WO2014091921A1 - 光学フィルムのロール体、その製造方法、偏光板及び表示装置 - Google Patents
光学フィルムのロール体、その製造方法、偏光板及び表示装置 Download PDFInfo
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- WO2014091921A1 WO2014091921A1 PCT/JP2013/081744 JP2013081744W WO2014091921A1 WO 2014091921 A1 WO2014091921 A1 WO 2014091921A1 JP 2013081744 W JP2013081744 W JP 2013081744W WO 2014091921 A1 WO2014091921 A1 WO 2014091921A1
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- film
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- optical film
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- roll body
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
Definitions
- the present invention relates to a roll body of an optical film, a manufacturing method thereof, a polarizing plate, and a display device. More specifically, it is a roll body of an optical film of a thin film stretched in an oblique direction, and the roll body of the optical film is less likely to cause a winding shift even when stored in a roll shape or moisture absorption during transportation, and stored.
- the present invention relates to a roll of an optical film having a uniform optical value that does not cause display unevenness even when used in a polarizing plate during or after transportation, a method for producing the same, a polarizing plate, and a display device.
- an optical film stretched in an oblique direction has been proposed (for example, see Patent Document 1). Since the optical film is stretched in an oblique direction (also simply referred to as oblique stretching) to give a desired phase difference, the optical film has a feature that the elastic modulus in the film plane has a maximum value in the oblique direction.
- polycarbonate or cycloolefin resin is preferably used.
- it has been proposed to use a cellulose ester resin for such applications for example, see Patent Document 2.
- the obliquely stretched optical film has optical anisotropy such as phase difference and mechanical anisotropy such as elastic modulus in the oblique direction.
- optical films using cellulose ester resins have a greater hygroscopic effect than other resins, and optical films with a film thickness of about 80 to 100 ⁇ m that are used as ordinary polarizing plate protective films are a major problem.
- a thin optical film with a film thickness of 50 ⁇ m or less is used for manufacturing a polarizing plate during storage in a long film roll or after transportation, it is difficult to obtain a polarizing plate with uniform characteristics and display unevenness occurs. I found it easy to do.
- the present invention has been made in view of the above problems and situations, and a solution to the problem is a thin film containing a cellulose ester and in which the direction of the maximum value of the elastic modulus in the film plane is inclined with respect to the longitudinal direction. It is a roll body of the optical film, and it is difficult for the roll body of the optical film to be deformed (winding deviation) due to moisture absorption during storage or transportation, and polarized during storage or after transportation. To provide a roll of an optical film having a uniform optical value that does not cause display unevenness even when used for a plate, a method for producing the same, a polarizing plate provided with the optical film, and a display device.
- the present inventor contains a cellulose ester in the process of examining the cause of the above-mentioned problem, and the direction of the maximum value of the elastic modulus in the film plane is inclined with respect to the longitudinal direction.
- a roll body of a thin optical film which has embossed portions with a specific height at both ends of the optical film, and the crush resistance rate (%) of the convex portions of the embossed portions is 50 for both embossed portions at both ends. % Or more of the optical film roll body, it is difficult for the roll body of the optical film to undergo winding deformation (winding deviation) due to moisture absorption during storage or transportation, and during storage or after transportation.
- the inventors have found that a roll of an optical film having a uniform optical value that does not cause display unevenness even when used for a polarizing plate is obtained, and the present invention has been achieved.
- Contains cellulose ester has a film thickness in the range of 15-50 ⁇ m, and the direction A of the maximum elastic modulus in the film surface measured at 23 ° C and 55% RH is inclined with respect to the longitudinal direction.
- the value of the ratio of the elastic modulus E B in the direction B perpendicular the elastic modulus E a direction a of the maximum value for it, roll of the optical film of the elongated is 1.4 ⁇ E a / E B Body
- the roll body of the optical film has an embossed portion having a height in the range of 1 to 20 ⁇ m in a region within 5% of the film width from both ends in the film width direction.
- the height of the convex part of the embossed part after being stored for 10 minutes at 23 ° C. and 55% RH in a state where a load of 1 kg is applied to a circular area of 5 mm in diameter on the surface of the embossed part is defined as D
- the crush resistance rate (%) defined by the following formula 1 is 50% or more for both embossed parts.
- the first aspect is characterized in that when the embossed portions at both ends in the width direction of the film are a and a ′, the difference between the crush resistance rates of the embossed portions a and a ′ is within 10%. Or the roll body of the optical film of Claim 2.
- the direction A of the maximum value of the elastic modulus in the film plane is in the range of 30 to 60 ° with respect to the longitudinal direction.
- Q represents an aromatic hydrocarbon ring, a non-aromatic hydrocarbon ring, an aromatic heterocyclic ring or a non-aromatic heterocyclic ring.
- Wa and Wb are each independently a hydrogen atom or a substituent bonded to an atom constituting Q, and Wa and Wb may be the same as or different from each other, and Wa and Wb are bonded to each other to form a ring. May be.
- R 3 represents a hydrogen atom or a substituent.
- m represents an integer of 0 to 2, and when m is 2, two R 3 s may be the same or different from each other.
- n represents an integer of 1 to 10, and when n is 2 or more, each of 2 or more of Q, L 2 , Wa, Wb, R 3 and m may be the same or different from each other .
- L 1 and L 2 are each independently an alkylene group, an alkenylene group, an alkynylene group, O, (C ⁇ O), (C ⁇ O) —O, NR L , S, (O ⁇ S ⁇ O) and ( C ⁇ O) —NR 2 represents a divalent linking group selected from the group consisting of L , a combination thereof, or a single bond.
- R L represents a hydrogen atom or a substituent.
- R 1 and R 2 each independently represents a substituent. ] 7).
- the additive according to any one of items 1 to 6, wherein the additive comprises a polycondensation ester of a dicarboxylic acid and a diol having a weight average molecular weight (Mw) in the range of 350 to 3000.
- Mw weight average molecular weight
- Item 8 The roll of optical film according to any one of items 1 to 7, wherein the winding length of the optical film is in the range of 1500 to 8000 m.
- the roll body of the optical film according to any one of items 1 to 8 is wrapped with a moisture-proof film vapor-deposited in aluminum on a resin film, and then the winding shaft portion is fastened with a string or a rubber band.
- the embossed portions are formed by embossing rollers at both ends in the width direction of the film, the embossed portions are formed by giving a temperature difference within a range of 5 to 20 ° C. to the surface temperature of the embossing rollers on both sides.
- a polarizing plate characterized in that the optical film fed out from the roll body of the optical film according to any one of items 1 to 9 is provided on at least one surface of the polarizer.
- a display device comprising the polarizing plate according to Item 12.
- the optical film roll body is less likely to undergo winding deformation (winding deviation), and has a uniform optical value that does not cause display unevenness even when used for polarizing plates during storage or after transportation.
- the roll body of the optical film which has, the manufacturing method of the roll body of the said optical film, a polarizing plate, and a display apparatus can be provided.
- An optical film that is obliquely stretched with respect to the film longitudinal direction is usually produced by an obliquely stretched tenter, but has mechanical anisotropy in the oblique direction due to the difference in the length of the left and right film runways when stretching. . Therefore, the physical property values of the left and right film ends at positions parallel to the film width are different, and even if the embossed portions are formed in the same manner as the optical film stretched in the width direction or the longitudinal direction at both ends of the film, It is estimated that the embossed portions at both ends are formed with different strengths.
- the roll body of the optical film of the present invention is formed by forming embossed portions at both ends having a higher crushing resistance ratio (%) than the conventional optical film in which the physical property values of the left and right film end portions are different by stretching diagonally. Even a thin optical film containing a highly hygroscopic cellulose ester can prevent deterioration of the roll shape of the roll body, uniform moisture absorption and moisture release from the end of the roll body, and stable It is thought that the roll body of the optical film which has a uniform optical characteristic was realizable.
- the schematic diagram which shows an example of the measuring method of the crushing tolerance rate of the convex part of an embossed part Schematic diagram of obliquely stretched tenter used in the present invention Schematic showing the track (rail pattern) of the rail of the tenter used in the manufacturing method of the present invention Schematic diagram showing an example of stretching equipment Schematic diagram showing an example of stretching equipment Schematic diagram showing an example of stretching equipment Schematic diagram showing an example of stretching equipment Schematic diagram showing another example of stretching device Schematic diagram showing another example of stretching device Schematic diagram showing an example of embossing equipment Schematic diagram of packaging form of roll of optical film
- the roll body of the optical film of the present invention is a roll body of an optical film of a thin film that contains a cellulose ester and in which the direction of the maximum elastic modulus in the film plane is inclined with respect to the longitudinal direction.
- the embossed portions having specific heights at both ends in the width direction of the film, and the crushing resistance ratio (%) expressed by the formula 1 of the convex portions of the embossed portions is 50% for both the embossed portions at both ends. It is the above.
- This feature is a technical feature common to the inventions according to claims 1 to 13.
- the crush resistance rate (%) is preferably 70% or more, and the difference in crush resistance rate (%) of the embossed portions at the left and right ends of the film. Is within 10%, since it is possible to further improve the deterioration of the winding shape by uniformly forming the embossed portions with high strength on the left and right, which is a preferable mode.
- the direction A of the maximum value of the elastic modulus in the film plane is preferably in the range of 30 to 60 ° with respect to the longitudinal direction, and the slow axis in the film plane is also in the range of 30 to 60 °. It is preferable that it exists in. Circularly polarized light with high productivity by laminating the slow axis in a direction within the above range and laminating with a polarizer having a transmission axis (or absorption axis) in the longitudinal direction with a roll-to-roll.
- a board can be manufactured.
- containing the compound having the structure represented by the general formula (A) as an additive has a feature that the compound has both functions of a phase difference increasing agent and a wavelength dispersion adjusting agent in one compound. Because it has high oblique stretchability and excellent anti-bleeding resistance due to moisture absorption when combined with a cellulose ester, the optical properties during roll storage and after transportation are uniform. Expresses excellent effects.
- the inclusion of a polycondensed ester of a dicarboxylic acid and a diol having a weight average molecular weight (Mw) in the range of 350 to 3000 as an additive is excellent in anti-bleeding properties and improves optical properties and physical properties. And can contribute to stabilization, which is preferable.
- the roll length of the roll body of the optical film of the present invention is in the range of 1500 to 8000 m, and can satisfy the crush resistance rate (%) of the embossed portion even in the vicinity of the core portion where the load is most applied. From the viewpoint of sex.
- the roll body of the optical film of the present invention is a form in which the winding shaft portion is fastened with a string or a rubber band after being wrapped with a moisture-proof film deposited on aluminum on a resin film. It is a preferred embodiment in that moisture can be released and the uniformity of optical properties and physical properties of the optical film is improved.
- the method for producing a roll body of an optical film for producing a roll body of an optical film according to the present invention comprises: pre-stretching in the film width direction within a range of 1 to 50% as a stretch ratio; It is a preferable manufacturing method from a viewpoint of forming the embossed part excellent in the said crushing resistance rate (%) to form in an embossed part in the both ends of a film width direction after that.
- embossed portions are formed by embossing rollers at both ends in the width direction of the film, it is obliquely stretched with a temperature difference within a range of 5 to 20 ° C. between the surface temperatures of the embossing rollers on both sides.
- This is a preferred embodiment for forming embossed portions having uniform left and right strengths on films having different physical properties on the left and right.
- the optical film fed from the roll of the optical film of the present invention can be suitably provided for a polarizing plate and a display device.
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
- the roll of the optical film of the present invention (hereinafter also referred to as the optical film of the present invention) contains a cellulose ester, has a film thickness in the range of 15 to 50 ⁇ m, and was measured at 23 ° C. and 55% RH.
- the roll body of the optical film has an embossed portion having a height in the range of 1 to 20 ⁇ m in a region within 5% of the film width from both ends in the film width direction. The height of the convex part of the embossed part after being stored for 10 minutes at 23 ° C.
- the crush resistance rate (%) defined by the following formula 1 is 50% or more for both embossed parts.
- the roll body of the optical film of the present invention is obtained by winding a long optical film in the longitudinal direction (direction perpendicular to the width direction of the film).
- the embossed part is a constant film consisting of minute continuous irregularities on the film in order to prevent the back and front surfaces of the wound films from coming into close contact with each other before winding the long film. It is a pattern with a width.
- a relatively concave shape is formed on the other surface (for example, the lower surface) of the film corresponding to the convex shape.
- FIG. 1 is a schematic view showing an example of a roll body of an optical film.
- a roll body 10 of an optical film has a core 12 and a long optical film 14 wound around the core 12 in the length direction of the film.
- the embossed part 16 is formed in the width direction both ends of the elongate optical film 14. As shown in FIG.
- FIG. 2 is a cross-sectional view showing an example of the vicinity of the embossed portion of the optical film.
- the height D 0 of the convex portion 16A constituting the embossed portion 16 is preferably in the range of 1 to 20 ⁇ m, more preferably in the range of 2 to 15 ⁇ m.
- the height D 0 of the convex portion 16A refers to the height from the film surface F (the film surface where the emboss is not formed) to the apex of the convex portion 16A. If the height of the convex portion 16A is less than 1 ⁇ m, the optical films are likely to adhere to each other, which is not preferable.
- the convex portion 16A is formed in a region within 5% of the film width length from both ends of the optical film.
- the width w of the convex portion 16A can be about 0.05 to 5 mm.
- the width w of the convex portion 16 ⁇ / b> A is expressed as a distance between two points where the convex portion 16 ⁇ / b> A intersects the film surface F in the cross section of the embossed portion 16.
- the distance b between the protrusions 16A and 16A is preferably in the range of 0.1 to 5 mm, and more preferably in the range of 0.5 to 2 mm.
- the interval b between the convex portions 16A and the convex portions 16A is represented by the distance between the points at which the two convex portions 16A intersect the film surface F in the cross section of the embossed portion 16.
- the width W of the embossed portion 16 is preferably in the range of 0.12 to 2.1% with respect to the width of the optical film. Specifically, the width W of the embossed portion 16 is in the range of 5 to 25 mm, preferably in the range of 10 to 20 mm, although it depends on the width of the optical film. If the width W of the embossed portion 16 is within the above range, an area that can be used as an optical film can be easily secured, and adhesion between the optical films can be prevented.
- the convex portion of the embossed portion of the optical film in the vicinity of the core is easily crushed by the own weight of the laminated optical film.
- the embossed portion is easily crushed, and when the convex portion of the embossed portion is crushed, the winding shape of the laminated optical film is deteriorated and the optical films are easily adhered to each other.
- Two problems arise at the close contact between each other. First, when the winding shape deteriorates, a difference occurs in the penetration of moisture from the film end into the inside of the roll body and the release of moisture from the inside of the roll body. Variations in the optical characteristics of these are likely to occur.
- the additive (for example, plasticizer) contained in the optical film tends to ooze out.
- the additive for example, plasticizer
- the additive is added to the optical film. A rough portion and a dense portion of the agent are generated, and the uniformity of the optical properties of the optical film is deteriorated.
- Such crushing of the convex portion of the embossed portion is particularly likely to occur when the film thickness of the optical film is reduced or the embossing is performed while the optical film is conveyed at a high speed.
- the strength of the embossed portion tends to be low at a portion having low physical properties due to the difference in physical properties between the left and right ends of the film.
- the roll body of the optical film of the present invention is such that even if force is applied to the embossed portion of the optical film, the convex portion of the embossed portion is not easily crushed, that is, the embossed portion has high strength (high elastic modulus). Even if the optical film is obliquely stretched and has an in-plane anisotropy, it suppresses the deterioration of the winding shape. Specifically, the crushing resistance rate (%) of the convex portion of the embossed portion measured by the following method needs to be 50% or more at the left and right ends of the film, and is 70% or more. Is more preferable.
