as a film tension detecting device for detecting the tension generated in the film in the roll,
- a second tension detecting device is provided.
- a load cell can be used as the film tension detection device.
- the load cell a known tensile or compression type can be used.
- a load cell is a device that detects a load acting on an applied point by converting it into an electrical signal using a strain gauge attached to the strain generating body.
- the load cell is installed in the left and right bearing portions of the guide roll 4 closest to the entrance of the extending portion 5, whereby the force of the running film on the roll, that is, in the film traveling direction generated in the vicinity of both side edges of the film.
- the tension is detected independently on the left and right.
- a strain gauge may be directly attached to a support that constitutes the bearing portion of the roll, and a load, that is, a film tension may be detected based on the strain generated in the support. The relationship between the generated strain and the film tension is measured in advance and is known.
- the position and the transport direction of the film are changed by, for example, the transport direction changing unit 3 so that the difference in film tension between the left and right sides of the guide roll 4 closest to the entrance of the stretching unit 5 becomes equal.
- the film can be stably held by the gripping tool at the entrance of the stretching portion 5, and the occurrence of obstacles such as detachment of the gripping tool can be reduced.
- the physical properties in the width direction of the film after oblique stretching by the stretching portion 5 can be stabilized.
- At least one guide roll 6 is provided on the downstream side of the stretching portion 5 in order to stabilize the track during running of the film that is obliquely stretched in the stretching portion 5.
- the transport direction changing unit 7 changes the transport direction of the stretched film transported from the stretching unit 5 to a direction toward the film winding unit 9.
- the film traveling direction at the entrance of the stretching portion 5 and the film traveling direction at the exit of the stretching portion 5 It is necessary to adjust the angle between the two.
- the traveling direction of the formed film is changed by the transport direction changing unit 3 to guide the film to the inlet of the stretching unit 5 and / or the traveling direction of the film from the outlet of the stretching unit 5 Is changed by the transport direction changing unit 7 to return the film to the direction of the film winding unit 9.
- the film formation and oblique stretching are continuously performed.
- the traveling direction of the film is changed by the transport direction changing unit 3 and / or the transport direction changing unit 7, and the film is formed by the film forming process and the winding process. 1, that is, as shown in FIG. 1, the traveling direction of the film fed out from the film feeding portion 2 (feeding direction) and the traveling direction of the film immediately before being wound up by the film winding portion 9 ( The width of the entire apparatus with respect to the film traveling direction can be reduced by matching the winding direction.
- the transport direction changing unit 3 and the film feeding unit 2 and the film winding unit 9 are arranged so as not to interfere with each other. It is preferable that the traveling direction of the film is changed by the transport direction changing unit 7.
- the transport direction changing units 3 and 7 as described above can be realized by a known method such as using an air flow roll or an air turn bar.
- the film cutting device 8 cuts the film stretched by the stretching section 5 (long obliquely oriented film) along a cross section including the width direction, and has a cutting member 8a.
- the cutting member 8a is composed of, for example, a scissor or a cutter (including a slitter, a strip-shaped blade (Thomson blade)), but is not limited thereto, and in addition, a rotating circular saw, a laser irradiation device, or the like It is also possible to configure.
- the film take-up unit 9 takes up a film conveyed from the stretching unit 5 via the conveyance direction changing unit 7, and includes, for example, a winder device, an accumulator device, and a drive device. It is preferable that the film winding unit 9 has a structure that can be slid in the horizontal direction in order to adjust the film winding position.
- the film take-up unit 9 can finely control the film take-up position and angle so that the film can be taken at a predetermined angle with respect to the outlet of the stretching unit 5. As a result, it is possible to obtain an obliquely oriented film with small variations in film thickness and optical value. In addition, it is possible to effectively prevent wrinkling of the film and to improve the winding property of the film, so that the film can be wound up in a long length.
- the stretched film is released from the exit of the stretching section 5 after being gripped by the gripping tool of the stretching section 5, and after both ends (both sides) of the film gripped by the gripping tool are trimmed as necessary. Then, the film is cut into a predetermined length by the film cutting device 8 and is wound up around a winding core (winding roll) sequentially to form a wound body of an obliquely oriented film.
- a winding core winding roll
- the masking film may be overlapped on the obliquely oriented film and taken up at the same time, or at least one of the obliquely oriented films overlapping by winding (preferably May be wound up with a tape or the like attached to both ends.
- the masking film is not particularly limited as long as it can protect the obliquely oriented film, and examples thereof include a polyethylene terephthalate film, a polyethylene film, and a polypropylene film.
- FIG. 2 is a plan view schematically showing an example of the rail pattern of the extending portion 5.
- this is an example, and the configuration of the extending portion 5 is not limited to this.
- the production of the long diagonally oriented film in the present embodiment is performed using a tenter (an oblique stretching machine) capable of oblique stretching as the stretching unit 5.
- This tenter is an apparatus that heats a long film to an arbitrary temperature at which it can be stretched and obliquely stretches it.
- This tenter includes a heating zone Z, a pair of rails Ri and Ro on the left and right, and a number of gripping tools Ci and Co that travel along the rails Ri and Ro to convey a film (in FIG. 2, a set of gripping tools). Only). Details of the heating zone Z will be described later.
- Each of the rails Ri and Ro is configured by connecting a plurality of rail portions with connecting portions (white circles in FIG. 2 are examples of connecting portions).
- the gripping tool Ci / Co is composed of a clip that grips both ends of the film in the width direction.
- the feeding direction D1 of the long film is different from the winding direction D2 of the elongated slanted oriented film after stretching, and forms a feeding angle ⁇ i with the winding direction D2.
- the feeding angle ⁇ i can be arbitrarily set to a desired angle in the range of more than 0 ° and less than 90 °.
- the rail pattern of the tenter has an asymmetric shape on the left and right. And a rail pattern can be adjusted now manually or automatically according to orientation angle (theta) given to the long diagonally oriented film which should be manufactured, a draw ratio, etc.
- orientation angle theta
- FIG. In the oblique stretching machine used in the manufacturing method of the present embodiment, it is preferable that the positions of the rail portions and the rail connecting portions constituting the rails Ri and Ro can be freely set and the rail pattern can be arbitrarily changed.
- the tenter gripping tool Ci ⁇ Co travels at a constant speed with a constant interval from the front and rear gripping tools Ci ⁇ Co.
- the traveling speed of the gripping tool Ci / Co can be selected as appropriate, but is usually 1 to 150 m / min.
- the difference in travel speed between the pair of left and right grippers Ci / Co is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less of the travel speed. This is because if there is a difference in the traveling speed on the left and right of the film at the exit of the stretching process, wrinkles and shifts will occur at the exit of the stretching process, so the speed difference between the left and right grippers Ci / Co is substantially the same speed. Is required.
- a high bending rate is often required for the rail that regulates the trajectory of the gripping tool, particularly at a location where the film is transported obliquely.
- the obliquely stretched tenter used for imparting the oblique orientation to the long film can freely set the orientation angle of the film by changing the rail pattern in various ways, and further, the orientation axis of the film It is preferred that the tenter be capable of orienting the (slow axis) in the left and right direction with high precision across the film width direction and controlling the film thickness and retardation with high precision.
- Both ends of the long film are gripped by the left and right grippers Ci ⁇ Co, and are conveyed in the heating zone Z as the grippers Ci • Co travel.
- the left and right grips Ci / Co are opposed to a direction substantially perpendicular to the film traveling direction (feeding direction D1) at the entrance portion (position A in the drawing) of the extending portion 5, and are asymmetric rails.
- Each travels on Ri and Ro, and the film gripped at the exit portion (position B in the figure) at the end of stretching is released.
- the film released from the gripping tool Ci / Co is wound around the core by the film winding portion 9 described above.
- Each of the pair of rails Ri and Ro has an endless continuous track, and the grippers Ci and Co that have released the film at the exit portion of the tenter travel on the outer rail and sequentially return to the entrance portion. It is supposed to be.
- the left and right gripping tools Ci and Co which are opposed to each other at the position A in the figure, move as the rails run on the rails Ri and Ro.
- the gripping tool Ci traveling on the Ri side (in-course side) has a positional relationship preceding the gripping tool Co traveling on the rail Ro side (out-course side).