- the crush resistance rate (%) of the convex part of the embossed part can be measured by the following method.
- 3 and 4 are partial cross-sectional views illustrating an example of a method for measuring the crush resistance ratio (%) of the convex portion of the embossed portion.
- a region including the embossed portion 16 of the optical film 14 is cut out to obtain a sample film 14A (see FIG. 4). Then, (in FIG. 3, the height D 0 of the projections before the addition of load) sample film 14A height D of the convex portion of the embossed portion 16 of the zero, measured at a thickness measuring instrument.
- a thickness measuring machine for example, a constant pressure thickness measuring machine (TECLOCK PG-02 Co., Ltd.) can be used.
- the sample film 14 ⁇ / b> A is placed on the stage 15.
- the weight 18 of a total of 1 kg which consists of the metal cylindrical rod 18A of diameter 5mm mounted perpendicularly
- it is stored for 10 minutes at 23 ° C. and 55% RH in a state where a load of 1 kg is applied to a circular region having a diameter of 5 mm on the surface of the embossed portion 16.
- the height D of the convex portion of the embossed portion 16 when the load is removed (excluding the weight) (the height D of the convex portion after applying the load in FIG. 3) is measured with a thickness measuring machine. To do.
- Crush resistance ratio (%) D / D 0 ⁇ 100 (%) The measurement is performed 10 times while arbitrarily changing the location of the embossed portion, and the average value of the crush resistance rate (%) is obtained.
- the adjustment of the crush resistance ratio (%) of the convex portion of the embossed portion is not particularly limited, and various methods can be adopted, but it is preferably performed under embossing conditions. Specifically, two or more of (1) the surface temperature of the embossing roller, (2) the surface temperature of the back roller, (3) the roller diameter of the embossing roller, and (4) the material of the back roller are adjusted in various combinations. be able to. Among these, it is preferable to adjust (1) the surface temperature of the embossing roller and (2) the surface temperature of the back roller, (3) more preferably adjust the diameter of the embossing roller, and (4) the back roller. It is particularly preferable to select the material. In order to increase the crush resistance rate of the convex portion of the embossed portion, for example, (1) it is preferable to increase the surface temperature of the embossed roller and (2) increase the surface temperature of the back roller.
- the roll of the optical film of the present invention is preliminarily stretched in the range of 1 to 50% as the stretch ratio in the width direction of the film in advance, and then stretched in an oblique direction with respect to the longitudinal direction of the film. It is preferable to form embossed portions at both ends in the direction in order to form embossed portions with excellent crush resistance ratio (%).
- the elastic modulus at both ends of the film is increased, the anisotropy due to subsequent oblique stretching can be relaxed, and the strength of the embossed portion can be increased.
- the surface temperature of the embossing rollers on both sides is set with a temperature difference within a range of 5 to 20 ° C. by oblique stretching.
- a left and right embossed portion can be formed on a film having mechanical anisotropy on the left and right, which is a preferred embodiment for preventing deterioration of the winding shape.
- the temperature difference can be appropriately determined depending on the difference in physical properties between the right and left films, but is more preferably a temperature difference within a range of 7 to 15 ° C.
- the crush resistance of the embossed portions a and a ′ is within 10% because the effect of suppressing deterioration of the winding shape of the roll body during storage or transportation is expressed.
- the difference in the crush resistance rate is more preferably within 5%, and further preferably within 3%.
- the direction A of the maximum value of the elastic modulus in the film plane and the slow axis are inclined with respect to the longitudinal direction, and in particular, the slow axis in the film plane is with respect to the longitudinal direction.
- it is suitably provided in a circularly polarizing plate that converts linearly polarized light having a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light).
- the optical film of the present invention is preferably a ⁇ / 4 plate.
- the ⁇ / 4 plate is designed so that the in-plane retardation value Ro is about 1/4 with respect to a predetermined light wavelength (usually in the visible light region).
- the ⁇ / 4 plate has a Ro (590) measured at a wavelength of 590 nm in the range of 120 to 160 nm.
- “Retardation of approximately 1/4 in the wavelength range of visible light” means a retardation value expressed by the following formula (i) measured at a wavelength of 450 nm, with a larger retardation at a wavelength of 400 to 700 nm. It is preferable that Ro (590) which is a retardation value measured at a certain Ro (450) and a wavelength of 590 nm satisfies 1 ⁇ Ro (590) / Ro (450) ⁇ 1.6. Furthermore, it is preferable that 1 ⁇ Ro (590) / Ro (450) ⁇ 1.3.
- Ro (450) is in the range of 100 to 125 nm
- the retardation value Ro (550) measured at a wavelength of 550 nm is in the range of 125 to 142 nm. It is more preferable that Ro (590) is a retardation film in the range of 130 to 152 nm.
- Formula (ii) is a formula for obtaining the retardation value Rt in the film thickness direction.
- the retardation value Rt measured at a wavelength of 550 nm is preferably in the range of 60 to 100 nm, and more preferably in the range of 70 to 90 nm.
- nx, ny, and nz are refractive indexes nx (maximum in-plane refractive index and refractive index in slow axis direction at 23 ° C. and 55% RH, 450 nm, 550 nm, and 590 nm, respectively. ), Ny (refractive index in the direction perpendicular to the slow axis in the film plane), nz (refractive index in the film thickness direction), and d is the thickness (nm) of the film.
- Ro and Rt can be measured using an automatic birefringence meter.
- Ro is calculated by measuring the birefringence at each wavelength in an environment of 23 ° C. and 55% RH.
- a circularly polarizing plate is obtained by laminating so that the angle between the slow axis of the ⁇ / 4 plate and the transmission axis (or absorption axis) of the polarizer is substantially 45 °.
- “Substantially 45 °” means a range of 40 to 50 °.
- the angle between the slow axis in the plane of the ⁇ / 4 plate and the transmission axis of the polarizer is preferably in the range of 41 to 49 °, more preferably in the range of 42 to 48 °, and 43 to 47.
- a range of ° is more preferable, and a range of 44 to 46 ° is most preferable. Therefore, in order to produce a circularly polarizing plate by roll-to-roll, the direction of the slow axis of the optical film of the present invention is preferably the above “substantially 45 °” direction.
- the direction A of the maximum value of the elastic modulus in the film surface measured at 23 ° C. and 55% RH is inclined with respect to the longitudinal direction. cage, the value of the ratio of the elastic modulus E B in the direction B perpendicular to it and the elastic modulus E a direction a of the maximum value, has a characteristic which is 1.4 ⁇ E a / E B.
- the value of the elastic modulus ratio (E A / E B ) is preferably 1.4 or more, and being in the range of 1.4 to 3.0 is the load on the film for oblique stretching. From the viewpoint of achieving both the object of the present invention for increasing the elastic modulus and forming an embossed portion having high strength, it is more preferably in the range of 1.6 to 2.5.
- the elastic modulus of the optical film was measured by conditioning the sample for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH, and according to the method described in JIS K7127, manufactured by a tensile tester, Orientec Co., Ltd.
- the elastic modulus is determined using Tensilon RTA-100.
- the shape of the test piece is No. 1 test piece, the test speed is 10 mm / min, measured in the direction of 0 ° to 15 ° with respect to the arbitrary direction, and the maximum value of the obtained elastic modulus is the maximum.
- the modulus of elasticity E a and direction as the direction a of the maximum value further obtains the elasticity modulus E B in the direction B perpendicular to the direction a, to calculate the value of the ratio (E a / E B).
- the direction A of the maximum value of the elastic modulus is inclined with respect to the longitudinal direction
- the inclination angle is preferably in the range of 30 to 60 ° with respect to the longitudinal direction of the film, and in the same manner as the above retardation, it is particularly preferably a “substantially 45 °” direction. “Substantially 45 °” means a range of 40 to 50 °.
- the angle is preferably in the range of 41 to 49 °, more preferably in the range of 42 to 48 °, still more preferably in the range of 43 to 47 °, and in the range of 44 to 46 °. Is most preferred.
- the maximum elastic modulus of the optical film of the present invention is preferably 2.0 GPa or more, preferably in the range of 3.0 to 8.0 GPa, and in the range of 3.5 to 7.0 GPa has high strength. It is more preferable for forming an embossed portion and achieving stabilization of the winding shape.
- the film thickness of the optical film of the present invention is in the range of 15 to 50 ⁇ m and more preferably in the range of 20 to 40 ⁇ m because demand for thinner polarizing plates and display devices is increasing. Within this range, a roll of an optical film that is thin and lightweight and has a stable winding shape can be obtained.
- the winding length of the roll of the optical film of the present invention is preferably in the range of 1500 to 8000 m, more preferably in the range of 2000 to 6000 m, considering productivity. According to this invention, it has an embossed part with high intensity
- the diameter of the core in the roll body of the present invention can be about 100 to 250 mm.
- the width of the optical film in the roll of the optical film of the present invention is about 1.2 to 4 m, preferably about 1.2 to 2.5 m.
- the optical film of the present invention preferably contains a cellulose ester and further contains an additive for improving optical properties and physical properties.
- the optical film of the present invention contains a cellulose ester as a main component.
- a main component means that the content rate of the cellulose ester in the said optical film is 55 mass% or more, Preferably it is 70 mass% or more.
- the cellulose ester according to the present invention preferably has an acyl group having 2 to 4 carbon atoms.
- the acyl group having 2 to 4 carbon atoms include an acetyl group, a propionyl group, and a butanoyl group.
- the ⁇ -1,4-bonded glucose unit constituting cellulose has free hydroxy groups at the 2nd, 3rd and 6th positions.
- the cellulose ester is a polymer obtained by acylating part or all of these hydroxy groups with an acyl group.
- the total acyl group substitution degree means the ratio in which all the hydroxy groups of cellulose located at the 2nd, 3rd and 6th positions are acylated per one glucose unit (100% acylation has a degree of substitution of 3). .
- acyl groups include acetyl, propionyl, butanoyl, heptanoyl, hexanoyl, octanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, hexadecanoyl, octadecanoyl, Examples thereof include an isobutanoyl group, a tert-butanoyl group, a cyclohexanecarbonyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, and a cinnamoyl group.
- an acetyl group, a propionyl group, a butanoyl group, a dodecanoyl group, an octadecanoyl group, a tert-butanoyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, a cinnamoyl group, and the like are more preferable, and an acetyl group is particularly preferable.
- a propionyl group and a butanoyl group (when the acyl group has 2 to 4 carbon atoms);
- Specific cellulose ester is at least selected from cellulose (di, tri) acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate benzoate and cellulose phthalate One type is preferred.
- cellulose esters are cellulose (di, tri) acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate and cellulose acetate butyrate.
- the cellulose triacetate preferably has an average degree of acetylation (bound acetic acid amount) of 54.0 to 62.5%, and more preferably cellulose triacetate having an average degree of acetylation of 58.0 to 62.5%. is there.
- Cellulose diacetate preferably has an average degree of acetylation (amount of bound acetic acid) of 51.0 to 56.0%.
- Commercially available products include L20, L30, L40, and L50 manufactured by Daicel Corporation, and Ca398-3, Ca398-6, Ca398-10, Ca398-30, and Ca394-60S manufactured by Eastman Chemical Japan Co., Ltd. .
- Cellulose acetate propionate or cellulose acetate butyrate has an acyl group having 2 to 4 carbon atoms as a substituent, the substitution degree of acetyl group is X, and the substitution degree of propionyl group or butyryl group is Y Those satisfying the following formulas (I) and (II) are preferred.
- Formula (I) 2.0 ⁇ X + Y ⁇ 2.95
- Formula (II) 0 ⁇ X ⁇ 2.5
- the method for measuring the degree of substitution of the acyl group can be measured according to ASTM-D817-96.
- the weight average molecular weight Mw of the cellulose ester is preferably in the range of 80000 to 300000, and more preferably in the range of 120,000 to 250,000, from the viewpoint of controlling the elastic modulus. Within the above range, it is easy to control the elastic modulus by stretching at the time of film formation, so that the winding shape of the film is stabilized and the anti-bleeding resistance of the additive is improved.
- the number average molecular weight (Mn) of the cellulose ester is preferably in the range of 30000 to 150,000 because the obtained optical film has high mechanical strength. Furthermore, cellulose esters having a number average molecular weight of 40,000 to 100,000 are preferably used.
- the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cellulose ester is preferably in the range of 1.4 to 3.0.
- the weight average molecular weight Mw and number average molecular weight Mn of the cellulose ester were measured using gel permeation chromatography (GPC).
- the measurement conditions are as follows.
- the raw material cellulose of the cellulose ester used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferable.
- a cotton linter is preferably used from the viewpoint of peelability during film formation.
- the cellulose ester made from these can be mixed suitably or can be used independently.
- the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.
- the cellulose ester according to the present invention can be produced by a known method.
- cellulose is esterified by mixing cellulose as a raw material, a predetermined organic acid (such as acetic acid or propionic acid), an acid anhydride (such as acetic anhydride or propionic anhydride), and a catalyst (such as sulfuric acid).
- a predetermined organic acid such as acetic acid or propionic acid
- an acid anhydride such as acetic anhydride or propionic anhydride
- a catalyst such as sulfuric acid
- the cellulose triester is hydrolyzed to synthesize a cellulose ester having a desired degree of acyl substitution.
- the cellulose ester is completed through steps such as filtration, precipitation, washing with water, dehydration, and drying.
- the cellulose ester according to the present invention is charged with 1 g in 20 ml of pure water (electric conductivity 0.1 ⁇ S / cm or less, pH 6.8), and has a pH of 6 to 6 when stirred in a nitrogen atmosphere at 25 ° C. for 1 hr.
- the electric conductivity is preferably in the range of 1 to 100 ⁇ S / cm.
- the cellulose ester according to the present invention can be specifically synthesized with reference to the method described in JP-A-10-45804.
- Examples of the additive contained in the optical film of the present invention include a plasticizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a retardation adjusting agent, an antistatic agent, and a release agent, preferably a plasticizer. It is an agent.
- a compound having a structure represented by the following general formula (A) is preferably used from the viewpoint of retardation adjustment. Since this compound has the characteristics of having both functions of a phase difference increasing agent and a wavelength dispersion adjusting agent in one compound, it has high suitability for oblique stretching, and stain resistance due to moisture absorption when combined with a cellulose ester. Since it is also excellent in stocking properties, it has an excellent effect on uniformity of optical properties during storage and after transportation of the roll body.
- Q in the general formula (A) represents an aromatic hydrocarbon ring, a non-aromatic hydrocarbon ring, an aromatic heterocyclic ring or a non-aromatic heterocyclic ring.
- the aromatic hydrocarbon ring may be a single ring or a condensed ring, but is preferably a single ring.
- Preferred examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. And is preferably a benzene ring.
- the non-aromatic hydrocarbon ring may be a single ring or a condensed ring, but is preferably a single ring.
- Preferred examples of the non-aromatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a norbornene ring, etc., preferably a cyclohexane ring or a cyclopentane ring. is there.
- the aromatic heterocyclic ring may be a monocyclic ring or a condensed ring, and is preferably a monocyclic ring.
- Preferred examples of the aromatic heterocycle include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, triazole ring, benzimidazole ring, Pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, perimidine ring, quinazoline ring, azulene ring, dibenzofuran ring, dibenzothiophene ring, dibenzocarbazole ring, benzodifuran ring, benzodithiophene ring, phenanthroline ring
- the non-aromatic heterocyclic ring may be a monocyclic ring or a condensed ring, and is preferably a monocyclic ring.
- Preferred examples of the non-aromatic heterocycle include tetrahydrofuran ring, tetrahydropyran ring, dioxolane ring, dioxane ring, pyrrolidine ring, pyridone ring, pyridazinone ring, imide ring, piperidine ring, dihydropyrrole ring, dihydropyridine ring, tetrahydropyridine ring, A piperazine ring, a morpholine ring, a piperidine ring and the like are included, and a pyridone ring, an imide ring or a pyrrolidine ring is preferable.