- one gripping tool Ci is first in position B at the end of film stretching.
- the straight line connecting the gripping tools Ci and Co is inclined by an angle ⁇ L with respect to the direction substantially perpendicular to the film winding direction D2.
- the long film is obliquely stretched at an angle of ⁇ L with respect to the width direction.
- substantially vertical indicates that the angle is in a range of 90 ⁇ 1 °.
- the heating zone Z of the stretching section 5 is composed of a preheating zone Z1, a stretching zone Z2, and a heat fixing zone Z3.
- the film gripped by the gripping tool Ci / Co passes through the preheating zone Z1, the stretching zone Z2, and the heat fixing zone Z3 in this order.
- the preheating zone Z1 and the stretching zone Z2 are separated by a partition, and the stretching zone Z2 and the heat fixing zone Z3 are separated by a partition.
- the preheating zone Z1 refers to a section in which the gripping tool Ci / Co that grips both ends of the film travels at the left and right (in the film width direction) at a constant interval at the entrance of the heating zone Z.
- the stretching zone Z2 refers to a section from when the gap between the gripping tools Ci and Co that grips both ends of the film opens until a predetermined gap is reached. At this time, the oblique stretching as described above is performed, but the stretching may be performed in the longitudinal direction or the transverse direction before and after the oblique stretching as necessary.
- the heat setting zone Z3 refers to a section after the stretching zone Z2 in which the interval between the gripping tools Ci and Co is constant, and the gripping tools Ci and Co at both ends travel in parallel with each other. .
- the stretched film passes through the heat setting zone Z3 and then passes through a section (cooling zone) in which the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg (° C.) of the thermoplastic resin constituting the film. May be.
- a rail pattern that narrows the gap between the gripping tools Ci and Co facing each other in advance may be used.
- the temperature of the preheating zone Z1 is Tg to Tg + 30 ° C.
- the temperature of the stretching zone Z2 is Tg to Tg + 30 ° C.
- the temperature of the heat setting zone Z3 and the cooling zone is Tg-30 to Tg + 20 ° C. with respect to the glass transition temperature Tg of the thermoplastic resin. It is preferable to set.
- the lengths of the preheating zone Z1, the stretching zone Z2, and the heat setting zone Z3 can be appropriately selected.
- the length of the preheating zone Z1 is usually 100 to 150% of the length of the stretching zone Z2, and the length of the heat setting zone Z3 The length is usually 50 to 100%.
- the draw ratio R (W / Wo) in the stretching step is preferably 1.3 to 3. 0, more preferably 1.5 to 2.8.
- the draw ratio is in this range, the thickness unevenness in the width direction of the film is preferably reduced.
- said draw ratio R is equal to a magnification (W2 / W1) when the interval W1 between both ends of the clip held at the tenter inlet portion becomes the interval W2 at the tenter outlet portion.
- the width of the stretched film is not particularly limited, but can be 500 to 4000 mm, preferably 1000 to 3000 mm.
- the method of oblique stretching in the stretching portion 5 is not limited to the above-described method.
- the oblique stretching may be performed by simultaneous biaxial stretching as disclosed in JP-A-2008-23775. Good.
- simultaneous biaxial stretching means that both ends in the width direction of the supplied long film are gripped by each gripping tool, and the long film is transported while moving each gripping tool, and the long film is transported.
- This is a method of stretching a long film in an oblique direction with respect to the width direction by making the moving speed of one gripping tool different from the moving speed of the other gripping tool while keeping the direction constant.
- oblique stretching may be performed by a technique disclosed in Japanese Patent Application Laid-Open No. 2011-11434.
- the orientation angle ⁇ is inclined in the range of, for example, greater than 0 ° and less than 90 ° with respect to the winding direction, and at least at a width of 1300 mm.
- the variation in the in-plane retardation Ro in the width direction is preferably 3 nm or less, and the variation in the orientation angle ⁇ is preferably 0.5 ° or less.
- the in-plane retardation value Ro (550) measured at a wavelength of 550 nm of the long oblique alignment film is preferably in the range of 120 nm to 160 nm, and more preferably in the range of 130 nm to 150 nm.
- the variation of the in-plane retardation Ro is 3 nm or less and preferably 1 nm or less at least 1300 mm in the width direction.
- a long diagonally oriented film is bonded to a polarizer to form a circularly polarizing plate.
- this is applied to an organic EL image display device, external light during black display is displayed. Color unevenness due to leakage of reflected light can be suppressed.
- the long oblique alignment film is used as a retardation film for a liquid crystal display device, for example, it becomes possible to improve the display quality.
- the variation in the orientation angle ⁇ is 0.5 ° or less and 0.3 ° or less at least at 1300 mm in the width direction. Preferably, 0.1 ° or less is most preferable.
- the in-plane retardation Ro of the long diagonally oriented film obtained by the production method of the present embodiment is selected as the optimum value depending on the design of the display device used.
- the average thickness of the long obliquely oriented film obtained by the production method of the present embodiment is 10 to 200 ⁇ m, preferably 10 to 60 ⁇ m, more preferably 15 to 35 ⁇ m from the viewpoint of mechanical strength. Moreover, since the thickness unevenness in the width direction of the long obliquely oriented film affects whether or not it can be wound, it is preferably 3 ⁇ m or less, and more preferably 2 ⁇ m or less.
- a polarizing plate protective film, a polarizer, and a ⁇ / 4 retardation film are laminated in this order, and the slow axis of the ⁇ / 4 retardation film and the absorption axis of the polarizer (or The angle formed with the transmission axis is 45 °.
- the polarizing plate protective film, the polarizer, and the ⁇ / 4 retardation film correspond to the protective film 313, the polarizer 312, and the ⁇ / 4 retardation film 311 in FIG. 3, respectively.
- it is preferable that a long polarizing plate protective film, a long polarizer, and a long ⁇ / 4 retardation film (long oblique alignment film) are laminated in this order.
- the circularly polarizing plate of this embodiment is manufactured by using a stretched polyvinyl alcohol doped with iodine or a dichroic dye as a polarizer, and laminating with a configuration of ⁇ / 4 retardation film / polarizer. be able to.
- the thickness of the polarizer is 5 to 40 ⁇ m, preferably 5 to 30 ⁇ m, particularly preferably 5 to 20 ⁇ m.
- the polarizing plate can be produced by a general method.
- the ⁇ / 4 retardation film subjected to the alkali saponification treatment is preferably bonded to one surface of a polarizer produced by immersing and stretching a polyvinyl alcohol film in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. .
- the polarizing plate can be constituted by further bonding a release film on the opposite surface of the polarizing plate protective film of the polarizing plate.
- the protective film and the release film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate, product inspection, and the like.
- FIG. 3 is a cross-sectional view showing a schematic configuration of the organic EL image display device 100 of the present embodiment.
- the configuration of the organic EL image display device 100 is not limited to this.
- the organic EL image display device 100 is configured by forming a circularly polarizing plate 301 on an organic EL element 101 via an adhesive layer 201.
- the organic EL element 101 includes a metal electrode 112, a light emitting layer 113, a transparent electrode (ITO, etc.) 114, and a sealing layer 115 on a substrate 111 made of glass, polyimide, or the like.
- the metal electrode 112 may be composed of a reflective electrode and a transparent electrode.
- the circularly polarizing plate 301 is formed by laminating a ⁇ / 4 retardation film 311, a polarizer 312, and a protective film 313 in order from the organic EL element 101 side.
- the polarizer 312 is a ⁇ / 4 retardation film 311 and a protective film 313. It is pinched by. The two are bonded so that the angle formed by the transmission axis of the polarizer 312 and the slow axis of the ⁇ / 4 retardation film 311 made of the long obliquely oriented film of this embodiment is about 45 ° (or 135 °).
- the circularly polarizing plate 301 is configured.
- a cured layer is laminated on the protective film 313.
- the cured layer not only prevents scratches on the surface of the organic EL image display device, but also has an effect of preventing warpage due to the circularly polarizing plate 301. Further, an antireflection layer may be provided on the cured layer.
- the thickness of the organic EL element 101 itself is about 1 ⁇ m.
- the light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Structures having various combinations such as a laminate of such a light emitting layer and an electron injection layer made of a perylene derivative, a hole injection layer, a light emitting layer, and a laminate of an electron injection layer are known.
- holes and electrons are injected into the light-emitting layer by applying a voltage to the transparent electrode and metal electrode, and the energy generated by the recombination of these holes and electrons excites the fluorescent material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state.
- the mechanism of recombination on the way is the same as that of a general diode, and as can be expected from this, the current and the light emission intensity show strong nonlinearity with rectification with respect to the applied voltage.
- an organic EL image display device in order to extract light emitted from the light emitting layer, at least one of the electrodes must be transparent, and a transparent electrode usually formed of a transparent conductor such as indium tin oxide (ITO) is used as an anode. It is used as.
- ITO indium tin oxide
- metal electrodes such as Mg—Ag and Al—Li are used.
- the light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the light emitting layer transmits light almost completely like the transparent electrode. As a result, the light that is incident from the surface of the transparent substrate when not emitting light, passes through the transparent electrode and the light emitting layer, and is reflected by the metal electrode again exits to the surface side of the transparent substrate.
- the display surface of the EL image display device looks like a mirror surface.
- the circularly polarizing plate of this embodiment is suitable for an organic EL image display device in which such external light reflection is particularly problematic.
- the organic EL element 101 when the organic EL element 101 is not emitting light, outside light incident from the outside of the organic EL element 101 due to indoor lighting or the like is absorbed by the polarizer 312 of the circularly polarizing plate 301 and the other half is transmitted as linearly polarized light. Then, the light enters the ⁇ / 4 retardation film 311.
- the light incident on the ⁇ / 4 retardation film 311 is arranged so that the transmission axis of the polarizer 312 and the slow axis of the ⁇ / 4 retardation film 311 intersect at 45 ° (or 135 °). The light is converted into circularly polarized light by passing through the ⁇ / 4 retardation film 311.
- the phase is inverted by 180 degrees and reflected as reverse circularly polarized light.
- the reflected light is incident on the ⁇ / 4 retardation film 311 and converted into linearly polarized light perpendicular to the transmission axis of the polarizer 312 (parallel to the absorption axis). Will not be emitted. That is, external light reflection at the organic EL element 101 can be reduced by the circularly polarizing plate 301.
- FIG. 4 is an explanatory view schematically showing an example of a method of cutting a long diagonally oriented film (hereinafter referred to as film F) in the width direction.
- film F a long diagonally oriented film
- arrow b the width direction perpendicular to the longitudinal direction in the film plane
- orientation direction in the figure indicates the direction of the slow axis of the film F, and when the angle (orientation angle) between the width direction of the film F and the slow axis direction is ⁇ (°), 0 ° ⁇ ⁇ ⁇ 90 °.
- a take-up roll 10 is provided on the stretching unit 5 side of the film cutting device 8, and the film F is cut by the cutting member 8a between the take-up roll 10 and the film take-up unit 9.
- the take-up roll 10 is composed of a nip roll 11.
- the nip roll 11 conveys the film F while being sandwiched between the two rolls 11a and 11b with a predetermined pressing force, thereby giving a predetermined take-up tension in the longitudinal direction in the entire width direction of the film F.
- the take-up tension T (N / m) of the film F by the take-up roll 10 is preferably adjusted between 100 N / m ⁇ T ⁇ 300 N / m, preferably 150 N / m ⁇ T ⁇ 250 N / m.
- tensile_strength refers to the tension
- the take-up tension is 100 N / m or less, sagging and wrinkles of the film F are likely to occur, and the retardation and orientation angle profile in the film width direction are also deteriorated.
- the take-up tension is 300 N / m or more, the variation of the orientation angle in the film width direction is deteriorated, and the width yield (taken efficiency in the width direction) is deteriorated.
- the fluctuation of the take-up tension with an accuracy of less than ⁇ 5%, preferably less than ⁇ 3%.
- variation in the take-up tension is ⁇ 5% or more, variations in optical characteristics in the width direction and the flow direction (conveying direction) increase.
- the load applied to the first roll (guide roll 6) on the outlet side of the stretching section 5, that is, the tension of the film is measured, and the value becomes constant.
- a method of controlling the rotation speed of the take-up roll 10 by a general PID control method can be mentioned.
- Examples of the method for measuring the load include a method in which a load cell is attached to the bearing portion of the guide roll 6 and a load applied to the guide roll 6, that is, a film tension is measured.
- a load cell a known tensile type or compression type can be used.
- tensile_strength provided to the film F is controlled by controlling the rotational speed of the winding roll 9a, for example. More specifically, when the length in the width direction of the film F is S 1 (m) and the tension applied to the film F in the longitudinal direction is Q (N), Q / S 1 is 5 to 100 N / A tension Q is applied to the film F so as to be m.
- tensile_strength exceeding 100 N / m with respect to the film F is provided to a longitudinal direction, but the tension
- the film F in a state where the tension applied to the film F is relaxed from a tension exceeding 100 N / m to a tension of 5 to 100 N / m, the film F is cut in the width direction by the cutting member 8a and wound. I try to take it.
- a plurality of rolls such as guide rolls may be placed between the take-up roll 10 and the film take-up unit 9.
- the reason why the tension applied to the film F is set in the above range is as follows.
- Q / S 1 exceeds 100 N / m
- the tension of the film F is too strong, and the film F is slightly broken at the moment when the blade of the cutting member 8a enters. It becomes easy to spread greatly in the alignment direction. As a result, chips that cause bright spots are likely to be generated.
- Q / S 1 is less than 5 N / m, the tension of the film F is too weak and it is difficult to secure a stable slitting point at the time of cutting. In this case, when the cutting position of the film F shifts at the time of cutting, the film F is easily torn in the orientation direction, and chips are easily generated.
- the film F can be prevented from tearing greatly in the orientation direction, or the position of the film F can be displaced during cutting, and the cutting locus shown in FIG. As shown, the film F can be cut straight in the width direction.
- disconnection can be suppressed as mentioned above, the cut
- the longitudinal tension Q applied to the film F may not be changed and may be constant.
- adjustment and control of tension during cutting such as adjustment of the rotation speed of the winding roll 9a during cutting, is unnecessary, the above-described effects can be obtained by a simple method.
- the take-up roll 10 takes the film F with a tension exceeding 100 N per unit length in the width direction, and the take-up roll 9a applies a tension Q to the taken-up film F. ing.
- the tension of the film F can be reduced even if the tension is reduced so that Q / S 1 is 100 N / m or less. Degradation of optical properties due to sagging and wrinkles can be suppressed.
- the nip roll 11 that sandwiches and transports the film F is used as the take-up roll 10, the nip roll 11 can easily apply a tension exceeding 100 N / m to the film F.
- the cutting method of the present embodiment described above is very effective particularly when the film F is a thin film having a thickness of 10 ⁇ m to 60 ⁇ m.
- the cutting method of the present embodiment is very effective particularly when the width of the film F is 1000 mm to 3000 mm.
- FIG. 5 is an explanatory view schematically showing another example of the method of cutting the film F in the width direction.
- a suction roll 12 may be used as the take-up roll 10.
- the suction roll 12 has a plurality of suction ports 12a on the roll surface, and conveys the film F while sucking the film F through the suction ports 12a. Even when such a suction roll 12 is used as the take-up roll 10, the film F can be taken up with a take-up tension exceeding 100 N / m.
- FIGS. 6A to 6C are explanatory views schematically showing still another example of the method of cutting the film F in the width direction, showing that the cutting in the width direction by the cutting member 8a proceeds in order. Yes.
- the tension applied in the longitudinal direction of the film F may be reduced as the cutting of the film F in the width direction proceeds.
- a tension of A (N) is applied to the film F
- B (N) may be applied
- the tension of C (N) may be applied to the film F when the cutting of the film F further proceeds.
- C ⁇ B ⁇ A the tension to be changed during the cutting of the film F may be three stages as described above, may be two stages, may be four stages or more, and is ultimately continuous. It may be.
- the take-up tension of the take-up roll 10 is made constant, There is a method in which the winding tension (rotational speed) is decreased stepwise or continuously as the film F is cut in the width direction. Conversely, the take-up tension of the take-up roll 9a is made constant, and the take-up tension of the take-up roll 10 is increased stepwise or continuously as the film F is cut in the width direction. Good.