- Wa and Wb in the general formula (A) are each independently a hydrogen atom or a substituent bonded to an atom constituting the ring of Q, and Wa and Wb may be the same as or different from each other. May combine with each other to form a ring.
- Wa and Wb are bonded to each other to form a ring, or at least one of Wa and Wb has a ring structure.
- Halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
- alkyl group methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.
- Cycloalkyl group cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.
- alkenyl group vinyl group, allyl group, etc.
- cycloalkenyl group (2-cyclopenten-1-yl, 2-cyclohexene-1- Yl group
- alkynyl group ethynyl group, propargyl group, etc.
- aryl group phenyl group, p-tolyl group, naphthyl group, etc.
- heteroaryl group (2-pyrrole
- R 3 in the general formula (A) represents a hydrogen atom or a substituent. There is no restriction
- Halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
- alkyl group methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.
- Alkenyl group vinyl group, allyl group, etc.
- alkynyl group ethynyl group, propargyl group, etc.
- cyano group hydroxy group, nitro group, carboxy group, alkoxy group (methoxy group, ethoxy group, isopropoxy group, tert- Butoxy group, n-octyloxy group, 2-methoxyethoxy group, etc.)
- acyloxy group formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, etc.
- alkoxycarbonyl group
- R 3 represents a hydrogen atom, a halogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), an alkenyl group (preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms), a hetero group.
- Aryl group preferably having 4 to 20 carbon atoms), hydroxy group, carboxy group, alkoxy group (preferably having 1 to 20 carbon atoms), aryloxy group (preferably having 6 to 20 carbon atoms), acyl group, acyloxy group, cyano A group or an amino group is preferable, and a hydrogen atom, a halogen atom, an alkyl group, a cyano group, or an alkoxy group is more preferable. These substituents may further have the same substituent.
- M in the general formula (A) represents an integer of 0 to 2, and is preferably 0.
- m 2
- two R 3 s may be the same or different from each other.
- n represents an integer of 1 to 10, preferably 1.
- each of 2 or more of Q, L 2 , Wa, Wb, R 3 and m may be the same as or different from each other.
- R L represents a hydrogen atom or a substituent.
- substituent represented by R L include an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.), cycloalkyl group (Cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), aryl group (phenyl group, p-tolyl group, naphthyl group, etc.), heteroaryl group (2-furyl group, 2-thienyl group, 2-pyrimidinyl) Group, 2-benzothiazolyl group, 2-pyridyl group and the like), cyano group and the like.
- R 1 and R 2 in formula (A) each independently represent a substituent.
- R 1 and R 2 may be the same or different from each other.
- R 1 and R 2 examples include the following.
- Halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
- alkyl group methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, etc.
- Cycloalkyl group cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.
- alkenyl group vinyl group, allyl group, etc.
- cycloalkenyl group (2-cyclopenten-1-yl, 2-cyclohexene-1- Yl group
- alkynyl group ethynyl group, propargyl group, etc.
- aryl group phenyl group, p-tolyl group, naphthyl group, etc.
- heteroaryl group 2-furyl group
- Amino group (amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, etc.), acylamino group (formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, Benzoylamino Etc.), alkyl and arylsulfonylamino groups (methylsulfonylamino group, butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, etc.), mercapto group, Alkylthio group (methylthio group, ethylthio group, n-hexadecylthio group, etc.), arylthio group (phenylthio
- R 1 and R 2 are an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), an aryl group (preferably a carbon number of 6 ⁇ 20 aryl groups) and heteroaryl groups (preferably aryl groups having 4 to 20 carbon atoms) are preferred, and aryl groups or cycloalkyl groups are more preferred.
- the aryl group is preferably a substituted or unsubstituted phenyl group, more preferably a phenyl group having a substituent, and still more preferably a phenyl group having a substituent at the 4-position.
- the cycloalkyl group is preferably a substituted or unsubstituted cyclohexyl group, more preferably a cyclohexyl group having a substituent, and further preferably a cyclohexyl group having a substituent at the 4-position.
- R 1 and R 2 may further have the same substituent.
- the compound having a structure represented by the general formula (A) is preferably a compound having a structure represented by the following general formula (B).
- Wa, Wb, R 3 , m, L 1 , L 2 , R L , R 1 and R 2 in the general formula (B) are Wa, Wb, R 3 , m, L 1 , L in the general formula (A). 2 , R L , R 1 and R 2 are defined similarly.
- the compound having a structure represented by the general formula (B) is preferably a compound having a structure represented by the following general formula (C).
- Wa, Wb, R 3 , m, L 1 , L 2 , R L , R 1 and R 2 in the general formula (C) are Wa, Wb, R 3 , m, L 1 , L in the general formula (A). 2 , R L , R 1 and R 2 are defined similarly.
- the formed ring is preferably a nitrogen-containing heterocycle.
- the compound having such a structure represented by the general formula (C) include the following compounds (C1) to (C6).
- R i to R iii each independently represents a hydrogen atom or a substituent.
- Q in the general formula (A) is a benzene ring
- Wa is a group containing an oxygen atom bonded to the benzene ring
- Wb is a group containing a nitrogen atom bonded to the benzene ring.
- the ring corresponding to Q in the general formula (A) is a naphthalene ring.
- trans isomer and cis isomer when there are geometrical isomers (trans isomer and cis isomer), any isomer may be used, but the trans isomer can give higher retardation expression than the cis isomer. ,preferable.
- a compound having a structure represented by general formula (A), general formula (B) or general formula (C) can be synthesized by a known method.
- the exemplified compound A5 can be synthesized as follows with reference to JP-A-2008-107767.
- the content of the compound having a structure represented by the general formula (A) used in the present invention is appropriately set to such an extent that the phase difference required for the optical film can be imparted.
- the content of the compound used in the present invention is preferably in the range of 1 to 10% by mass and more preferably in the range of 2 to 8% by mass with respect to the cellulose ester.
- the content of the compound is 1% by mass or more, sufficient retardation can be imparted to the optical film, and if it is 10% by mass or less, the optical film has excellent bleed resistance.
- the compound used in the present invention can be combined with another phase difference adjusting agent.
- a nitrogen-containing heterocyclic compound having a pyrrole ring, a pyrazole ring, a triazole ring, or an imidazole ring is also preferable to use as a compound that exhibits the same effect as the compound having the structure represented by the general formula (A).
- the nitrogen-containing heterocyclic compounds having the structure represented by the general formula (1) the nitrogen-containing heterocyclic compounds having the specific ring structure are preferable.
- the nitrogen-containing heterocyclic compound is characterized by controlling the hydrogen bonding property of the cellulose ester by CH / ⁇ interaction with the cellulose ester, and having both functions of a phase difference increasing agent and a wavelength dispersion adjusting agent with one compound. It has excellent anti-bleeding properties due to moisture absorption when combined with a cellulose ester, and has a high effect of suppressing disturbance of the winding shape when producing a long roll of 5000 m or more. In particular, when the roll body is tightly wound, sticking failure or the like is likely to occur. Therefore, when winding the roll body relatively loosely (also referred to as loose winding), the effect of suppressing disturbance of the winding shape is high.
- 1,3,5-triazine phase difference increasing agents and the like have a weak CH / ⁇ interaction, so they are slightly inferior in anti-bleeding property, and additives that have exuded on the surface of the roll body cause slippage of the film. It may induce a disturbance in the winding shape of the roll body.
- CH / ⁇ interaction refers to the compatibility of hydrogen bond donating sites such as cellulose esters (for example, hydrogen atoms of hydroxy groups) and hydrogen bond accepting sites (for example, carbonyl oxygen atoms of ester groups) with additives. It is a bond interaction between the hydrogen bonding site present in the main chain or side chain of the resin and the ⁇ electrons of the additive aromatic compound. Due to this CH / ⁇ interaction, the above-mentioned bleeding resistance is excellent.
- NICS nucleus-independent chemical shift
- This NICS value is an index used for quantification of aromaticity by magnetic properties. If the ring is aromatic, the ring current effect strongly shields the center of the ring, and conversely if it is antiaromatic. Anti-shielding (J. Am. Chem. Soc. 1996, 118, 6317). Depending on the magnitude of the NICS value, it is possible to determine the strength of the ring current, that is, the degree of contribution of ⁇ electrons to the aromaticity of the ring. Specifically, it represents the chemical shift (calculated value) of a virtual lithium ion arranged directly in the center of the ring, and the larger the value, the stronger the ⁇ property.
- a pyrrole ring (-14.87), a thiophene ring (-14.09) furan rather than an aromatic hydrocarbon such as a benzene ring (-7.98) or a naphthalene ring (-8.11).
- 5-membered aromatic heterocycles such as ring (-12.42), pyrazole ring (-13.82), or imidazole ring (-13.28), triazole ring (-13.18), oxadiazole ring ( 6-12 membered aromatic hydrocarbon rings such as -12.44) or thiazole ring (-12.82) have larger NICS values, and such aromatic 5-membered rings or aromatic 6-membered rings It is predicted that the CH / ⁇ interaction can be strengthened by using the compound having the above (the NICS value is shown in parentheses).
- a 1 , A 2 and B are each independently an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2- An ethenyl group), a cycloalkyl group (cyclohexyl group, cyclopentyl group, 4-n-dodecylcyclohexyl group, etc.), an aromatic hydrocarbon ring or an aromatic heterocycle.
- an aromatic hydrocarbon ring or an aromatic heterocycle is preferable, and a 5-membered or 6-membered aromatic hydrocarbon ring or an aromatic heterocycle is particularly preferable.
- the structure of the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring is not limited, but for example, benzene ring, pyrrole ring, pyrazole ring, imidazole ring, 1,2,3-triazole ring, 1,2 , 4-triazole ring, tetrazole ring, furan ring, oxazole ring, isoxazole ring, oxadiazole ring, isoxadiazole ring, thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring, isothiadiazole ring, etc. .
- the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring represented by A 1 , A 2 and B is an alkyl group (methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group). N-octyl group, 2-ethylhexyl group, etc.) and aromatic hydrocarbon ring groups (phenyl group, p-tolyl group, naphthyl group, etc.).
- a 1 , A 2 and B represent a benzene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4-triazole ring. It is preferable because a retardation film having excellent optical property variation effects and excellent durability can be obtained.
- T 1 and T 2 each independently represents a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring or a 1,2,4-triazole ring.
- a pyrazole ring, a triazole ring or an imidazole ring is preferable because a resin composition excellent in retardation fluctuation suppression effect against humidity fluctuation and excellent in durability can be obtained. It is particularly preferred.
- the pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring and imidazole ring represented by T 1 and T2 may be tautomers.
- the nitrogen-containing heterocyclic compound is particularly preferably a compound having a structure represented by the following general formula (2).
- A represents a pyrazole ring
- Ar 1 and Ar 2 each represent an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may have a substituent.
- R 1 represents a hydrogen atom, an alkyl group, or an acyl group. Represents a sulfonyl group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, q represents an integer of 1 to 2, and n and m represent an integer of 1 to 3.
- the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Ar 1 and Ar 2 may be the 5-membered or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring mentioned in the general formula (1), respectively. preferable. Examples of the substituent for Ar 1 and Ar 2 include the same substituents as those shown for the compound having the structure represented by the general formula (1).
- R 1 examples 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).
- 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.
- Q represents an integer of 1 to 2
- n and m represent an integer of 1 to 3.
- the molecular weight of the compound having the structure represented by the general formula (1) or (2) is not particularly limited, but the smaller the value, the better the compatibility with the resin, and the larger, the greater the effect of suppressing fluctuations in the optical value with respect to changes in environmental humidity. Is high, it is preferably 150 to 2000, more preferably 200 to 1500, and more preferably 300 to 1000.
- the compound having the structure represented by the general formula (1) or (2) can be appropriately adjusted and contained in the optical film, but the addition amount is 0.1 to 10 in the optical film. It is preferable to contain 1% by mass, particularly 1 to 5% by mass, and particularly preferably 2 to 5% by mass.
- the addition amount varies depending on the type of cellulose ester and the type of the compound, but the optimum value of the addition amount can be determined by the desired retardation value of the optical film of the present invention.
- plasticizers include polyesters (also referred to as polycondensation esters in the present application), polyhydric alcohol esters, polyhydric carboxylic acid esters (including phthalic acid esters), glycolate compounds, fatty acid esters and phosphoric acid esters, etc. Is included. These may be used alone or in combination of two or more.
- a preferable plasticizer for the optical film of the present invention is a polycondensed ester containing a repeating unit obtained by reacting a dicarboxylic acid and a diol.
- the dicarboxylic acid constituting the polycondensed ester is an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid or an alicyclic dicarboxylic acid, preferably an aromatic dicarboxylic acid.
- the dicarboxylic acid may be one kind or a mixture of two or more kinds.
- the diol constituting the polycondensed ester is an aromatic diol, an aliphatic diol or an alicyclic diol, preferably an aliphatic diol, more preferably a diol having 1 to 4 carbon atoms.
- the diol may be one type or a mixture of two or more types.
- the polycondensed ester preferably contains a repeating unit obtained by reacting at least a dicarboxylic acid containing an aromatic dicarboxylic acid and a diol having 1 to 4 carbon atoms.
- the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid are preferably used. More preferably, it contains a repeating unit obtained by reacting a dicarboxylic acid containing an acid with a diol having 1 to 4 carbon atoms.
- the both ends of the molecule of the polycondensed ester may or may not be sealed, but are preferably sealed from the viewpoint of reducing the moisture permeability of the film.
- the polycondensed ester is preferably a compound having a structure represented by the following general formula (I) or (II).
- n is an integer of 1 or more.
- Formula (I) B- (GA) n -GB Formula (II) C- (AG) n -AC A in the general formulas (I) and (II) is a divalent group derived from an alkylene dicarboxylic acid having 3 to 20 carbon atoms (preferably 4 to 12 carbon atoms), and has 4 to 20 carbon atoms (preferably 4 to 4 carbon atoms). 12) a divalent group derived from an alkenylene dicarboxylic acid or a divalent group derived from an aryl dicarboxylic acid having 8 to 20 carbon atoms (preferably 8 to 12).
- Examples of the divalent group derived from an alkylenedicarboxylic acid having 3 to 20 carbon atoms in A include 1,2-ethanedicarboxylic acid (succinic acid), 1,3-propanedicarboxylic acid (glutaric acid), 1 Divalent groups derived from 1,4-butanedicarboxylic acid (adipic acid), 1,5-pentanedicarboxylic acid (pimelic acid), 1,8-octanedicarboxylic acid (sebacic acid) and the like are included.
- Examples of the divalent group derived from alkenylene dicarboxylic acid having 4 to 20 carbon atoms in A include a divalent group derived from maleic acid, fumaric acid and the like.
- divalent groups derived from aryl dicarboxylic acids having 8 to 20 carbon atoms in A include 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid, 1,4-benzene.
- divalent groups derived from naphthalenedicarboxylic acid such as dicarboxylic acid and 1,5-naphthalenedicarboxylic acid are included.
- A may be one type or two or more types may be combined. Among these, A is preferably a combination of an alkylene dicarboxylic acid having 4 to 12 carbon atoms and an aryl dicarboxylic acid having 8 to 12 carbon atoms.
- G in the general formulas (I) and (II) is a divalent group derived from an alkylene glycol having 2 to 20 (preferably 2 to 12) carbon atoms, and has 6 to 20 (preferably 6 to 12) carbon atoms. ) Or a divalent group derived from an oxyalkylene glycol having 4 to 20 (preferably 4 to 12) carbon atoms.