- FIG. 7A and 7B are explanatory diagrams for explaining the tension per unit length in the width direction of the uncut region R before and during the cutting of the film F.
- region R of the film F refers to the area
- the width of the uncut region R is S 1 (m) which is the same as the width of the film F as shown in FIG. In the state before cutting F), the tension per unit length in the width direction of the uncut region R is Q / S 1 (N / m).
- the width of the uncut region R of the film F becomes S 2 (m) as the film F is cut in the width direction, the width of the uncut region R is increased.
- the tension per unit length in the direction is Q / S 2 (N / m).
- S 2 ⁇ S 1 (Q / S 1 ) ⁇ (Q / S 2 ).
- FIG. 8 and 9 are explanatory diagrams schematically showing still another example of the method of cutting the film F in the width direction.
- the cutting member 8 a is configured by a band-shaped blade along the width direction of the film F, the cutting member 8 a is moved downward from above the film F, and simultaneously in the entire width direction of the film F (width Cutting is performed without causing a time difference between the one end side and the other end side in the hand direction.
- the cutting member 8 a having a belt-like blade is rotated so that the film F is cut with a time difference between the one end side and the other end side in the width direction.
- the time difference in which the blade enters in the width direction can be significantly shortened compared to the method of cutting from the lateral direction as shown in FIG. And the generation of chips (chips) during cutting can be suppressed.
- FIGS. 10A and 10B are explanatory views schematically showing still another example of the method of cutting the film F in the width direction.
- the film F may be cut by a double-edged method. That is, the film F may be cut by disposing the cutting members 8a on the upper surface side and the lower surface side of the film F and moving the cutting members 8a in the width direction.
- the film F is loosened by the pushing force when cutting with a blade, and the slitting point is shifted.
- the slitting point is stabilized because the film F is cut as if it is held down from above and below.
- the both blades (cutting member 8a) to be used may be blades (rotary cutters) that move in the width direction while rotating as shown in FIG. 10A, or the width without rotating as shown in FIG. 10B. It may be a blade that moves in the hand direction.
- FIG. 11A and FIG. 11B are explanatory views schematically showing still another example of the method of cutting the film F in the width direction.
- the cutting member 8a is disposed on the upper surface side of the film F to be cut
- the receiving portion 8b made of a roll or the like is disposed on the lower surface side
- the cutting member 8a is received while receiving the film F at the receiving portion 8b.
- the film F may be cut by moving in the width direction.
- the blade used in that case may be a rotary blade such as a rotary cutter as shown in FIG. 11A, or a cutter that moves in the width direction without rotating as shown in FIG. 11B. Good.
- the receiving portion 8b is on the side opposite to the blade side, the slack of the film F caused by the pressing on the blade side can be suppressed as in the case of FIG. 10A and FIG. 10B. Sting point is stabilized. Note that only the blade is assumed to move, but the receiving portion 8b may move together with the blade.
- the film F can be cut by appropriately combining the configurations and methods shown in the drawings.
- the film F when cutting the film F with a time difference in the width direction as shown in FIGS. 10 and 11, it is of course possible to combine the techniques for reducing the longitudinal tension as shown in FIG.
- the film F is composed of a single layer having a long oblique orientation.
- the film F may be a laminated film in which a long polarizing film is bonded to a long oblique orientation film.
- this laminated film may further contain a protective film. Even when such a laminated film is used as a long optical film and cut in the lateral direction, the same effect as that of this embodiment can be obtained by applying the cutting method of this embodiment described above.
- thermoplastic resin film As a long film, the thermoplastic resin film is stretched by the stretching section 5 of the manufacturing apparatus 1 (see FIG. 1) shown in FIG. After producing a film, the long diagonally oriented film was cut
- DCP dicyclopentadiene
- MTF 1,4-methano-1,4,4a, 9a-tetrahydrofluorene Norbornene system consisting of 140 parts
- MTD 8-methyl-tetracyclo [4.4.0.12, 5.17,10] -dodec-3-ene
- MTD 8-methyl-tetracyclo
- This hydrogenated ring-opened polymer had a weight average molecular weight (Mw) of 31,000, a molecular weight distribution (Mw / Mn) of 2.5, a hydrogenation rate of 99.9%, and a Tg of 134 ° C.
- Mw weight average molecular weight
- Mw / Mn molecular weight distribution
- Hg hydrogenation rate
- the pellets were melt extruded using a short shaft extruder having a coat hanger type T die (Mitsubishi Heavy Industries, Ltd .: screw diameter 90 mm, T die lip material is tungsten carbide, peel strength 44N from molten resin). Molded to produce a cycloolefin polymer film.
- a long unoriented film A 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. Unoriented film A was wound up on a roll.
- the above-obtained norbornene-based resin unoriented film A is stretched by the method shown below by the stretching portion 5 (see FIG. 2 and the like) of the production apparatus 1 of the present embodiment, and the long obliquely oriented film A 'I got.
- both ends of the unoriented film A sent from the film feeding section 2 are connected to the first clip as the preceding holding tool Ci and the first clip as the delaying holding tool Co. Grip with 2 clips.
- the unoriented film A is gripped, the unoriented film A is gripped by moving the clip levers of the first and second clips with the clip closer.
- both ends of the unoriented film A are simultaneously held by the first and second clips, and the line connecting the holding positions at both ends is parallel to the axis parallel to the width direction of the film.
- the gripped unoriented film A is conveyed while being gripped by the first and second clips, and is heated by passing through the preheating zone Z1, the stretching zone Z2, and the heat fixing zone Z3 in the heating zone Z.
- a long diagonally oriented film A ′ stretched in the direction is obtained.
- the film moving speed during heating and stretching was 10 m / min. Further, the temperature of the preheating zone Z1 was 140 ° C., the temperature of the stretching zone Z2 was 140 ° C., and the temperature of the heat setting zone Z3 was 137 ° C. The stretching ratio of the film before and after stretching was 2.0 times, and the thickness of the film after stretching was 50 ⁇ m.
- trimming treatment was applied to both ends of the obtained long obliquely oriented film A ′ so that the final film width was 1400 mm.
- the average value of the in-plane retardation Ro of the obtained film was 140 nm, and the average value of the orientation angle ⁇ was 45 °.
- the cycloolefin polymer film constituting the long obliquely oriented film A ′ obtained by the above steps is also referred to as a COP film.
- the inside of the Kolben was depressurized to 4 ⁇ 10 2 Pa or less, and after excess pyridine was distilled off at 60 ° C., the inside of the Kolben was depressurized to 1.3 ⁇ 10 Pa or less and the temperature was raised to 120 ° C. Most of the acid and benzoic acid formed were distilled off. Finally, 100 g of water is added to the collected toluene layer, and after washing with water at room temperature for 30 minutes, the toluene layer is separated, and the toluene is distilled off at 60 ° C. under reduced pressure (4 ⁇ 10 2 Pa or less). A mixture of A-1, A-2, A-3, A-4 and A-5 was obtained.
- 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
- Ester Compound 1 >> 251 g of 1,2-propylene glycol, 278 g of phthalic anhydride, 91 g of adipic acid, 610 g of benzoic acid, 0.191 g of tetraisopropyl titanate as an esterification catalyst, 2 L four-neck equipped with a thermometer, stirrer, and slow cooling tube The flask was charged and gradually heated with stirring until it reached 230 ° C. in a nitrogen stream. The ester compound 1 was obtained by carrying out a dehydration condensation reaction for 15 hours, and distilling off unreacted 1,2-propylene glycol under reduced pressure at 200 ° C. after completion of the reaction.
- the ester compound 1 has an ester of benzoic acid at the end of a polyester chain formed by condensation of 1,2-propylene glycol, phthalic anhydride and adipic acid.
- the acid value of the ester compound 1 was 0.10, and the number average molecular weight was 450.
- Fine particle additive liquid 1 After 11 parts by mass of fine particles (Aerosil R972V manufactured by Nippon Aerosil Co., Ltd.) and 89 parts by mass of ethanol were stirred and mixed with a dissolver for 50 minutes, dispersion was performed with Manton Gorin to prepare a fine particle dispersion 1.
- fine particle dispersion 1 1 part by mass of the fine particle dispersion 1 was slowly added while sufficiently stirring the dissolution tank containing 99 parts by mass of methylene chloride. 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 1.
- the dope solution was uniformly cast on a stainless steel belt support using an endless belt casting apparatus.
- the solvent was evaporated until the residual solvent amount in the cast (cast) film was 75%, and the film was peeled off from the stainless steel belt support.
- the peeled cellulose ester film was stretched 1.1 times in the width direction by a transverse stretching tenter.
- the temperature conditions of the transverse stretching tenter oven at that time were adjusted to 160 ° C. for the preheating zone, 165 ° C. for the stretching zone, 172 ° C. for the holding zone, and 110 ° C. for the cooling zone.
- the tenter clip marks at both ends of the film are trimmed, the drying temperature is 130 ° C., and the drying is finished while the long film is conveyed in the drying zone using a number of rolls, and then wound in the winding process. It was wound up as a circular body. As described above, a roll-like long film (long film original fabric) was obtained.
- the long film of cellulose resin obtained above was obliquely stretched using the stretched portion 5 shown in FIG. 2 to obtain a long diagonally oriented film B ′.
- the film moving speed is 10 m / min
- the temperature of the preheating zone Z1 is 187 ° C.
- the temperature of the stretching zone Z2 is 186 ° C.
- the temperature of the heat setting zone Z3 is 170 ° C.
- the stretching ratio is 2.0 times.
- the long diagonally-oriented film B ' was manufactured on the same conditions as the manufacturing method of the cycloolefin film mentioned above.
- the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water.
- the methylene chloride phase is concentrated and dehydrated.
- a solution having a polycarbonate concentration of 20% was obtained.
- the polycarbonate (copolymer A) obtained by removing the solvent from this solution had a molar ratio of biscresol fluorene to bisphenol A of 70:30 (polymer yield 97%). Further, this polymer had an intrinsic viscosity of 0.674 and a Tg of 226 ° C.
- This dope was poured on a stainless steel belt with a dew point controlled to 12 ° C. or less by blowing dry air and peeled off.
- the residual solvent concentration at that time was 35% by mass. Thereafter, when the residual solvent concentration was 2% by mass, the width was kept and dried. Then, it was dried until the residual solvent concentration became 1% by mass or less. By doing so, the polycarbonate film (long film C) was obtained.
- the gripped unstretched film is heated by passing the preheating zone, the stretching zone, and the heat setting zone in the heating zone by the first and second clips, and stretched in the width direction, and is a long obliquely oriented film.
- C ' was obtained.
- the film conveyance speed during heating and stretching was 10 m / min.
- the stretch ratio of the film before and after stretching was doubled so that the thickness of the film after stretching was 51 ⁇ m and the width was 1800 mm.
- the polycarbonate film constituting the long oblique alignment film C ′ obtained by the above steps is also referred to as a PC film.
- Example 1 While winding the long diagonally oriented film A ′ made of a COP film by the film winding unit 9, the film cutting device 8 (cutting member 8a) shown in FIG. 4 is moved in the width direction for each predetermined length. Disconnected. At this time, the long diagonally oriented film A ′ was cut in a state where a tension of 5 N per unit length in the width direction was applied to the long diagonally oriented film A ′ in the longitudinal direction. During the cutting of the long oblique alignment film A ′, the tension applied in the longitudinal direction is constant (5 N / m), and the blade of the cutting member 8a enters the upper surface earlier than the lower surface of the long oblique alignment film A ′. I did it.
- the obliquely oriented film (obliquely oriented film after cutting) obtained as described above was bonded to one side of the polarizer using a 5% polyvinyl alcohol aqueous solution as an adhesive.
- the lamination was performed so that the transmission axis of the polarizer and the slow axis of the obliquely oriented film were oriented at 45 °.
- a Konica Minolta-tack film KC6UA manufactured by Konica Minolta Opto Co., Ltd.
- alkali saponification treatment was similarly bonded to the other surface of the polarizer to produce a circularly polarizing plate.
- Example 2 when the long diagonally oriented film A ′ is cut in the width direction, the tension applied in the longitudinal direction is set to 30 N per unit length in the width direction, and the tension is constant during cutting (30 N / m). ). The rest is the same as in the first embodiment.
- Example 3 when the long diagonally oriented film A ′ is cut in the width direction, the tension applied in the longitudinal direction is 80 N per unit length in the width direction, and the tension is constant during cutting (80 N / m). ). The rest is the same as in the first embodiment.
- Example 4 the winding tension of the winding roll is such that the tension applied to the uncut region is always 80 N / m as the cutting of the long diagonally oriented film A ′ in the width direction proceeds. (N) was reduced as cutting progressed. The rest is the same as in the first embodiment.
- Comparative Example 1 when the long diagonally oriented film A ′ was cut in the width direction, the tension applied in the longitudinal direction was 3N per unit length in the width direction, and the tension was constant during cutting (3 N / m ). The rest is the same as in the first embodiment.
- Example 5 the long diagonally oriented film A ′ was cut by the method shown in FIG. That is, the cutting member was moved downward from above the long obliquely oriented film A ′, and the long obliquely oriented film A ′ was simultaneously cut in the entire width direction. The rest is the same as in the second embodiment.
- Example 6 the long diagonally oriented film A ′ was cut by the method shown in FIG. That is, the cutting member is rotated within the cross section of the film including the width direction so that a time difference occurs between one end side and the other end side in the width direction of the long oblique alignment film A ′. Was cut off. The rest is the same as in the second embodiment.
- Example 7 the long diagonally oriented film A ′ was cut by the method shown in FIG. 10A. That is, when the cutting member is moved in the width direction and the long diagonally oriented film A ′ is cut, the blades of the cutting member enter the both sides of the upper and lower surfaces of the long diagonally oriented film A ′ at the same time. Then, the long diagonally oriented film A ′ was cut. The rest is the same as in the second embodiment.
- Example 8 the long diagonally oriented film A ′ was cut by the method of FIG. 11A. That is, when cutting the long diagonally oriented film A ′ by moving the cutting member in the width direction, the blade of the cutting member is installed on the upper surface side of the long diagonally oriented film A ′, and the roll is installed on the lower surface side. And the rotary cutter as a cutting member was pressed against the film from the upper surface of the long diagonally oriented film A ′ in close contact with the roll installed on the lower surface side, and the long diagonally oriented film A ′ was cut. The rest is the same as in the second embodiment.
- Example 9 the film cutting device 8 (cutting member 8a) shown in FIG. 4 was moved in the width direction while winding the long obliquely oriented film B ′ made of a cellulose film by the film winding unit 9. It cut
- Comparative Example 3 when the long diagonally oriented film B ′ is cut in the width direction, the tension applied in the longitudinal direction is 3 N per unit length in the width direction, and the tension is constant during cutting (3 N / m ). The rest is the same as in the first embodiment.
- Example 10 the film cutting device 8 (cutting member 8a) shown in FIG. 4 was moved in the width direction while winding the long diagonally oriented film C ′ made of PC film by the film winding unit 9. It cut
- Table 1 shows the results of bright spot evaluation for the circularly polarizing plates of Examples 1 to 4 and Comparative Examples 1 and 2.
- Example 4 even when the tension applied to the film in the longitudinal direction is constant regardless of the progress of cutting in the width direction, there is an effect of suppressing the generation of bright spots, In particular, as in Example 4, the effect of suppressing the generation of bright spots is increased by reducing the tension applied in the longitudinal direction with the progress of cutting in the width direction. This is presumably because as the cutting in the width direction proceeds, the tension applied to the uncut region of the film decreases, the film becomes difficult to tear, and the generation of chips is further suppressed.
- Table 2 shows the results of evaluation of bright spots for the circularly polarizing plates of Examples 5 to 8.
- Table 3 shows the evaluation results of the bright spots for the circularly polarizing plates of Examples 9 to 10 and Comparative Examples 3 to 4.
- the long diagonally oriented film is cut in the width direction in a state where a tension of 5 to 100 N / m (in the longitudinal direction is applied to the long diagonally oriented film.
- a tension of 5 to 100 N / m in the longitudinal direction is applied to the long diagonally oriented film.
- the long diagonally oriented film is cut in the width direction as a single unit, but the long polarizing film is bonded to the long diagonally oriented film to form the long circular polarizing plate first. And even if this circularly-polarizing plate was cut
- a cycloolefin polymer film, a cellulose ester film, and a polycarbonate film are used as the long diagonally oriented film, but even when a film made of another resin material (for example, acrylic) is used, It was found that the same evaluation results as described above can be obtained by cutting with an appropriate tension.