- Examples of the divalent group derived from an alkylene glycol having 2 to 20 carbon atoms in G include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1, 3-butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol ( Neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylol) Heptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanedio ,
- divalent groups derived from aryl glycols having 6 to 20 carbon atoms in G include 1,2-dihydroxybenzene (catechol), 1,3-dihydroxybenzene (resorcinol), 1,4-dihydroxybenzene Divalent groups derived from (hydroquinone) and the like are included.
- divalent group derived from oxyalkylene glycol having 4 to 12 carbon atoms in G are derived from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and the like. Divalent groups are included.
- G may be one type or two or more types may be combined. Among these, G is preferably an alkylene glycol having 2 to 12 carbon atoms.
- B in the general formula (I) is a monovalent group derived from an aromatic ring-containing monocarboxylic acid or an aliphatic monocarboxylic acid.
- the aromatic ring-containing monocarboxylic acid in the monovalent group derived from the aromatic ring-containing monocarboxylic acid is a carboxylic acid containing an aromatic ring in the molecule, and not only those in which the aromatic ring is directly bonded to a carboxy group, Also included are those in which an aromatic ring is bonded to a carboxy group via an alkylene group or the like.
- monovalent groups derived from aromatic ring-containing monocarboxylic acids include benzoic acid, para-tert-butyl benzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethyl benzoic acid, ethyl benzoic acid, and normal propyl benzoic acid. , Monovalent groups derived from aminobenzoic acid, acetoxybenzoic acid, phenylacetic acid, 3-phenylpropionic acid and the like.
- Examples of monovalent groups derived from aliphatic monocarboxylic acids include monovalent groups derived from acetic acid, propionic acid, butanoic acid, caprylic acid, caproic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid and the like. Is included. Among these, a monovalent group derived from an alkyl monocarboxylic acid having 1 to 3 carbon atoms in the alkyl portion is preferable, and an acetyl group (a monovalent group derived from acetic acid) is more preferable.
- C in the general formula (II) is a monovalent group derived from an aromatic ring-containing monoalcohol or an aliphatic monoalcohol.
- An aromatic ring-containing monoalcohol is an alcohol containing an aromatic ring in the molecule, and includes not only those in which an aromatic ring is directly bonded to an OH group, but also those in which an aromatic ring is bonded to an OH group via an alkylene group or the like.
- Examples of the monovalent group derived from an aromatic ring-containing monoalcohol include a monovalent group derived from benzyl alcohol, 3-phenylpropanol and the like.
- Examples of monovalent groups derived from aliphatic monoalcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, isohexanol, cyclohexyl alcohol, octanol, isooctanol, Monovalent groups derived from 2-ethylhexyl alcohol, nonyl alcohol, isononyl alcohol, tert-nonyl alcohol, decanol, dodecanol, dodecahexanol, dodecaoctanol, allyl alcohol, oleyl alcohol and the like are included. Of these, monovalent groups derived from alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol and isopropanol are preferred.
- the weight average molecular weight of the polycondensed ester is preferably in the range of 350 to 3000, and more preferably in the range of 400 to 1500. If the weight average molecular weight is within the above range, the anti-bleeding property of the polycondensed ester according to the present invention from the optical film can be satisfied, and the intended effect can be obtained.
- the weight average molecular weight can be measured by the gel permeation chromatography (GPC).
- polycondensation ester Specific examples of the polycondensation ester are shown below. First, a specific example of a polycondensed ester in which both ends are sealed with an “aromatic group” is shown.
- P-1 acetyl esterified product of both ends of a condensate (weight average molecular weight 950) comprising adipic acid / phthalic acid / ethanediol (1/1/2 molar ratio)
- P-2 succinic acid / phthalic acid / ethane Acetyl esterified compound at both ends of a condensate (weight average molecular weight 2500) consisting of diol / (1/1/2 molar ratio)
- P-3 glutaric acid / isophthalic acid / 1,3-propanediol (1/1 / Acetyl esterified product at both ends of a condensate (weight average molecular weight 1300) consisting of 2 mole ratio)
- P-4 Succinic acid / glutaric acid / adipic acid / terephthalic acid / isophthalic acid / ethanediol / 1,2-propanediol Propyl este
- Preferred examples of the aliphatic polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, trimethylolpropane , Pentaerythritol, trimethylolethane, xylitol and the like.
- triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol, trimethylolpropane, xylitol and the like are preferable.
- the monocarboxylic acid is not particularly limited, and may be an aliphatic monocarboxylic acid, an alicyclic monocarboxylic acid, an aromatic monocarboxylic acid, or the like. In order to increase the moisture permeability of the film and make it less likely to volatilize, alicyclic monocarboxylic acids or aromatic monocarboxylic acids are preferred. One kind of monocarboxylic acid may be used, or a mixture of two or more kinds may be used. Further, all of the OH groups contained in the aliphatic polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
- the aliphatic monocarboxylic acid is preferably a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms.
- the number of carbon atoms of the aliphatic monocarboxylic acid is more preferably 1-20, and still more preferably 1-10.
- aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanoic acid, undecylic acid, lauric acid, tridecylic acid , Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid; undecylenic acid, Examples include unsaturated fatty acids such as oleic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid. Of these, acetic acid or a mixture of ace
- Examples of the alicyclic monocarboxylic acid include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid and the like.
- aromatic monocarboxylic acids examples include benzoic acid; one having 1 to 3 alkyl or alkoxy groups (for example, methoxy group or ethoxy group) introduced into the benzene ring of benzoic acid (for example, toluic acid); benzene ring Aromatic monocarboxylic acids having two or more (for example, biphenyl carboxylic acid, naphthalene carboxylic acid, tetralin carboxylic acid, etc.) are included, and benzoic acid is preferred.
- polyhydric alcohol ester compound examples include compounds described in paragraphs [0058] to [0061] of JP-A-2006-113239.
- the polyvalent carboxylic acid ester compound is an ester compound of a divalent or higher, preferably 2 to 20 valent polycarboxylic acid and an alcohol compound.
- the polyvalent carboxylic acid is preferably a divalent to 20-valent aliphatic polyvalent carboxylic acid, a 3- to 20-valent aromatic polyvalent carboxylic acid, or a 3- to 20-valent alicyclic polyvalent carboxylic acid. .
- polyvalent carboxylic acids include trivalent or higher aromatic polyvalent carboxylic acids or derivatives such as trimellitic acid, trimesic acid, pyromellitic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, oxalic acid Contains aliphatic polycarboxylic acids such as fumaric acid, maleic acid, and tetrahydrophthalic acid, and oxypolycarboxylic acids such as tartaric acid, tartronic acid, malic acid, and citric acid, and suppresses volatilization from the film. For this, oxypolycarboxylic acids are preferred.
- the alcohol compound examples include an aliphatic saturated alcohol compound having a straight chain or a side chain, an aliphatic unsaturated alcohol compound having a straight chain or a side chain, an alicyclic alcohol compound, or an aromatic alcohol compound.
- the carbon number of the aliphatic saturated alcohol compound or the aliphatic unsaturated alcohol compound is preferably 1 to 32, more preferably 1 to 20, and further preferably 1 to 10.
- Examples of the alicyclic alcohol compound include cyclopentanol, cyclohexanol and the like.
- the aromatic alcohol compound include benzyl alcohol and cinnamyl alcohol.
- the molecular weight of the polyvalent carboxylic acid ester compound is not particularly limited, but is preferably in the range of 300 to 1000, more preferably in the range of 350 to 750.
- the molecular weight of the polyvalent carboxylic acid ester plasticizer is preferably larger from the viewpoint of suppressing bleeding out; it is preferably smaller from the viewpoint of moisture permeability and compatibility with cellulose acetate.
- polyvalent carboxylic acid ester compounds include triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), benzoyl tributyl citrate, acetyl triphenyl citrate, acetyl tribenzyl citrate Rate, dibutyl tartrate, diacetyl dibutyl tartrate, tributyl trimellitic acid, tetrabutyl pyromellitic acid and the like.
- ATEC acetyl triethyl citrate
- ATBC acetyl tributyl citrate
- benzoyl tributyl citrate acetyl triphenyl citrate
- acetyl tribenzyl citrate Rate dibutyl tartrate
- diacetyl dibutyl tartrate diacetyl dibutyl tartrate
- tributyl trimellitic acid
- the polyvalent carboxylic acid ester compound may be a phthalic acid ester compound.
- the phthalic acid ester compound include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dicyclohexyl terephthalate and the like.
- glycolate compounds include alkylphthalyl alkyl glycolates.
- alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl Ethyl glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl Glycolate, butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl
- the ester compound includes a fatty acid ester compound, a citrate ester compound, a phosphate ester compound, and the like.
- Examples of fatty acid ester compounds include butyl oleate, methylacetyl ricinoleate, and dibutyl sebacate.
- Examples of the citrate ester compound include acetyltrimethyl citrate, acetyltriethyl citrate, and acetyltributyl citrate.
- Examples of the phosphoric acid ester compound include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, biphenyl diphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc., preferably triphenyl phosphate. .
- polyester compounds glycolate compounds, and phosphate ester compounds are preferable, and polyester compounds are particularly preferable.
- the content of the plasticizer is preferably in the range of 1 to 20% by mass, more preferably in the range of 1.5 to 15% by mass with respect to the cellulose acetate.
- the content of the plasticizer is within the above range, the effect of imparting plasticity can be exhibited, and the resistance to the plasticizer from seeping out from the optical film is excellent.
- the optical film of the present invention preferably contains an ultraviolet absorber.
- the ultraviolet absorber is intended to improve durability by absorbing ultraviolet rays of 400 nm or less, and in particular, the transmittance at a wavelength of 370 nm is preferably 10% or less, more preferably 5% or less, and further Preferably it is 2% or less.
- the UV absorbers preferably used in the present invention are benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers, particularly preferably benzotriazole UV absorbers and benzophenone UV absorbers. .
- These are commercially available products made by BASF Japan and can be preferably used.
- a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as an ultraviolet absorber.
- the optical film of the present invention preferably contains two or more kinds of ultraviolet absorbers.
- a polymeric ultraviolet absorber can be preferably used, and in particular, a polymer type ultraviolet absorber described in JP-A-6-148430 is preferably used.
- the method of adding the UV absorber can be added to the dope after dissolving the UV absorber in an alcohol such as methanol, ethanol or butanol, an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane or a mixed solvent thereof. Or you may add directly in dope composition.
- an alcohol such as methanol, ethanol or butanol
- an organic solvent such as methylene chloride, methyl acetate, acetone or dioxolane or a mixed solvent thereof.
- inorganic powders that do not dissolve in organic solvents use a dissolver or sand mill in the organic solvent and cellulose ester to disperse them before adding them to the dope.
- the amount of UV absorber used is not uniform depending on the type of UV absorber and the operating conditions, but when the dry film thickness of the optical film is 15 to 50 ⁇ m, it is 0.5 to 10% by mass relative to the optical film.
- the range is preferably 0.6 to 4% by mass.
- Antioxidants are also referred to as deterioration inhibitors. When a liquid crystal image display device or the like is placed in a high humidity and high temperature state, the optical film may be deteriorated.
- the antioxidant has a role of delaying or preventing the optical film from being decomposed by, for example, the residual solvent amount of halogen in the optical film or phosphoric acid of the phosphoric acid plasticizer. It is preferable to contain.
- a hindered phenol compound is preferably used.
- 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino)- 1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oct Decyl-3- (3,5-di-t-butyl-4-hydroxyphenyl
- 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] is preferred.
- hydrazine-based metal deactivators such as N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine and tris (2,4-di- A phosphorus processing stabilizer such as t-butylphenyl) phosphite may be used in combination.
- the amount of these compounds added is preferably in the range of 1 ppm to 1.0% by mass ratio with respect to the cellulose ester, and more preferably in the range of 10 to 1000 ppm.
- the optical film may further contain fine particles (matting agent) as necessary in order to improve the slipperiness of the surface.
- the fine particles may be inorganic fine particles or organic fine particles.
- inorganic fine particles include silicon dioxide (silica), titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Examples include magnesium silicate and calcium phosphate. Of these, silicon dioxide and zirconium oxide are preferable, and silicon dioxide is more preferable in order to reduce an increase in haze of the obtained film.
- Examples of fine particles of silicon dioxide include Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600, NAX50 (manufactured by Nippon Aerosil Co., Ltd.), Sea Hoster KE-P10, KE-P30, KE-P50, KE-P100 (manufactured by Nippon Shokubai Co., Ltd.) and the like are included.
- Aerosil R972V, NAX50, Seahoster KE-P30 and the like are particularly preferable because they reduce the coefficient of friction while keeping the turbidity of the resulting film low.
- the primary particle diameter of the fine particles is preferably in the range of 5 to 50 nm, more preferably in the range of 7 to 20 nm.
- a larger primary particle size has a greater effect of increasing the slipperiness of the resulting film, but transparency tends to decrease. Therefore, the fine particles may be contained as secondary aggregates having a particle diameter in the range of 0.05 to 0.3 ⁇ m.
- the size of the primary particles or the secondary aggregates of the fine particles was determined by observing the primary particles or secondary aggregates with a transmission electron microscope at a magnification of 500,000 to 2,000,000 times, and measuring 100 primary particles or secondary aggregates. It can be determined as an average value of the particle diameter.
- the content of the fine particles is preferably in the range of 0.05 to 1.0% by mass, and preferably in the range of 0.1 to 0.8% by mass with respect to the whole cellulose acetate including the low substitution degree component. More preferred.
- the method for producing an optical film roll of the present invention includes (1) a step of preparing a dope by dissolving a cellulose ester and an additive in a solvent, and (2) casting the dope on an endless metal support.
- the step (5) is a step including stretching in the width direction or longitudinal direction (preliminary stretching).
- the method for producing a roll body of an optical film of the present invention includes (1) a step of preparing a dope by dissolving a cellulose ester and an additive in a solvent, and (2) flowing the dope onto an endless metal support. (3) evaporating the solvent from the cast dope to obtain a web, (4) peeling the web from the metal support, (5 ′) drying the web, (6) film A step of embossing both ends in the width direction, (7) a step of winding the film, then (5) a step of unwinding and stretching the film, and (6 ′) trimming both ends in the width direction of the film. Then, a step of embossing both ends, (7 ′) a step of winding up the film may be used.
- Step of preparing dope In a melting pot, a cellulose ester and an additive are dissolved in a solvent to prepare a dope.
- the solvent contained in the dope may be a single type or a combination of two or more types. From the viewpoint of increasing production efficiency, it is preferable to use a combination of a good solvent and a poor solvent for cellulose ester.
- a good solvent refers to a solvent that dissolves cellulose ester alone
- a poor solvent refers to a solvent that swells cellulose ester or does not dissolve alone. Therefore, the good solvent and the poor solvent differ depending on the average acyl group substitution degree of the cellulose ester.
- good solvents include organic halogen compounds such as dichloromethane, dioxolanes, acetone, methyl acetate, and methyl acetoacetate, and preferably dichloromethane or methyl acetate.
- Examples of poor solvents include methanol, ethanol, n-butanol, cyclohexane, and cyclohexanone. In order to suppress the bleeding of the additive in the optical film constituting the roll body, methanol or ethanol is preferable.
- the poor solvent may be one type or a mixture of two or more types.
- the content ratio of the poor solvent having a large absolute value of the difference from the SP value (solubility parameter) of the additive is preferably the largest.
- the good solvent is more than the poor solvent in order to increase the solubility of the cellulose ester.
- the mixing ratio of the good solvent and the poor solvent is preferably in the range of 70 to 98% by mass for the good solvent and in the range of 2 to 30% by mass for the poor solvent.
- the concentration of the cellulose ester in the dope is preferably higher in order to reduce the drying load, but it is difficult to filter if the concentration of the cellulose ester is too high. Therefore, the concentration of the cellulose ester in the dope is preferably in the range of 10 to 35% by mass, more preferably in the range of 15 to 25% by mass.
- Methods for dissolving cellulose ester in a solvent include, for example, a method of dissolving under heating and pressure, a method of adding a poor solvent to cellulose ester to swell, a method of further adding a good solvent, and a cooling dissolution method. sell.
- dissolve under a heating and pressurization is preferable.
- stirring and dissolving while heating to a temperature in the range where the solvent is boiling or higher under normal pressure and the solvent does not boil under pressure the generation of bulk undissolved material called gel or mako can be suppressed.
- the heating temperature is preferably higher from the viewpoint of increasing the solubility of the cellulose ester, but if it is too high, the pressure needs to be increased, and the productivity is lowered. Therefore, the heating temperature is preferably in the range of 45 to 120 ° C., more preferably in the range of 60 to 110 ° C., and even more preferably 70 ° C. to 105 ° C.
- the obtained dope may contain insoluble matters such as impurities contained in the cellulose ester as a raw material. Such an insoluble matter can become a bright spot foreign material in the obtained film. In order to remove such insoluble matter and the like, it is preferable to further filter the obtained dope.
- the dope is cast from the slit of the pressure die onto an endless metal support (for example, a stainless belt or a rotating metal drum).
- an endless metal support for example, a stainless belt or a rotating metal drum.
- the die is preferably a pressure die that can adjust the slit shape of the die part and easily adjust the film thickness uniformly.
- Examples of the pressure die include a coat hanger die and a T-die.
- the surface of the metal support is preferably mirror-finished.
- Casting can also be performed by preparing a plurality of dopes and casting the plurality of dopes on a smooth band or drum as a support.
- two or more kinds of dopes may be cast on the support at the same time, or separately on the support.
- the dope on the support side can be cast first and dried to some extent on the support, and then overlaid on the support.
- a film having a laminated structure can be produced by appropriately combining simultaneous casting (also referred to as co-casting) and sequential casting.
- the film may be produced by casting and laminating a solution containing cellulose acylate from a plurality of casting openings provided at intervals in the traveling direction of the metal support.
- the methods described in JP-A Nos. 158414, 1-122419, and 11-198285 can be applied.
- it may be formed into a film by casting a cellulose acylate solution from two casting ports.
- JP-B-60-27562, JP-A-61-94724, JP-A-61-947245 It can be carried out by the methods described in JP-A Nos. 61-104813, 61-158413, and 6-134933.
- the dope film is preferably dried in an atmosphere in the range of 40 to 100 ° C.
- an atmosphere in the range of 40 to 100 ° C. it is preferable to apply hot air in the range of 40 to 100 ° C. to the upper surface of the web or to heat it with infrared rays or the like.
- a method for evaporating the solvent there are a method in which air is applied to the surface of the dope film, a method in which heat is transferred by liquid from the back surface of the belt, a method in which heat is transferred from the front and back by radiant heat, etc.
- a method of transferring heat from the back surface of the liquid with a liquid is preferable.
- the obtained web is peeled off at the peeling position on the metal support.
- the temperature at the peeling position on the metal support is preferably in the range of 10 to 40 ° C, more preferably in the range of 11 to 30 ° C.
- the residual solvent amount of the web when peeling at the peeling position on the metal support depends on the drying conditions and the length of the metal support, but is preferably in the range of 50 to 120% by mass.
- a web having a large amount of residual solvent is too soft and tends to impair flatness, and wrinkles and streaks in the casting direction (MD direction) due to peeling tension tend to occur.
- the residual solvent amount of the web at the peeling position can be set so that wrinkles and lines in the casting direction (MD direction) can be suppressed.
- the amount of residual solvent in the web is defined by the formula described later.
- the peeling tension when peeling the web from the metal support can usually be 300 N / m or less.
- stretching and obtaining a film after drying a web The web obtained by peeling from a metal support body is dried.
- the web may be dried while being conveyed by a large number of rollers arranged above and below, or may be dried while being conveyed while fixing both ends of the web with clips.
- the method of drying the web may be a method of drying with hot air, infrared rays, a heating roller, microwaves, or the like, and a method of drying with hot air is preferable because it is simple.
- the drying temperature of the web can be about 40 to 250 ° C., preferably about 40 to 160 ° C.
- the optical film having a desired retardation is obtained by stretching the web.
- the retardation of the optical film can be controlled by adjusting the magnitude of the tension applied to the web.
- the stretching of the web includes the width direction (TD direction), the dope casting direction (MD direction), and the stretching in the oblique direction. In the present invention, it is necessary to stretch at least the oblique direction described later. .
- the web may be stretched uniaxially or biaxially.
- Biaxial stretching is preferably stretching in the oblique direction and the width direction (TD direction).
- Biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching.
- the sequential biaxial stretching includes a method of sequentially performing stretching in different stretching directions, a method of performing stretching in the same direction in multiple stages, and the like.
- Simultaneous biaxial stretching includes a mode in which stretching is performed in one direction and the tension in the other direction is relaxed and contracted.
- the stretch ratio depends on the thickness of the optical film to be obtained and the required retardation value, it is finally possible to stretch the film in the range of 50 to 150% in the oblique direction to maximize the elastic modulus in the film plane.
- the value of the ratio of the elastic modulus E B in the direction B perpendicular to it and the elastic modulus E a direction a value, preferably to a 1.4 ⁇ E a / E B, more preferably 60-120 %.
- uniform optical characteristics can be imparted without satisfying the relationship of the elastic modulus ratio and without breakage due to stretching.
- the elastic modulus may be stretched within a range of 1 to 50% in the width direction (TD direction) as preliminary stretching before oblique stretching. This is a preferred embodiment from the viewpoint of forming an embossed portion having a high crush resistance ratio (%). More preferably, it is in the range of 5 to 30%. By pre-stretching in this range, the elastic modulus can be increased and the crush resistance rate (%) of the embossed portion can be improved.
- the web stretching temperature is preferably in the range of 120 ° C to 200 ° C, more preferably in the range of 150 ° C to 200 ° C, and still more preferably in the range of 150 ° C to 190 ° C.
- the web stretching method is not particularly limited, and preferred is a tenter stretching method in which both ends of the web are fixed with clips or pins and the gap between the clips or pins is widened.
- a tenter stretching method in which both ends of the web are fixed with clips or pins and the gap between the clips or pins is widened.
- an oblique stretching tenter is used. Is preferred.
- the residual solvent of the web at the start of stretching is preferably 20% by mass or less, more preferably 15% by mass or less.
- the film obtained after stretching is further dried.
- the drying temperature is preferably in the range of 110 to 190 ° C, and more preferably in the range of 120 to 170 ° C. If the drying temperature is too low, it is difficult to sufficiently remove the solvent by evaporation.
- the method for drying the film can be performed, for example, by a method of applying hot air while transporting the film.
- the roll body of the optical film of the present invention is an optical film stretched obliquely with respect to the film longitudinal direction.
- an apparatus capable of oblique stretching obliquely stretched tenter
- the diagonally stretched tenter used in the present invention 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 is oriented with high precision evenly on the left and right across the width direction of the film.
- a film stretching apparatus that can control the film thickness and the retardation with high accuracy is preferable.
- the orientation angle is the direction of orientation by stretching of resin molecules in the film.
- FIG. 5 is a schematic view of an obliquely stretchable intermediate used in the method for producing an obliquely stretched film of the present invention.
- this is an example, and the present invention is not limited to this.
- the unstretched film 100 is held at the positions of the right film holding start point 102-1 and the left film holding start point 102-2.
- the film is conveyed and stretched by the tenter 104 in the oblique direction indicated by the locus 103-1 of the right film holding means and the locus 103-2 of the left film holding means, and the right film holding end point 105- 1. Grasping is released by the film holding end point 105-2 on the left side, and the conveyance is controlled by the guide roller 108-2 on the tenter outlet side to form the obliquely stretched film 106.
- the unstretched film is stretched obliquely at an angle of the film stretching direction 109 (referred to as an orientation angle ⁇ ) with respect to the film feeding direction 107-1.
- the orientation angle ⁇ defines the angle of the direction A indicating the maximum value of the elastic modulus in the fill surface as referred to in the present invention with respect to the film longitudinal direction.
- the distances X 1 and X 2 between the main shaft position of the guide roller 108-1 closest to the entrance of the obliquely stretched tenter and the gripping tool at the entrance of the obliquely stretched tenter are in the range of 20 to 100 cm.
- the distance is preferably 20 to 60 cm, and more preferably 20 to 40 cm.
- X 1 is the distance of the gripper (clip gripping portion) in the main shaft position and the right side of the film holding start point 102-1 of the guide rollers 108-1
- X 2 is the main axis of the guide roller 108-1 This is the distance between the position and the gripping tool (clip gripping portion) at the film holding start point 102-2 on the left side.
- the orientation angle ⁇ is the orientation angle when the longitudinal direction is 0 °.
- a mechanism capable of adjusting the position of the guide roller and the clip gripping part is 1 to 5 inches (1 inch is 2.54 cm), and the diameter of the guide roller 108-1 closest to the entrance of the obliquely stretched tenter is in the range of 1 to 20 cm.
- a mechanism capable of further installing a roller in the vicinity of the entrance portion of the obliquely stretched tenter is provided.
- the production of the obliquely stretchable optical film of the present invention is preferably carried out using the above-mentioned tenter that can be stretched obliquely.
- This tenter is prepared by subjecting a long film to its traveling direction (film width) in an oven heating environment. This is a device that widens in an oblique direction with respect to the moving direction of the midpoint of the direction.
- the tenter includes an oven, a pair of rails on the left and right on which a gripping tool for transporting the film travels, and a number of gripping tools that travel on the rails.
- Both ends of the film fed from the film roller and sequentially supplied to the inlet portion of the tenter are gripped by a gripping tool, the film is guided into the oven, and the film is released from the gripping tool at the outlet portion of the tenter.
- the film released from the gripping tool is wound around the core.
- Each of the pair of rails has an endless continuous track, and the gripping tool which has released the grip of the film at the exit portion of the tenter travels outside and is sequentially returned to the entrance portion.
- the rail shape of the tenter is an asymmetric shape on the left and right according to the orientation angle ⁇ , the stretching ratio, etc. given to the stretched film to be manufactured, and can be finely adjusted manually or automatically.
- a long optical film is stretched, and the orientation angle ⁇ can be set to an arbitrary angle within a range of preferably 10 ° to 80 ° with respect to the winding direction after stretching.
- the gripping tool of the tenter is configured to travel at a constant speed with a certain distance from the front and rear gripping tools.
- the traveling speed of the gripping tool can be selected as appropriate, but is usually in the range of 10 to 100 m / min.
- the difference in travel speed between the pair of left and right grippers is usually 1% or less, preferably 0.5% or less, more preferably 0.1% or less of the travel speed. This is because if there is a difference in the traveling speed between the left and right sides of the film at the exit of the stretching process, wrinkles and shifts will occur at the exit of the stretching process, so the speed difference between the right and left gripping tools is required to be substantially the same speed. Because. In general tenter devices, etc., there are speed irregularities that occur on the order of seconds or less depending on the period of the sprocket teeth that drive the chain, the frequency of the drive motor, etc. This does not correspond to the speed difference described in the invention.
- each rail part and the rail connecting part can be freely set. Therefore, when an arbitrary entrance width and exit width are set, the stretch ratio is set accordingly. be able to. (A circle in FIG. 6 is an example of a connecting portion.)
- a large bending rate is often required for the rail that regulates the trajectory of the gripping tool. In order to avoid interference between gripping tools due to sudden bending or local stress concentration, it is desirable that the trajectory of the gripping tool draws an arc at the bent portion.
- FIG. 6 shows the rail track (rail pattern) of the tenter used in the manufacturing method of the present invention.
- the traveling direction DR1 at the tenter inlet of the unstretched film is different from the traveling direction DR2 at the tenter outlet side of the stretched film, and thus, even in a stretched film having a relatively large orientation angle ⁇ , it is wide and uniform. Optical characteristics can be obtained.
- the feeding angle ⁇ i is an angle formed by the traveling direction D1 at the tenter entrance and the traveling direction DR2 on the tenter exit side of the stretched film.
- the feeding angle ⁇ i is set at 30 ° ⁇ i ⁇ 60 °. More preferably, it is set at 35 ° ⁇ i ⁇ 55 °.
- the optical film is sequentially gripped at both ends (both sides) by the left and right grippers at the tenter entrance (position a), and travels as the grippers travel.
- the left and right grips CL and CR that face the direction substantially perpendicular to the film traveling direction (DR1) at the entrance of the tenter (position a) run on the left and right asymmetric rails, preheat zone, stretch Pass through an oven with zones and cooling zones.
- substantially perpendicular indicates that the angle formed by the straight line connecting the aforementioned gripping tools CL and CR and the film feeding direction DR1 is within 90 ⁇ 1 °.
- the film temperature at the time of diagonally stretching in the stretching zone has a gradient in the width direction. It is preferable to take a method of adjusting, a method of adjusting so that the preheating temperature in the preheating zone or the holding temperature in the holding zone, and the cooling temperature in the cooling zone have a gradient in the width direction.
- Preheating zone refers to the section that runs while the interval between the gripping tools gripping both ends is kept constant at the oven entrance.
- the stretching zone refers to an interval until the gap between the gripping tools gripping both ends starts to become constant again.
- the holding zone refers to a section in which the temperature in the zone is set to be equal to or higher than the glass transition temperature Tg (° C.) of the cellulose ester constituting the film in a period in which the interval between the gripping tools after the stretching zone becomes constant again.
- the cooling zone is a section in which the temperature in the zone is set to be equal to or lower than the glass transition temperature Tg (° C.) of the cellulose ester constituting the film in a period in which the interval between the gripping tools after the stretching zone becomes constant again.
- the temperature of each zone is Tg to (Tg + 30) ° C.
- the temperature of the stretching zone is Tg to (Tg + 30) ° C.
- the temperature of the holding zone is Tg to (Tg + 30) with respect to the glass transition temperature Tg of the cellulose ester.
- the temperature of the cooling zone is preferably set to Tg to (Tg + 30) ° C.
- the opening degree of the nozzle that sends warm air into the temperature-controlled room in the preheating zone, the stretching zone, the holding zone, or the cooling zone is differentiated in the width direction.
- a known method such as a method of adjusting the temperature and controlling the heating by arranging the heaters in the width direction can be used.
- the gradient in the width direction of the film temperature during oblique stretching in the stretching zone is preferably in the range of 0.5 to 10.0 ° C, more preferably in the range of 1.0 to 5.0 ° C, and most preferably 1. It is in the range of 5 to 3.0 ° C. If the temperature is in the range of 0.5 to 10.0 ° C., the effect of temperature gradient is recognized, the effect of uniforming the elastic modulus in the film width direction is obtained, and the retardation value Ro is uniform in the film width direction. Is obtained.
- the preheating temperature in the preheating zone, the holding temperature in the holding zone, and the gradient of the cooling temperature in the cooling zone in the width direction are preferably in the range of 0.5 to 10.0 ° C., more preferably 1.0 to 5.0. It is in the range of ° C, most preferably in the range of 1.5 to 3.0 ° C. If the temperature is in the range of 0.5 to 10.0 ° C., the effect of temperature gradient is recognized, the effect of uniforming the elastic modulus in the film width direction is obtained, and the retardation value Ro is uniform in the film width direction. Is obtained.
- a method of adjusting the film residual solvent to have a gradient in the width direction when stretching in the width direction before the oblique stretching according to the present invention is preferable to employ a method of adjusting the stretching temperature so as to have a gradient in the width direction.
- the gradient of the film residual solvent in the width direction is preferably in the range of 0.5 to 20.0% by mass, more preferably in the range of 2.0 to 15.0% by mass, and most preferably 4.0 to 12%. The difference is in the mass% range. If it is within the range of 0.5 to 20.0% by mass, the effect of residual solvent gradient is recognized, the effect of uniforming the elastic modulus in the film width direction is obtained, and the film width direction is uniform. A retardation value Ro is obtained.