- the present invention can be used for manufacturing a circularly polarizing plate for preventing external light reflection of an organic EL image display device.
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Abstract
Description
本実施形態の斜め配向フィルムの製造装置(詳細は後述する)にて延伸対象となる長尺フィルムとしては、特に限定されず、熱可塑性樹脂から構成されているフィルムであれば何でも良いが、例えば、延伸後のフィルムを光学用途に使用する場合には、所望の波長に対して透明な性質を有する樹脂からなるフィルムが好ましい。このような樹脂としては、ポリカーボネート系樹脂、ポリエーテルスルフォン系樹脂、ポリエチレンテレフタレート系樹脂、ポリイミド系樹脂、ポリメチルメタクリレート系樹脂、ポリスルフォン系樹脂、ポリアリレート系樹脂、ポリエチレン系樹脂、ポリ塩化ビニル系樹脂、脂環構造を有するオレフィンポリマー系樹脂(脂環式オレフィンポリマー系樹脂)、セルロースエステル系樹脂などが挙げられる。
脂環式オレフィンポリマー系樹脂としては、特開平05-310845号公報に記載されている環状オレフィンランダム多元共重合体、特開平05-97978号公報に記載されている水素添加重合体、特開平11-124429号公報に記載されている熱可塑性ジシクロペンタジエン系開環重合体およびその水素添加物等を挙げることができる。
好ましいセルロースエステル系樹脂フィルムとしては、下記式(1)および(2)を満たすセルロースアシレートが挙げられる。また、下記一般式(A)で表される化合物を含有するものが更に好ましい。
式(1) 2.0≦Z1<3.0
式(2) 0≦X<3.0
(式(1)および(2)において、Z1はセルロースアシレートの総アシル置換度を表し、Xはセルロースアシレートのプロピオニル置換度およびブチリル置換度の総和を表す。)
(I)WaおよびWbが互いに結合して環を形成してもよく、
(II)WaおよびWbの少なくとも一つが環構造を有してもよく、または
(III)WaおよびWbの少なくとも一つがアルケニル基またはアルキニル基であってもよい。
本実施形態に係るセルロースアシレートフィルムは、セルロールアシレートを主成分として含有する。例えば、本実施形態に係るセルロースアシレートフィルムは、フィルムの全質量(100質量%)に対して、セルロースアシレートを好ましくは60~100質量%の範囲で含む。また、セルロースアシレートの総アシル基置換度は、2.0以上3.0未満であり、2.2~2.7であることがより好ましい。
カラム:Shodex K806、K805、K803G(昭和電工株式会社製)を3本接続して使用する;
カラム温度:25℃;
試料濃度:0.1質量%;
検出器:RI Model 504(GLサイエンス社製);
ポンプ:L6000(日立製作所株式会社製);
流量:1.0ml/min
校正曲線:標準ポリスチレンSTK standard ポリスチレン(東ソー株式会社製)Mw=1000000~500の13サンプルによる校正曲線を使用する。13サンプルは、ほぼ等間隔に用いる。
本実施形態の製造方法により得られた長尺斜め配向フィルムは、後述するセルロースエステル以外の高分子成分を適宜混合したものでもよい。混合される高分子成分はセルロースエステルと相溶性に優れるものが好ましく、フィルムにした時の透過率が80%以上、更に好ましくは90%以上、更に好ましくは92%以上であることが好ましい。
リタデーションを調整するために添加する化合物としては、欧州特許911,656A2号明細書に記載されているような、二つ以上の芳香族環を有する芳香族化合物を使用することができる。
本実施形態におけるセルロースエステルフィルムは、セルロースエステルと、カルボキシル基、ヒドロキシル基、アミノ基、アミド基、およびスルホン酸基から選ばれる置換基を有し、かつ、重量平均分子量が500~200,000の範囲内であるビニル系化合物のポリマーまたはオリゴマーとを含有することが好ましい。当該セルロースエステルと、当該ポリマーまたはオリゴマーとの含有量の質量比が、95:5~50:50の範囲内であることが好ましい。
本実施形態では、マット剤として微粒子を斜め配向フィルム中に含有させることができ、これによって、斜め配向フィルムが長尺フィルムの場合、搬送や巻き取りをしやすくすることができる。
その他、カオリン、タルク、ケイソウ土、石英、炭酸カルシウム、硫酸バリウム、酸化チタン、アルミナ等の無機微粒子、カルシウム、マグネシウム等のアルカリ土類金属の塩等の熱安定剤を加えてもよい。更に界面活性剤、剥離促進剤、帯電防止剤、難燃剤、滑剤、油剤等も加えてもよい。
本実施形態に係るポリカーボネート系樹脂としては、特に限定なく種々のものを使用でき、化学的性質及び物性の点から、芳香族ポリカーボネート樹脂が好ましく、特に、フルオレン骨格を有するポリカーボネートや、ビスフェノールA系ポリカーボネート樹脂が好ましい。その中でも、ビスフェノールAにベンゼン環、シクロヘキサン環、および脂肪族炭化水素基等を導入したビスフェノールA誘導体を用いたものがより好ましい。さらに、ビスフェノールAの中央の炭素に対して、非対称に上記官能基が導入された誘導体を用いて得られた、単位分子内の異方性を減少させた構造のポリカーボネート樹脂が特に好ましい。
上述した樹脂からなる本実施形態の長尺フィルムは、以下に示す溶液流延法、溶融流延法のどちらでも製膜することができる。以下、各製膜法について説明する。なお、以下では、長尺フィルムとして、例えばセルロースエステル系樹脂フィルムを製膜する場合について説明するが、他の樹脂フィルムの製膜についても勿論適用することができる。
フィルムの着色抑制、異物欠点の抑制、ダイラインなどの光学欠点の抑制、フィルムの平面性、透明度に優れるなどの観点からは、長尺フィルムを溶液流延法で製膜することが好ましい。
本実施形態に係るセルロースエステル系樹脂フィルムを溶液流延法で製造する場合のドープを形成するのに有用な有機溶媒は、セルロースアセテート、その他の添加剤を同時に溶解するものであれば制限なく用いることができる。
本実施形態に係るセルロースエステル系樹脂フィルムは、溶液流延法によって製造することができる。溶液流延法では、樹脂および添加剤を溶剤に溶解させてドープを調製する工程、ドープをベルト状もしくはドラム状の金属支持体上に流延する工程、流延したドープをウェブとして乾燥する工程、金属支持体から剥離する工程、延伸または幅保持する工程、更に乾燥する工程、仕上がったフィルムを巻き取る工程により行われる。
残留溶媒量(質量%)={(M-N)/N}×100
なお、Mはウェブまたはフィルムを製造中または製造後の任意の時点で採取した試料の質量(g)であり、NはMを115℃で1時間の加熱した後の質量(g)である。
溶融流延法は、後述する斜め延伸後のフィルムの厚み方向のリタデーションRtを小さくすることが容易となり、残留揮発性成分量が少なくフィルムの寸法安定性にも優れる等の観点から、好ましい製膜法である。溶融流延法は、樹脂および可塑剤などの添加剤を含む組成物を、流動性を示す温度まで加熱溶融し、その後、流動性のセルロースアセテートを含む溶融物を流延してフィルムを製膜する方法をいう。溶融流延によって形成される方法は、溶融押出(成形)法、プレス成形法、インフレーション法、射出成形法、ブロー成形法、延伸成形法などに分類できる。これらの中で、機械的強度および表面精度などに優れるフィルムが得られる溶融押出法が好ましい。また、溶融押出法で用いる複数の原材料は、通常、予め混錬してペレット化しておくことが好ましい。
本実施形態における長尺フィルムの厚さは、20~400μm、より好ましくは30~200μmである。また、本実施形態では、後述する延伸ゾーンに供給される長尺フィルムの流れ方向(搬送方向)の厚みムラσmは、後述する斜め延伸テンター入口でのフィルムの引取張力を一定に保ち、配向角やリタデーションといった光学特性を安定させる観点から、0.30μm未満、好ましくは0.25μm未満、さらに好ましくは0.20μm未満である必要がある。長尺フィルムの流れ方向の厚みムラσmが0.30μm以上となると、長尺斜め配向フィルムのリタデーションや配向角といった光学特性のバラツキが顕著に悪化する。