- the residual solvent amount is defined by the following formula.
- Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100
- M is the mass of the sample collected before the web or film is stretched
- N is the mass after heating M at 115 ° C. for 1 hour.
- the film residual solvent In order to give the film residual solvent a gradient in the width direction, it can be performed by adjusting the drying conditions.
- the opening degree of the nozzle that sends the warm air into the temperature-controlled room is adjusted, and the heater is controlled by heating in the width direction. It can be done by a technique.
- the length of the preheating zone, the stretching zone and the cooling zone can be appropriately selected.
- the length of the preheating zone is usually 100 to 150% and the length of the fixed zone is usually 50 to 100% with respect to the length of the stretching zone. .
- the support of the film is maintained at the time of stretching, and after stretching in a state where the volatile content is 5% by volume or more, the volatile content is reduced while shrinking. It is also preferable to lower the value.
- To maintain the support of the film means to grip both side edges without impairing the film property of the film.
- the state of 5% by volume or more may always be maintained in the stretching operation process, and the state of the volatile content is maintained at 5% by volume or more only in a part of the stretching operation process. May be.
- the entrance position is a starting point, and that the section of 50% or more of the entire stretching section and the volatile content rate are 12% by volume or more.
- the volatile fraction (unit: volume%) represents the volume of the volatile component contained per unit volume of the film, and is a value obtained by dividing the volatile component volume by the film volume.
- the stretching ratio R (((W ⁇ W0) / W0) ⁇ 100) in the stretching step is preferably in the range of 50 to 150%, more preferably in the range of 60 to 120%. When the stretching ratio is within this range, it is preferable because uneven thickness in the width direction is reduced. In the stretching zone of the oblique stretching tenter, if the stretching temperature is differentiated in the width direction, the width direction thickness unevenness can be further improved.
- W0 represents the width of the film before stretching
- W represents the width of the film after stretching.
- the guide roller closest to the entrance of the tenter is a driven roller that guides the running of the film, and is rotatably supported by bearings (not shown).
- a known material can be used for the roller, but it is preferable to reduce the weight by applying a ceramic coat to prevent the film from being scratched or by applying chrome plating to a light metal such as aluminum. .
- This roller is provided to stabilize the trajectory when the film travels.
- one of the rollers on the upstream side of this roller is nipped by pressing a rubber roller. This is because by using such a nip roller, it is possible to suppress fluctuations in the drawing tension in the film flow direction.
- a pair of bearings at both ends (left and right) of the guide roller closest to the entrance of the tenter are provided with a first tension detecting device and a second film tension detecting device for detecting the tension generated in the film in the roller.
- 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 on the left and right bearings of the guide roller closest to the entrance of the diagonally stretched tenter, so that the force that the running film exerts on the roller, i.e., the tension in the film traveling direction that is generated near both side edges of the film, It 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 roller, 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 film tension detection device as described above is provided so that the tension in the vicinity of both side edges of the film in the guide roller closest to the entrance of the oblique stretching tenter is detected because the position and direction of the film is the same as that of the film stretching device. If there is a deviation with respect to the position and direction of the entrance, depending on the amount of deviation, there will be a difference in the tension in the vicinity of both side edges of the film in the guide roller closest to the entrance of the obliquely stretched tenter. This is because the degree of deviation is determined by detecting this tension difference.
- the load acting on the rollers will be roughly equal on the left and right, and if the positions are shifted, the left and right films There is a difference in tension.
- the gripping by the gripping tool at the entrance of the film stretching apparatus is stable.
- a method for changing the film transport direction is required.
- a known method such as an air flow roller can be used. It is preferable that the apparatus (winder apparatus, accumulator apparatus, drive apparatus, etc.) after the obliquely extending tenter exit is slidable in the lateral direction.
- FIGS. 8A and 8B show manufacturing patterns of the oblique stretching according to the various inventions described above.
- a film feeding device 110 a transport direction changing device 111, a winding device 112, and a film forming device 113 are shown.
- the film feeding device 110 is slidable and pivotable so that the film can be fed at a predetermined angle with respect to the obliquely stretched tenter entrance, or the film feeding device 110 is slidable, and the transport direction changing device It is preferable that the film can be sent to the entrance of the obliquely stretched tenter by 111.
- the film feeding device and the transport direction changing device as described above, it becomes possible to further narrow the width of the entire manufacturing apparatus, and to finely control the film feeding position and angle, It becomes possible to obtain a diagonally stretched film having small variations in film thickness and optical value and excellent uniformity in elastic modulus. Further, by making the film feeding device and the transport direction changing device movable, it is possible to effectively prevent the left and right clips from being caught in the film.
- the take-up device 112 can finely control the film take-up position and angle by forming the film so that the film can be taken at a predetermined angle with respect to the obliquely stretched tenter outlet, and there are variations in film thickness and optical value. It is possible to obtain a diagonally stretched film that is small and excellent in elasticity uniformity. Therefore, the generation of wrinkles in the film can be effectively prevented, and the winding property of the film is improved, so that the film can be wound up in a long length.
- the take-up tension T (N / m) of the stretched film is adjusted in the range of 100 N / m ⁇ T ⁇ 300 N / m, preferably 150 N / m ⁇ T ⁇ 250 N / m.
- the film is less likely to sag and wrinkle, and the retardation, the profile in the width direction of the orientation axis, the uniformity of the elastic modulus is high, and the width Variation in orientation angle in the hand direction and width yield (efficiency in the width direction) are good.
- the fluctuation of the take-up tension T it is preferable to control the fluctuation of the take-up tension T with an accuracy of less than ⁇ 5%, preferably less than ⁇ 3%.
- the variation in the take-up tension T is less than ⁇ 5%, the optical characteristics vary in the width direction and the flow direction, and the uniformity of the elastic modulus increases.
- general PID control is performed so that the load applied to the first roller at the tenter outlet, that is, the film tension is measured and the value is kept constant.
- a method of controlling the rotation speed of the take-up roller by a method is mentioned.
- Examples of the method for measuring the load include a method in which a load cell is attached to a bearing portion of a roller and a load applied to the roller, that is, a film tension is measured.
- a load cell a known tensile type or compression type can be used.
- the stretched film is released from the tenter exit after being gripped by the gripper, trimmed at both ends (both sides) of the film, and then wound around a winding core (winding roller) to roll the stretched film.
- a winding core winding roller
- both ends of the film held by the tenter holding tool may be trimmed before being wound on the winding roller.
- the masking film before winding, for the purpose of preventing blocking between the films, the masking film may be overlapped and wound up at the same time, or at least one of the stretched films, preferably wound up with tape or the like attached to both ends. Also good.
- the masking film is not particularly limited as long as it can protect the film, and examples thereof include a polyethylene terephthalate film, a polyethylene film, and a polypropylene film.
- the orientation angle ⁇ is preferably in the range of 30 ° to 60 ° with respect to the winding direction, and the width direction is at least 1300 mm.
- the variation of the in-plane retardation Ro is preferably 4 nm or less, and the variation of the orientation angle ⁇ is preferably 1.0 ° or less.
- the variation of the in-plane retardation Ro of the obliquely stretched film of the present invention is 4 nm or less, preferably 3 nm or less, at least 1300 mm in the width direction.
- the variation in the orientation angle ⁇ of the obliquely stretched film of the present invention is 1.0 ° or less, preferably 0.80 ° or less, at least 1300 mm in the width direction. If the variation in the orientation angle ⁇ is 1.0 ° or less, a stretched film is bonded to a polarizing plate to obtain a circularly polarizing plate, and even if this is installed on a liquid crystal display device, no light leakage occurs and the contrast is lowered. I won't let you.
- the optimum value of the in-plane retardation value Ro of the obliquely stretched film of the present invention is selected depending on the design of the display device used.
- FIG. 9 is a schematic diagram illustrating an example of the embossing apparatus 20.
- the embossing apparatus includes an embossing roller 22 and a back roller 24 disposed so as to face the embossing roller 22 with the film 14 interposed therebetween.
- the roller diameter of the embossing roller 22 is preferably in the range of 30 to 60 cm, and more preferably in the range of 30 to 50 cm.
- the roller diameter of the embossing roller is more than 60 cm, the distance between the heat source (arranged inside the embossing roller) and the surface of the embossing roller is too large, and temperature unevenness may occur on the surface of the embossing roller. Therefore, a portion having a high elastic modulus and a portion having a low elastic modulus are generated in the embossed portion to be formed, and a portion having a low elastic modulus is easily crushed.
- the roller diameter of the embossing roller is less than 30 cm, the rotation axis is likely to be shaken; the height of the convex portion of the embossing formed tends to vary. The embossed part formed higher than the set height tends to be crushed.
- the embossing roller is provided with a temperature adjustment mechanism, and the temperature can be adjusted appropriately.
- the temperature can be controlled by blowing air for adjusting the temperature inside the embossing roller, or by pressing a temperature-controlled roller from the inside or the outside of the embossing roller.
- the whole embossing roller can be installed in a thermostat.
- the temperature of the crown roller or peeling roller can also be controlled.
- a preferred example of the embossing roller is a rotating roller having a structure in which a heat source is incorporated therein.
- a heat source for example, an apparatus that heats a roller shell by incorporating a sheathed heater and a heat medium inside the roller to generate heat can be used, and the temperature can be controlled by a thermocouple and a control panel incorporated in the roller.
- the material of the back roller is preferably made of metal in order to uniformly cool the film on which the embossed portion is formed.
- metal type for example, SUS, titanium, stainless steel, chromium, copper and the like are preferable.
- the metal back roller is easier to cool the film more uniformly than, for example, a rubber back roller, so that the cellulose ester is easily crystallized uniformly, and an embossed portion having high strength (high elastic modulus) is formed. Can do.
- the clearance between the embossing roller 22 and the back roller 24 can be about 1 ⁇ m to 30 ⁇ m, preferably about 1 to 15 ⁇ m.
- the nip pressure between the embossing roller 22 and the back roller 24 can be about 100 to 10,000 Pa.
- the nip pressure is preferably in the range of 500 to 4000 Pa, more preferably 1000 to 3000 Pa.
- the embossing roller 22 and the back roller 24 nip both ends in the width direction of the film 14, and emboss the both ends in the width direction of the film.
- the surface temperature of the embossing roller 22 is preferably in the range of 150 to 350 ° C., more preferably in the range of 160 to 300 ° C., further preferably in the range of 180 to 250 ° C., and 180 to 220 ° C. It is especially preferable to set the range.
- the film can be sufficiently melted, and even when cooled, the cellulose ester can be sufficiently crystallized, and the embossed portion having high strength Easy to form. Moreover, the film does not melt too much, and sticking of the melt of the film to the embossing roller can be prevented.
- the surface temperature of the embossing roller 22 is (Tg + 20 ° C.) to (Tg + 50 ° C.) with respect to the glass transition temperature (Tg) of the film. ) Is preferable.
- the surface temperature of the embossing rollers on both sides is within a range of 5 to 20 ° C. It is preferable to form the embossed portion with a difference.
- an embossed portion is formed with a high-temperature embossing roller at the end portion having a low elastic modulus, and the surface temperature of the embossing roller is set within a range of 5 to 20 ° C. at the end portion having a high elastic modulus. It is preferable to form an embossed part with the embossing roller set in (1).
- the surface temperature difference is more preferably in the range of 7 to 15 ° C.
- the surface temperature of the back roller 24 depends on the surface temperature of the embossing roller 22, but is preferably in the range of 30 to 100 ° C, more preferably in the range of 50 to 80 ° C.
- the surface temperature of the back roller is in the range of 30 to 100 ° C.
- the film is not rapidly cooled, the cellulose ester is easily crystallized uniformly, and an embossed portion having a high elastic modulus is obtained.
- the cellulose ester contained in the film can be easily cooled and crystallized, and the thermal expansion of the film can be suppressed to prevent undulation of the front and back surfaces of the film near the embossed portion.
- the undulations of the front and back surfaces of the film near the embossed portion occur, the films are likely to stick to each other and the film is easily torn.
- the film conveyance speed during embossing is preferably in the range of 30 to 120 m / min, more preferably in the range of 40 to 120 m / min, and still more preferably in the range of 60 to 100 m / min.
- the productivity can be improved, and the pressure of the embossing roller and the heat of the embossing roller and the back roller can be easily transmitted to the film, thereby being included in the film.
- a cellulose ester is crystallized uniformly, and an embossed part with high strength is obtained.
- Step of winding film The obtained long optical film is wound in the length direction of the film (perpendicular to the width direction) using a winder.
- the winding method is not particularly limited, and may be a constant torque method, a constant tension method, a taper tension method, or the like.
- the winding tension when winding the optical film can be about 50 to 170N.
- the winding length is in the range of 1500 to 8000 m, so that the formed embossed portion can be prevented from being crushed and the productivity is improved.
- the method for producing a roll of the optical film of the present invention is not limited to the solution casting film forming method, and the film may be formed by a melt film forming method.
- the melt film-forming method is a molding method in which a composition containing an additive such as a resin and a plasticizer is heated and melted to a temperature exhibiting fluidity, and then a melt containing a fluid cellulose ester is cast.
- the heating and melting molding method can be classified into a melt extrusion molding method, a press molding method, an inflation method, an injection molding method, a blow molding method, a stretch molding method, and the like.
- the melt extrusion method is preferable from the viewpoint of mechanical strength and surface accuracy.
- the plurality of raw materials used in the melt extrusion method are usually preferably kneaded and pelletized in advance.
- a known method can be applied. For example, dry cellulose acylate, plasticizer, and other additives are fed to an extruder with a feeder and kneaded using a single-screw or twin-screw extruder. It can be obtained by extruding into a strand from a die, water cooling or air cooling and cutting.
- the additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.
- a small amount of additives such as fine particles and antioxidants are preferably mixed in advance in order to mix uniformly.
- the extruder used for pelletization preferably has a method of processing at as low a temperature as possible so that pelletization is possible so that the shearing force is suppressed and the resin does not deteriorate (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 put into a feeder as it is, supplied to an extruder, heated and melted, and then directly formed into a film without being pelletized.
- the melting temperature is in the range of 200 to 300 ° C.
- T A film is cast from the die, the film is nipped by a cooling roller and an elastic touch roller, and solidified on the cooling roller.
- 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.
- Stainless steel fiber sintered filter is made by compressing the stainless fiber body in a complicatedly intertwined state, and sintering and integrating the contact points. The density is changed according to the thickness and compression amount of the fiber, and the filter is filtered. The accuracy can be adjusted.
- Additives such as plasticizers and fine 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 roller side when the film is nipped by the cooling roller and the elastic touch roller is preferably in the range of Tg or more and Tg + 110 ° C. or less of the film.
- a known elastic touch roller can be used as the elastic touch roller having an elastic surface used for such a purpose.
- the elastic touch roller is also called a pinching rotary body, and a commercially available one can also be used.
- the film obtained as described above is subjected to a stretching process by the stretching operation after passing through the step of contacting the cooling roller.
- the stretching method a known roller stretching machine or tenter can be preferably used.
- the stretching temperature is usually preferably in the temperature range of Tg to (Tg + 60) ° C. of the resin constituting the film.
- the roll body of the optical film of the present invention is preferably in a storage form in which a roll film portion is wrapped with a resin film, in particular, a moisture-proof film vapor-deposited on the resin film with aluminum, and then the winding shaft portion is fastened with a string or rubber band.
- the peripheral surface of the optical film film wound on the cylindrical core (201) and the left and right side surfaces The whole is covered with a sheet-like packaging material (203), and both ends in the roll circumferential direction of the packaging material (203) are overlapped with each other. 204) is applied to the packaging material (203) so that there is substantially no gap in the contact portion between the ends, preventing dust and the like from entering the inside, and outside the left and right ends of the roll film.
- the joints between the peripheral surfaces of the core (201) protruding from the outer periphery (201a) and (201a) and the left and right ends of the packaging material (203) are fastened with a string or rubber band (205).
- the left and right ends are fastened with multiple layers of gummed tape, and the winding shaft portion is fastened with a string or rubber band rather than having a gap substantially without sealing inside,
- the roll body can be appropriately absorbed and dehumidified during storage or transportation, which is a preferred embodiment for enhancing the uniformity of the optical properties and physical properties of the optical film.
- the packaging material (203) examples include a film of a polyolefin-based synthetic resin such as polyethylene and polypropylene, and a film of a polyester-based synthetic resin such as polyethylene terephthalate and polyethylene naphthalate.
- the thickness of the packaging material (203) is preferably 10 ⁇ m or more from the viewpoint of maintaining moisture permeability, and is preferably 100 ⁇ m or less from the viewpoint of handling such as rigidity. Further, since the moisture permeability of the packaging material (203) ⁇ ⁇ varies depending on the thickness of the synthetic resin film constituting the packaging material (203) ⁇ , adjusting the thickness of the synthetic resin film allows the penetration of the packaging material (203). The wettability can be adjusted as appropriate.
- the moisture permeability of the packaging material (203) is 10 g / m 2 or less per day as defined in JIS Z0208, it is possible to prevent the deterioration of the winding shape and the foreign matter failure, resulting in that. Since it becomes difficult to generate
- the roll body of the optical film is a packaging material having a moisture permeability of 5 g / m 2 or less per day as defined in JIS Z 0208 ( 203), and more preferably, a packaging material (203) having a moisture permeability of 1 g / m 2 or less.
- polyolefin-type synthetic resin films such as polyethylene and a polypropylene
- the thickness of the packaging material (203) made of these composite materials is preferably 1 ⁇ m or more from the viewpoint of maintaining moisture permeability, and is preferably 50 ⁇ m or less from the viewpoint of handling such as rigidity. Since the moisture permeability of the packaging material (203) varies depending on the thickness of the composite material, the moisture permeability of the packaging material (203) can be appropriately adjusted by adjusting the thickness.
- a composite material in which metal thin films are bonded and laminated has high moisture permeation preventive properties and is lightweight, so that it can be particularly preferably used in handling.
- the packaging material (203) can exhibit the above effect by winding the roll of the optical film of the present invention at least once, but it may be wound twice or more.
- the roll body of the optical film of the present invention packaged in the above-described packaging form provides an optical film having uniform optical characteristics without deterioration in winding shape even during long-term storage in a warehouse or transportation by truck or ship. Can do.
- the arithmetic average roughness Ra of the optical film surface of the present invention is generally in the range of 1.3 to 4.0 nm, preferably in the range of 1.6 to 3.5 nm.
- the dimensional change rate (%) of the optical film of the present invention is preferably less than 0.5%, more preferably less than 0.3%, and most preferably. It is less than 0.1%.
- defects failures in the film
- the defects referred to here are the rapid evaporation of the solvent in the drying step in film formation by the solution casting method. It refers to voids (foaming defects) in the film generated due to the cause, foreign substances in the film forming stock solution, and foreign substances (foreign object defects) in the film due to foreign substances mixed in the film forming.
- a defect having a diameter of 5 ⁇ m or more is 1 piece / 10 cm square or less in the film plane. More preferably, it is 0.5 piece / 10 cm square or less, and particularly preferably 0.1 piece / 10 cm square or less.
- the diameter of the above defect indicates the diameter when the defect is circular, and when the defect is not circular, the range of the defect is determined by observing with a microscope according to the following method, and the maximum diameter (diameter of circumscribed circle) is determined.
- the defect range is measured by the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope.
- the defect is accompanied by a change in surface shape such as transfer of a roller scratch or an abrasion, the size is confirmed by observing the defect with reflected light of a differential interference microscope.
- the film When the number of defects is larger than 1/10 cm square, for example, when the film is tensioned during processing in a later process, the film may be broken starting from the defects and productivity may be reduced. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
- the elongation at break in at least one direction is preferably 4% or more, more preferably 10% in the measurement based on JIS-K7127-1999. That's it.
- the upper limit of the elongation at break is not particularly limited, but the elongation at break tends to decrease by performing stretching at a high stretching ratio, and pre-stretching is preferably performed in the TD direction as in the present invention. Thereafter, by performing oblique stretching, the breaking elongation is preferably 30% or less, and more preferably 20% or less.
- the optical film of the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. In order to achieve excellent transparency expressed by such total light transmittance, it is necessary not to introduce additives and copolymerization components that absorb visible light, or to remove foreign substances in the polymer by high-precision filtration. It is effective to reduce the diffusion and absorption of light inside the film. Also, reduce the surface roughness of the film surface by reducing the surface roughness of the film contact portion (cooling roller, calendar roller, drum, belt, coating substrate in solution casting, transport roller, etc.) during film formation. It is effective to reduce the diffusion and reflection of light on the film surface.
- the long optical film drawn out from the roll of the optical film of the present invention is preferably stretched obliquely so that the slow axis angle (that is, the orientation angle ⁇ ) is preferably “substantially 45 ° relative to the longitudinal direction”.
- the long circularly polarizing plate can be formed by laminating with a long polarizer having a transmission axis (or absorption axis) in the longitudinal direction and a roll-to-roll.
- the circularly polarizing plate is preferably manufactured through a step of removing the embossed portion of the optical film and a step of bonding the optical film from which the embossed portion has been removed and a polarizer.
- the circularly polarizing plate can be provided in a liquid crystal display device or an organic electroluminescence image display device.
- organic electroluminescence image display device By applying the circularly polarizing plate to an organic electroluminescence image display device as an example, the specular reflection of the metal electrode of the organic electroluminescence light emitter can be achieved.
- the shielding effect is expressed (hereinafter, organic electroluminescence is simply referred to as organic EL).
- the polarizer is preferably sandwiched between the optical film of the present invention and the protective film.
- a protective film other cellulose ester-containing films are suitably used.
- a commercially available cellulose ester film for example, Konica Minoltack KC8UX, KC5UX, KC4UX, KC8UCR3, KC4SR, KC4BR, KC4CR, KC4DR, KC4FR , KC4KR, KC8UY, KC6UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC2UA, KC4UA, KC6UAKC, 2UAH, KC4UAH, KC6UAH, T , Fujitac TD60UL, Fujitac TD40UL, Fujitac R02, Fujitac R06 Manufactured by Film Corporation) is preferably used.
- the thickness of the protective film is preferably used.
- the polarizer is an element that passes only light having a polarization plane in a certain direction, and examples thereof include a polyvinyl alcohol polarizing film.
- the polyvinyl alcohol polarizing film includes those obtained by dyeing iodine on a polyvinyl alcohol film and those obtained by dyeing a dichroic dye.
- the polarizer can be obtained by uniaxially stretching a polyvinyl alcohol film and then dyeing; or after dying a polyvinyl alcohol film and uniaxially stretching, and preferably by further performing a durability treatment with a boron compound.
- the film thickness of the polarizer is preferably in the range of 5 to 30 ⁇ m, and more preferably in the range of 5 to 15 ⁇ m.
- polyvinyl alcohol film examples include an ethylene unit content of 1 to 4 mol%, a degree of polymerization of 2000 to 4000, a degree of saponification of 99.0 to 99 described in JP2003-248123A, JP2003-342322A, and the like. 99 mol% ethylene-modified polyvinyl alcohol is preferably used. Moreover, it is preferable to produce a polarizer by producing a polarizer by the method described in JP2011-1000016A, JP4691205A, and JP4804589A, and attaching the polarizer to the optical film of the present invention.
- the bonding of the optical film of the present invention and the polarizer is not particularly limited, but can be performed using a completely saponified polyvinyl alcohol adhesive after saponifying the optical film. Moreover, although it can also bond together using an active energy ray hardening adhesive etc., a photocurable adhesive is used from the point etc. which the elasticity modulus of the obtained adhesive bond layer is high and it is easy to suppress a deformation
- Preferred examples of the photocurable adhesive include ( ⁇ ) cationic polymerizable compound, ( ⁇ ) photocationic polymerization initiator, and ( ⁇ ) a wavelength longer than 380 nm, as disclosed in JP 2011-08234 A. And a photo-curable adhesive composition containing each component of a photosensitizer exhibiting maximum absorption in the light of ( ⁇ ) and a naphthalene-based photosensitization aid.
- other photocurable adhesives may be used.
- the polarizing plate includes (1) a pretreatment step for easily adhering the surface of the optical film to which the polarizer is bonded, and (2) at least one of the adhesive surfaces of the polarizer and the optical film. (3) A bonding step of bonding the polarizer and the optical film through the obtained adhesive layer, and 4) A polarizer and the optical film are bonded through the adhesive layer. It can manufacture by the manufacturing method including the hardening process which hardens an adhesive bond layer in the match
- Pretreatment process In the pretreatment step, an easy adhesion treatment is performed on the adhesive surface of the optical film with the polarizer.
- easy adhesion processing is performed on the bonding surface of each optical film with the polarizer. Examples of the easy adhesion treatment include corona treatment and plasma treatment.
- the photocurable adhesive is applied to at least one of the adhesive surfaces of the polarizer and the optical film.
- the application method is not particularly limited. For example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
- various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
- the method of pressurizing with a roller etc. and spreading uniformly can also be utilized.
- Bonding process For example, when a photocurable adhesive is applied to the surface of the polarizer in the previous application step, an optical film is superimposed thereon. When a photocurable adhesive is applied to the surface of the optical film in the previous application step, a polarizer is superimposed thereon. In addition, when a photocurable adhesive is cast between the polarizer and the optical film, the polarizer and the optical film are superposed in that state.
- the optical film is superimposed on the both surfaces of the polarizer via the photocurable adhesive.
- both sides if the optical film is superimposed on one side of the polarizer, the polarizer side and the optical film side, and if the optical film is superimposed on both sides of the polarizer,
- the film is pressed with a roll or the like from the film side).
- the material of the roll metal, rubber or the like can be used.
- the rollers arranged on both sides may be made of the same material or different materials.
- the active energy ray is irradiated to the uncured photocurable adhesive to cure the adhesive layer containing the epoxy compound or the oxetane compound.
- the overlapped polarizer and the optical film are bonded via the photocurable adhesive.
- an active energy ray is applied from either one of the optical films in a state where the optical film is superimposed on both surfaces of the polarizer via a photocurable adhesive. It is advantageous to irradiate and simultaneously cure the photocurable adhesive on both sides.
- active energy rays visible rays, ultraviolet rays, X-rays, electron beams and the like can be used, and since they are easy to handle and have a sufficient curing rate, electron beams or ultraviolet rays are generally preferably used.
- the acceleration voltage is preferably in the range of 5 to 300 kV, more preferably in the range of 10 to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetrating force through the sample is too strong and the electron beam rebounds. There is a risk of damaging the polarizer.
- the irradiation dose is in the range of 5 to 100 kGy, more preferably in the range of 10 to 75 kGy.
- the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the transparent optical film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.
- Arbitrary appropriate conditions can be employ
- the dose of ultraviolet rays in the range of 50 ⁇ 1500mJ / cm 2 in accumulated light amount, and even more preferably in the range of within the range of 100 ⁇ 500mJ / cm 2.
- the thickness of the adhesive layer is not particularly limited, but is usually in the range of 0.01 to 10 ⁇ m, and preferably in the range of 0.5 to 5 ⁇ m.
- the polarizing plate provided with the optical film of the present invention can be used for various display devices.
- a TN (Twisted Nematic) method an STN (Super Twisted Nematic) method, an IPS (In-Plane Switching) method, an OCB (Optically Compensated Birefringence) method, a VA (MicV) method, a VA (M) method, a VA method
- a TN Transmission Nematic
- STN Super Twisted Nematic
- IPS In-Plane Switching
- OCB Optically Compensated Birefringence
- VA Mov
- VA VA
- VA method a method
- PVA including patterned vertical alignment
- HAN hybrid aligned nematic
- the VA (MVA, PVA) method is preferable.
- the polarizing plate (circular polarizing plate) provided with the optical film of the present invention is preferable because it is arranged in the liquid crystal display device or on the surface portion to improve visibility. Especially, it is easy to express the effect of the said visibility by arrange
- the polarizing plate (circular polarizing plate) provided with the optical film of the present invention can be particularly preferably used for an organic EL image display device.
- the configuration of the organic EL display device is shown below, but is not limited thereto.
- the polarizer is combined with the optical film of the present invention.
- a polarizing plate (circular polarizing plate) according to the present invention sandwiched between protective films is provided to constitute an organic EL image display device. In this case, it is necessary to arrange the optical film of the present invention on the organic EL element side.
- the organic 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, Alternatively, a structure having various combinations such as a laminate of such a light-emitting layer and an electron injection layer made of a perylene derivative, or a stack of these hole injection layer, light-emitting layer, and electron injection layer is known. It has been.
- holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the phosphor 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 in the middle is the same as that of a general diode, and as can be predicted from this, the current and the emission intensity show strong nonlinearity with rectification with respect to the applied voltage.
- At least one of the electrodes needs to be transparent, and is usually formed of a transparent conductor such as indium tin oxide (ITO).
- ITO indium tin oxide
- the electrode is preferably used as the anode.
- metal electrodes such as Mg—Ag and Al—Li are used.
- the circularly polarizing plate having the optical film of the present invention can be applied to an organic EL image display device comprising a large screen having a screen size of 20 inches or more, that is, a diagonal distance of 50.8 cm or more.
- the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted to the surface side of the transparent substrate.
- the display surface of the organic EL image display device looks like a mirror surface.
- an organic EL image display device including an organic EL element having a transparent electrode on the surface side of an organic light emitting layer that emits light by applying a voltage and a metal electrode on the back side of the organic light emitting layer, the surface side of the transparent electrode ( By providing a circularly polarizing plate on the viewing side), light passing through it is transmitted through the transparent substrate, transparent electrode, and organic thin film, reflected by the metal electrode, and again transmitted through the organic thin film, transparent electrode, and transparent substrate. Then, since the circularly polarizing plate makes the linearly polarized light again, this linearly polarized light is orthogonal to the polarization direction of the polarizing plate, and cannot pass through the polarizing plate. As a result, the mirror surface of the metal electrode can be completely shielded.
- the obtained dope was uniformly cast on a stainless steel band support using a belt casting apparatus under the conditions of a dope temperature of 35 ° C. and a width of 1.8 m.
- the solvent in the obtained dope film was evaporated until the residual solvent amount reached 100% to obtain a web, and then the web was peeled from the stainless steel band support.
- the obtained web was further dried at 35 ° C. and then slit so as to have a width of 1.6 m.
- the web was pre-stretched 10% in the width direction (TD direction) by a tenter.
- the residual solvent amount at the start of stretching was 40% by mass, and the stretching temperature was 160 ° C.
- the film was stretched 100% in the direction of 45 ° obliquely with respect to the longitudinal direction (the film feed direction 107 in FIG. 5) by the oblique stretching tenter shown in FIG.
- the residual solvent amount of the web at the start of stretching was 20%, and the stretching temperature was 180 ° C.
- the obtained film was dried at 125 ° C. for 15 minutes while being conveyed by a number of rollers in the drying apparatus, slitted to a width of 2.4 m, and the height of the convex portion was 10 ⁇ m at both ends in the width direction.
- the embossed part (the width W of the embossed part: 15 mm) having a width w of the convex part of 100 ⁇ m and an interval between the convex parts of 1000 ⁇ m was formed. Embossing was performed under the following conditions.