次に、上述した長尺フィルムを幅手方向に対して斜め方向に延伸して長尺状の斜め配向フィルムを製造する、斜め配向フィルムの製造方法および製造装置について説明する。
図1は、斜め配向フィルムの製造装置1の概略の構成を模式的に示す平面図である。製造装置1は、長尺フィルムの搬送方向上流側から順に、フィルム繰り出し部2と、搬送方向変更部3と、ガイドロール4と、延伸部5と、ガイドロール6と、搬送方向変更部7と、フィルム切断装置8と、フィルム巻き取り部9とを備えている。なお、延伸部5の詳細については後述する。
次に、上述した延伸部5の詳細について説明する。図2は、延伸部5のレールパターンの一例を模式的に示す平面図である。但し、これは一例であって、延伸部5の構成はこれに限定されるものではない。
本実施形態の製造方法により得られた長尺斜め配向フィルムにおいては、配向角θが巻取方向に対して、例えば0°より大きく90°未満の範囲に傾斜しており、少なくとも1300mmの幅において、幅方向の、面内リタデーションRoのバラツキが3nm以下、配向角θのバラツキが0.5°以下であることが好ましい。また、前記長尺斜め配向フィルムの、波長550nmで測定した面内リタデーション値Ro(550)が、120nm以上160nm以下の範囲にあることが好ましく、130nm以上150nm以下の範囲であることがさらに好ましい。
本実施形態の円偏光板は、偏光板保護フィルム、偏光子、λ/4位相差フィルムがこの順で積層されており、λ/4位相差フィルムの遅相軸と偏光子の吸収軸(または透過軸)とのなす角度が45°である。なお、上記の偏光板保護フィルム、偏光子、λ/4位相差フィルムは、それぞれ、図3の保護フィルム313、偏光子312、λ/4位相差フィルム311にそれぞれ対応している。本実施形態においては、長尺状偏光板保護フィルム、長尺状偏光子、長尺状λ/4位相差フィルム(長尺斜め配向フィルム)がこの順で積層して形成されることが好ましい。
図3は、本実施形態の有機EL画像表示装置100の概略の構成を示す断面図である。なお、有機EL画像表示装置100の構成は、これに限定されるものではない。
次に、上述したフィルム切断装置8を用いたフィルムの切断方法について説明する。図4は、長尺斜め配向フィルム(以下、フィルムFと記載する)を幅手方向に切断する手法の一例を模式的に示す説明図である。なお、図4では、フィルムFの長手方向(フィルム搬送方向)を矢印aで示し、フィルム面内で長手方向に垂直な幅手方向を矢印bで示している。なお、他の図面でも上記と同様に表記するものとする。また、図中の配向方向は、フィルムFの遅相軸の方向を指し、フィルムFの幅手方向と遅相軸方向とのなす角度(配向角)をθ(°)とすると、0°<θ<90°である。
以下、本実施形態における斜め配向フィルムの製造に関する具体例な実施例について、比較例も挙げながら説明する。なお、本発明は、以下の実施例に限定されるものではない。以下の実施例では、長尺フィルムとしての熱可塑性樹脂フィルムを成膜後、図2で示した製造装置1(図1参照)の延伸部5によって熱可塑性樹脂フィルムを延伸し、長尺斜め配向フィルムを作製した後、フィルム切断装置8によって長尺斜め配向フィルムを切断し、個々の斜め配向フィルムを製造した。以下、より具体的に説明する。なお、以下では、「部」あるいは「%」の表記を用いるが、特に断らない限り、これらは「質量部」あるいは「質量%」を表すものとする。
窒素雰囲気下で、脱水したシクロヘキサン500部に、1-ヘキセン1.2部、ジブチルエーテル0.15部、トリイソブチルアルミニウム0.30部を室温で反応器に入れ混合した後、45℃に保ちながら、トリシクロ[4.3.0.12,5]デカ-3,7-ジエン(ジシクロペンタジエン、以下、DCPと略記)20部、1,4-メタノ-1,4,4a,9a-テトラヒドロフルオレン(以下、MTFと略記)140部、および8-メチル-テトラシクロ[4.4.0.12,5.17,10]-ドデカ-3-エン(以下、MTDと略記)40部からなるノルボルネン系モノマー混合物と、六塩化タングステン(0.7%トルエン溶液)40部とを、2時間かけて連続的に添加し重合した。重合溶液にブチルグリシジルエーテル1.06部とイソプロピルアルコール0.52部を加えて重合触媒を不活性化し重合反応を停止させた。
《糖エステル化合物1の合成》
以下の工程により、糖エステル化合物1を合成した。
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
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℃
1,2-プロピレングリコール251g、無水フタル酸278g、アジピン酸91g、安息香酸610g、エステル化触媒としてテトライソプロピルチタネート0.191gを、温度計、撹拌器、緩急冷却管を備えた2Lの四つ口フラスコに仕込み、窒素気流中230℃になるまで、撹拌しながら徐々に昇温した。15時間脱水縮合反応させ、反応終了後200℃で未反応の1,2-プロピレングリコールを減圧留去することにより、エステル化合物1を得た。エステル化合物1は、1,2-プロピレングリコール、無水フタル酸およびアジピン酸が縮合して形成されたポリエステル鎖の末端に安息香酸のエステルを有する。エステル化合物1の酸価は0.10、数平均分子量は450であった。
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い、微粒子分散液1を調整した。
メチレンクロライド、エタノール、セルロースアセテートプロピオネート、下記の化合物(B)、前述した糖エステル化合物1、エステル化合物1、微粒子添加液1を下記記載の組成となるようドープ液を密閉容器に投入し、攪拌しながら溶解してドープ液を調製した。
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1 5.0質量部
エステル化合物1 2.5質量部
微粒子添加液1 1質量部
温度計、撹拌機、還流冷却器付き反応器(容器)に、まず、イオン交換水152400質量部、25質量%水酸化ナトリウム水溶液84320質量部を入れた。その後、前記容器に、HPLC分析で純度99.8質量%の9,9-ビス(4-ヒドロキシ-3-メチルフェニル)フルオレン(ビスクレゾールフルオレン)34848質量部、2,2-ビス(4-ヒドロキシフェニル)プロパン(ビスフェノールA)9008質量部、及びハイドロサルファイト88質量部を入れ、これらを前記容器内の液体に溶解させた。
COPフィルムからなる長尺斜め配向フィルムA’を、フィルム巻き取り部9によって巻き取りながら、図4で示したフィルム切断装置8(切断部材8a)を幅手方向に移動させて所定の長さごとに切断した。このとき、長尺斜め配向フィルムA’に対して、幅手方向の単位長さあたり5Nの張力を長手方向に付与した状態で、長尺斜め配向フィルムA’を切断した。なお、長尺斜め配向フィルムA’の切断中、長手方向に付与する張力は一定(5N/m)とし、切断部材8aの刃は長尺斜め配向フィルムA’の下面よりも上面に先に入るようにした。
次に、厚さ120μmのポリビニルアルコールフィルムを、一軸延伸し(温度110℃、延伸倍率5倍)、ヨウ素0.075g、ヨウ化カリウム5g、水100gからなる水溶液に60秒間浸漬し、次いでヨウ化カリウム6g、ホウ酸7.5g、水100gからなる68℃の水溶液に浸漬した。浸漬後のフィルムを水洗、乾燥し、偏光子を得た。続いて、上記のようにして得られた斜め配向フィルム(切断後の斜め配向フィルム)を、ポリビニルアルコール5%水溶液を粘着剤として、上記偏光子の片面に貼合した。その際、偏光子の透過軸と斜め配向フィルムの遅相軸とが45°の向きになるように貼合した。そして、偏光子のもう一方の面に、アルカリケン化処理をしたコニカミノルタタックフィルムKC6UA(コニカミノルタオプト(株)製)を、同様に貼り合わせて円偏光板を作製した。
実施例2では、長尺斜め配向フィルムA’の幅手方向への切断時に、長手方向に付与する張力を、幅手方向の単位長さあたり30Nとし、切断中は張力を一定(30N/m)とした。それ以外は、実施例1と同様である。
実施例3では、長尺斜め配向フィルムA’の幅手方向への切断時に、長手方向に付与する張力を、幅手方向の単位長さあたり80Nとし、切断中は張力を一定(80N/m)とした。それ以外は、実施例1と同様である。
実施例4では、長尺斜め配向フィルムA’の幅手方向への切断が進行するに伴い、未切断領域に付与される張力が常に80N/mとなるように、巻取ロールの巻取張力(N)を切断が進む中で減少させた。それ以外は、実施例1と同様である。
比較例1では、長尺斜め配向フィルムA’の幅手方向への切断時に、長手方向に付与する張力を、幅手方向の単位長さあたり3Nとし、切断中は張力を一定(3N/m)とした。それ以外は、実施例1と同様である。
比較例2では、長尺斜め配向フィルムA’の幅手方向への切断時に、長手方向に付与する張力を、幅手方向の単位長さあたり150Nとし、切断中は張力を一定(150N/m)とした。それ以外は、実施例1と同様である。
実施例5では、図8の手法によって長尺斜め配向フィルムA’を切断した。すなわち、切断部材を長尺斜め配向フィルムA’の上方から下方に移動させ、長尺斜め配向フィルムA’を幅手方向全体で同時に切断した。それ以外は、実施例2と同様である。
実施例6では、図9の手法によって長尺斜め配向フィルムA’を切断した。すなわち、切断部材を幅手方向を含むフィルム断面内で回転させ、長尺斜め配向フィルムA’の幅手方向の一端側と他端側とで時間差が生じるようにして長尺斜め配向フィルムA’を切断した。それ以外は、実施例2と同様である。
実施例7では、図10Aの手法によって長尺斜め配向フィルムA’を切断した。すなわち、切断部材を幅手方向に移動させて長尺斜め配向フィルムA’を切断する際に、切断部材の刃が長尺斜め配向フィルムA’の上面と下面の両面に対して同時に入るようにして、長尺斜め配向フィルムA’を切断した。それ以外は、実施例2と同様である。
実施例8では、図11Aの手法によって長尺斜め配向フィルムA’を切断した。すなわち、切断部材を幅手方向に移動させて長尺斜め配向フィルムA’を切断する際に、切断部材の刃を長尺斜め配向フィルムA’の上面側に設置し、下面側にロールを設置し、下面側に設置したロールに密着した長尺斜め配向フィルムA’の上面から切断部材としてのロータリーカッターをフィルムに押し当てて、長尺斜め配向フィルムA’を切断した。それ以外は、実施例2と同様である。
実施例9では、セルロースフィルムからなる長尺斜め配向フィルムB’を、フィルム巻き取り部9によって巻き取りながら、図4で示したフィルム切断装置8(切断部材8a)を幅手方向に移動させて所定の長さごとに切断した。このとき、長尺斜め配向フィルムB’の幅手方向への切断が進行するに伴い、未切断領域に付与される張力が常に80N/mとなるように、巻取ロールの巻取張力(N)を切断が進む中で減少させた。それ以外は、実施例1と同様である。
比較例3では、長尺斜め配向フィルムB’の幅手方向への切断時に、長手方向に付与する張力を、幅手方向の単位長さあたり3Nとし、切断中は張力を一定(3N/m)とした。それ以外は、実施例1と同様である。
実施例10では、PCフィルムからなる長尺斜め配向フィルムC’を、フィルム巻き取り部9によって巻き取りながら、図4で示したフィルム切断装置8(切断部材8a)を幅手方向に移動させて所定の長さごとに切断した。このとき、長尺斜め配向フィルムC’の幅手方向への切断が進行するに伴い、未切断領域に付与される張力が常に80N/mとなるように、巻取ロールの巻取張力(N)を切断が進む中で減少させた。それ以外は、実施例1と同様である。
比較例4では、長尺斜め配向フィルムC’の幅手方向への切断時に、長手方向に付与する張力を、幅手方向の単位長さあたり3Nとし、切断中は張力を一定(3N/m)とした。それ以外は、実施例1と同様である。
実施例1~10、比較例1~4にて得られた円偏光板を鏡の上に設置した。このとき、円偏光板の偏光子よりも斜め配向フィルムが鏡側となるように、円偏光板を設置した。そして、円偏光板に対して上方(鏡とは反対側)から光を当てて、反射光の漏れを示す輝点を目視にて観察した。このとき、輝点がなく、反射光の漏れがない場合は、全面均一な黒表示となる。
B:10枚中の1枚の円偏光板において、斜め配向フィルムの長手方向の先頭および最後尾に相当する部分で輝点が1~3個観察された。
C:10枚中の2~5枚の円偏光板において、斜め配向フィルムの長手方向の先頭および最後尾に相当する部分で輝点が1~10個観察された。
D:10枚中の6~9枚の円偏光板において、斜め配向フィルムの長手方向の先頭および最後尾に相当する部分で輝点が1~15個観察された。
E:10枚全ての円偏光板において、斜め配向フィルムの長手方向の先頭および最後尾に相当する部分で輝点が観察された。
9a 巻取ロール
10 引取ロール
11 ニップロール(引取ロール)
12 サクションロール(引取ロール)
F フィルム(長尺斜め配向フィルム、長尺光学フィルム)
Claims (11)
- 互いに直交する長手方向および幅手方向に対して配向方向が傾斜した長尺斜め配向フィルムを含む長尺光学フィルムを切断して、個々の光学フィルムを製造する光学フィルムの製造方法であって、
前記長尺光学フィルムの前記幅手方向の長さをS1(m)とし、前記長尺光学フィルムに対して前記長手方向に付与する張力をQ(N)としたとき、
Q/S1が5~100N/mとなるように前記長尺光学フィルムに張力Qを付与した状態で、切断部材により、前記長尺光学フィルムを、前記幅手方向を含む断面に沿って切断することを特徴とする光学フィルムの製造方法。 - 前記長尺光学フィルムの切断中において、前記張力Qは一定であることを特徴とする請求項1に記載の光学フィルムの製造方法。
- 前記切断部材を前記幅手方向に移動させて前記長尺光学フィルムを切断する際に、前記切断部材によって切断された領域を除く未切断領域の前記幅手方向の長さをS2(m)としたとき、
前記幅手方向への切断の進行に伴って、Q/S2が5~100N/mの範囲に収まるように、前記張力Qを減少させることを特徴とする請求項1に記載の光学フィルムの製造方法。 - 引取ロールにより、前記幅手方向の単位長さあたり100Nを超える張力で前記長尺光学フィルムを引き取り、引き取られた前記長尺光学フィルムに対して、巻取ロールにより、前記張力Qを付与することを特徴とする請求項1から3のいずれかに記載の光学フィルムの製造方法。
- 前記引取ロールは、前記長尺光学フィルムを挟み込んで搬送するニップロールであることを特徴とする請求項4に記載の光学フィルムの製造方法。
- 前記引取ロールは、前記長尺光学フィルムを吸引しながら搬送するサクションロールであることを特徴とする請求項4に記載の光学フィルムの製造方法。
- 前記長尺光学フィルムの上面側および下面側に前記切断部材を配置し、各切断部材を前記幅手方向に移動させて前記長尺光学フィルムを切断することを特徴とする請求項1から6のいずれかに記載の光学フィルムの製造方法。
- 前記長尺光学フィルムの上面側に前記切断部材を配置し、下面側に受け部を配置し、前記受け部で前記長尺光学フィルムを受けながら、前記切断部材を前記幅手方向に移動させて前記長尺光学フィルムを切断することを特徴とする請求項1から6のいずれかに記載の光学フィルムの製造方法。
- 前記長尺光学フィルムの厚さは、10μm~60μmであることを特徴とする請求項1から8のいずれかに記載の光学フィルムの製造方法。
- 前記長尺光学フィルムの前記幅手方向の長さは、1000mm~3000mmであることを特徴とする請求項1から9のいずれかに記載の光学フィルムの製造方法。
- 前記長尺光学フィルムは、前記長尺斜め配向フィルムに対して、前記幅手方向に透過軸を有する長尺状の偏光フィルムが貼り付けられた積層フィルムであることを特徴とする請求項1から10のいずれかに記載の光学フィルムの製造方法。
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