- Embossed roller Material: Stainless steel Roller diameter: 30cm Surface temperature: Right embossed roller with respect to the longitudinal direction 180 ° C Left embossing roller for longitudinal direction 190 °C Back roller: Material: Metal (stainless steel) Temperature: 60 ° C Film transport speed: 90 m / min Transport tension: 120 N / m Clearance between emboss roller and back roller: 27 ⁇ m Nip pressure between emboss roller and back roller: 1000Pa Thus obtained long optical film having a width of 2.4 m, a length of 4000 m, and a film thickness of 15 ⁇ m was wound in the length direction to obtain a roll body 101 of the optical film.
- a region including the embossed portion 16 of the optical film 14 is cut out to obtain a sample film 14A (see FIG. 4). Then, (in FIG. 3, the height D 0 of the projections before the addition of load) sample film 14A height D of the convex portion of the embossed portion 16 of the zero, measured at a thickness measuring instrument.
- a thickness measuring machine a constant pressure thickness measuring machine (TECLOCK PG-02 Co., Ltd.) was used.
- the sample film 14 ⁇ / b> A is placed on the stage 15.
- the weight 18 of a total of 1 kg which consists of the metal cylindrical rod 18A of diameter 5mm mounted perpendicularly
- it is stored for 10 minutes at 23 ° C. and 55% RH in a state where a load of 1 kg is applied to a circular region having a diameter of 5 mm on the surface of the embossed portion 16.
- the height D of the convex portion of the embossed portion 16 when the load is removed (excluding the weight) (the height D of the convex portion after applying the load in FIG. 3) is measured with a thickness measuring machine. To do.
- Crush resistance ratio (%) D / D 0 ⁇ 100 (%) The measurement was carried out 10 times arbitrarily changing the location of the embossed part, and the average value of the crush resistance rate (%) was obtained.
- the elastic modulus in the optical film surface is measured by conditioning the sample for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 55% RH, and according to the method described in JIS K7127, a tensile tester Orientec Co., Ltd.
- the elastic modulus was determined using Tensilon RTA-100.
- the shape of the test piece is No. 1 test piece, the test speed is 10 mm / min, measured in the direction of 0 ° to 15 ° with respect to the arbitrary direction, and the maximum value of the obtained elastic modulus is the maximum.
- the elastic modulus and its direction were taken as the maximum value A, and the elastic modulus in the direction B perpendicular to the direction A was determined, and the ratio (B / A) was calculated.
- the angle of the slow axis in the optical film is measured by adjusting the humidity of the produced optical film at 23 ° C. and 55% RH, and then setting the direction of the slow axis to the automatic birefringence meter KOBRA-21AWR (Oji Scientific Instruments) )).
- the direction of the slow axis was determined by determining the angle of the slow axis in the film plane with the film longitudinal direction as 0 °.
- the retardation value Ro is measured by measuring the birefringence at the following wavelengths in an environment of 23 ° C. and 55% RH.
- Ro (450) measured at a wavelength of 450 nm is in the range of 100 to 125 nm
- Ro (550) measured at the wavelength of 550 nm is in the range of 125 to 142 nm
- Ro (590 ) Is in the range of 130 to 152 nm, and is a retardation film which is a ⁇ / 4 plate.
- nx and ny are refractive indexes nx (also referred to as the maximum refractive index in the plane of the film and the refractive index in the slow axis direction) at 23 ° C. and 55% RH, 450 nm, 550 nm, and 590 nm, ny. (Refractive index in the direction perpendicular to the slow axis in the film plane), and d is the thickness (nm) of the film.
- the roll body of the produced optical film was packaged using a moisture-proof film in which aluminum was deposited on a 30 ⁇ m-thick polyethylene resin film, and the end of the core was fastened with a rubber band. (See FIG. 10.)
- the packaged optical film roll was placed in a warehouse at 30 to 40 ° C. and 65 to 85% RH, and placed on a gantry so that the length direction of the core was horizontal and stored for one month. And the state of winding of the roll body after one month passed was visually observed and evaluated as follows.
- A No change or winding deviation of wrinkles or the like is observed on the roll surface.
- ⁇ Slight wrinkles are observed on the roll surface, but no winding deviation is observed.
- ⁇ Weak wrinkles are observed on the roll surface. Less than a winding deviation of less than X is observed: There is a strong wrinkle on the surface to the inside of the roll, and a winding deviation of 1 cm or more is recognized.
- the embossed portion of the optical film fed out from the roll of the optical film was slit and removed, and then bonded to a polarizer by the following procedure to produce a circularly polarizing plate.
- a laminated body in which a PVA layer having a thickness of 7 ⁇ m is formed on an amorphous PET base material is produced by air-assisted stretching at a stretching temperature of 130 ° C., and then the stretched laminated body is dyed with iodine or potassium iodide.
- a colored laminate is produced, and the colored laminate is further stretched integrally with an amorphous PET substrate so that the total draw ratio becomes 5.94 times by stretching in boric acid water at a stretching temperature of 65 degrees.
- the optical film laminated body (polarizer) containing the PVA layer of was obtained.
- the amorphous PET substrate was peeled off after the polarizer was bonded to the optical film, and only the PVA layer (polarizing film) was used.
- Triarylsulfonium hexafluorophosphate was blended as a 50% propylene carbonate solution, and the solid content of triarylsulfonium hexafluorophosphate was shown below.
- the above-prepared photocurable adhesive was applied to a dry thickness of 5 ⁇ m to form a photocurable adhesive layer. Formed.
- An optical film in which a photocurable adhesive layer is formed is disposed on one surface of the produced polarizer, and a protective film in which a photocurable adhesive layer is formed is disposed on the other surface.
- a laminate of film / photocurable adhesive layer / polarizer / photocurable adhesive layer / protective film was obtained.
- the obtained laminate was laminated with a roll-to-roll so that the longitudinal direction was matched with a roller machine.
- the slow axis of the optical film was bonded in a 45 ° oblique direction with respect to the absorption axis of the polarizer.
- the circularly polarizing plate 201 was obtained by irradiating an electron beam from both sides of the laminated laminate to cure the photocurable adhesive layer.
- the line speed was 20 m / min
- the acceleration voltage was 250 kV
- the irradiation dose was 20 kGy.
- an organic EL device having the configuration described in FIG. 8 of the same publication was produced according to the method described in the examples of Japanese Patent Application Laid-Open No. 2010-20925. Cut out the produced circularly polarizing plate on the surface opposite to the substrate of the organic EL element, and pasted it via an acrylic adhesive so that the optical film 101 side of the circularly polarizing plate becomes the organic EL element surface, An organic EL image display device was produced.
- a circularly polarizing plate and an organic EL image display device were manufactured using the roll members 102 to 130 of the optical film, respectively.
- the optical film is cut out every leaf and bonded in a 45 ° oblique direction with respect to the absorption axis of the polarizer to produce a circularly polarizing plate. did.
- the organic EL image display device produced above was lit in a dark room at 23 ° C. and 55% RH, and display unevenness was observed.
- the film thickness of the optical film, the ratio of the elastic modulus in the direction A perpendicular to the direction A of the maximum value of the elastic modulus in the film plane, and the height of the convex part of the embossed part are the present invention.
- the rolls 101 to 104, 106, 107, and 109 to 122 of the optical film of the present invention which are within the range and have a crush resistance ratio (%) of 50% or more at the embossed portions at both ends, It can be seen that the display unevenness after storage is excellent.
- the embossed portion is easily crushed by its own weight, so that winding deviation is observed and display unevenness occurs.
- the roll body 108 of the optical film in which the height of the convex portion of the embossed portion is out of the range is easy to bend in the center in the width direction of the roll body, and it is difficult to maintain the flatness as the optical film. Degradation was seen in both spots.
- the roll body 120 of the optical film having the elastic modulus ratio value E A / E B of less than 1.4, and the roll bodies 121 to 127 of the optical film having low crush resistance ratio (%) of the left and right embossed portions are wound. It is clear that the shift and display unevenness are inferior.
- the rolls 116 and 119 of the optical film of the present invention in which the angle of oblique stretching is set to 20 ° and 70 ° with respect to the roll 113 of the optical film of the present invention the display of the organic EL image display device is visually observed. As a result, the contrast was observed to be slightly low.
- Example 2 In the production of the roll body 102 of the optical film of Example 1, the rolls 201 to 201 of the optical film were similarly manufactured except that the pre-stretching ratio in the width direction (TD direction) was performed under the conditions shown in Table 2. 206 was produced.
- Example 2 In addition to the evaluation of winding deviation and display unevenness performed in Example 1, the following haze evaluation was performed on the produced roll body of the optical film.
- the obtained optical film was conditioned at 23 ° C. and 55% RH for 5 hours or more.
- the haze of the obtained optical film was measured according to JIS K-7136 under the conditions of 23 ° C. and 55% RH (haze meter) (model: NDH 2000, Nippon Denshoku Co., Ltd.). Manufactured) and evaluated according to the following criteria.
- Haze is less than 0.5% ⁇ : Haze is 0.5% to less than 1.0% ⁇ : Haze is 1.0% or more Table 2 shows the above evaluation results.
- Example 3 In the production of the roll body 102 of the optical film of Example 1, the film thickness and the temperature of the embossing roller were adjusted to change the average crush resistance ratio (%) of the left and right embossed portions, and the roll of the optical film described in Table 3 Body 301-306 was produced.
- the length direction of the core (core) in a warehouse form of 30 to 40 ° C. and 65 to 85% RH in the following AC packaging forms (see FIG. 10): Stored horizontally for 2 months. And the state of winding of the roll body after 2 months passed is visually observed in the same manner as in Example 1, evaluation of winding deviation, and the optical film is fed out from the roll body of each optical film, as in Example 1. Then, a circularly polarizing plate and an organic EL image display device were prepared, and display unevenness was evaluated.
- Packaging form A A roll body of an optical film was packaged using a moisture-proof film packaging material in which aluminum was deposited on a polyethylene resin film having a thickness of 50 ⁇ m, and the end portion of the core was fastened with a rubber band.
- the packaging material had a moisture permeability of 0.5 g / m 2 held for 24 hours in an environment of a temperature of 40 ° C. and a humidity of 90% RH based on the calcium chloride-cup method defined in JIS Z208.
- Packaging form B A roll of optical film is packaged using a packaging material in which aluminum is vapor-deposited on a 50 ⁇ m thick polyethylene resin film, and the end of the core is double-fastened with vinyl tape (gum tape), inside the package Was sealed.
- Packaging form C A roll of optical film was packaged using a polyethylene resin film having a thickness of 50 ⁇ m as a packaging material, and the end of the core was fastened with a rubber band.
- the moisture permeability of the packaging material according to the above conditions was 5.0 g / m 2 .
- Table 3 shows that the rolls 301 and 302 of the optical film adopting the packaging form A are superior to the other packaging forms B and C in terms of winding slip and display unevenness.
- Example 4 In preparation of the roll body 102 of the optical film of Example 1, as the additive 1, the compound A36 having a structure represented by the general formula (A), the following phase difference adjusting agent a, phase difference adjusting agent b, phase difference adjustment A polycondensation ester having the composition described in Table 4 was prepared as a polycondensation ester of dicarboxylic acid and diol as additive c, ethyl cellulose (substitution degree 2.8), and additive 2, and the same mass part as in Example 1 was used. In the same manner, optical film rolls 401 to 412 were produced. In that case, the packaging form of Example 1 was employ
- the packaging form of Example 1 was employ
- ⁇ Additive 2 Synthesis of polycondensed ester> (Synthesis of polycondensation ester used for optical film 401) 310 g of ethylene glycol, 415 g of terephthalic acid, 365 g of adipic acid, 300 g of acetic acid, and 0.21 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, stirrer, and slow cooling tube, and a nitrogen stream The temperature is gradually increased while stirring until the temperature reaches 230 ° C.
- the polycondensation ester was obtained by carrying out dehydration condensation reaction for 15 hours, and distilling off unreacted ethylene glycol under reduced pressure at 200 ° C. after completion of the reaction.
- the acid value was 0.10 and the number average molecular weight was 1000.
- Synthesis of polycondensation ester used for optical film 402 310 g of ethylene glycol, 730 g of adipic acid, 300 g of acetic acid, and 0.21 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2 L four-necked flask equipped with a thermometer, a stirrer, and a quick cooling tube, and heated to 230 ° C. in a nitrogen stream.
- the temperature is gradually raised while stirring until The polycondensation ester was obtained by carrying out dehydration condensation reaction for 15 hours, and distilling off unreacted ethylene glycol under reduced pressure at 200 ° C. after completion of the reaction.
- the acid value was 0.10 and the number average molecular weight was 1000.
- Example 1 Using the produced optical film roll body, the winding deviation and display unevenness were evaluated in the same manner as in Example 1.
- Example 5 In preparation of the roll body 102 of the optical film of Example 1, as cellulose ester, cellulose ester 1, 3 and the following cellulose ester 4, as additive 1, following compound 1 and 2, general formula (1) or (2)
- the following compounds 3 to 10 having the structure shown below, Exemplified compound P-8 as a polycondensation ester of dicarboxylic acid and diol as additive 2, and the same mass part as in Example 1, with a film thickness of 30 ⁇ m and a winding length of 6000 m Except that, optical film rolls 501 to 514 were produced in the same manner.
- the packaging form of Example 1 was employ
- Example 2 In addition to the evaluation of winding deviation and display unevenness performed in Example 1 on the produced optical film rolls 501 to 514, the following winding shape was evaluated.
- ⁇ Roll shape of optical film roll evaluation of winding quality> Visually observe the appearance of the 6000 m roll produced above and visually observe the winding quality of the optical film roll (horse spine failure due to loose winding, uneven deformation failure), and take up according to the following criteria: The quality was evaluated.
- the direction of the elastic modulus in the film plane is inclined with respect to the longitudinal direction, and the roll body is less likely to cause winding deviation due to moisture absorption during storage or transportation, and Since it has a uniform optical value even during storage or after transportation, it has excellent suitability for use as a protective film for polarizing plates and an optical film for display devices such as liquid crystal display devices.
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Abstract
Description
前記光学フィルムのロール体は、フィルム幅手方向の両端部からフィルム幅手長の5%以内の領域に、高さが1~20μmの範囲内であるエンボス部を有し、
当該エンボス部の表面上の直径5mmの円領域に、1kgの荷重を加えた状態で23℃・55%RH下において10分間保存した後の当該エンボス部の凸部の高さをDとし、前記荷重を加える前の当該エンボス部の凸部の高さをDoとしたとき、下記式1で定義されるつぶれ耐性率(%)が、両端のエンボス部とも50%以上であることを特徴とする光学フィルムのロール体。
2.前記つぶれ耐性率(%)が、70%以上であることを特徴とする第1項に記載の光学フィルムのロール体。
〔上記一般式(A)において、Qは、芳香族炭化水素環、非芳香族炭化水素環、芳香族複素環又は非芳香族複素環を表す。Wa及びWbは、それぞれ独立に、Qを構成する原子に結合する水素原子又は置換基であり、WaとWbとは互いに同じでも異なっていてもよく、WaとWbは互いに結合して環を形成してもよい。R3は、水素原子又は置換基を表す。mは、0~2の整数を表し、mが2の場合、2つのR3は互いに同じでも異なっていてもよい。nは、1~10の整数を表し、nが2以上である場合、2以上のQ、L2、Wa、Wb、R3及びmのそれぞれは、互いに同一であっても異なっていてもよい。L1及びL2は、それぞれ独立に、アルキレン基、アルケニレン基、アルキニレン基、O、(C=O)、(C=O)-O、NRL、S、(O=S=O)及び(C=O)-NRLからなる群より選ばれる2価の連結基であるか、それらの組合せか又は単結合を表す。RLは、水素原子又は置換基を表す。R1及びR2は、それぞれ独立に、置換基を表す。〕
7.添加剤として、重量平均分子量(Mw)が350~3000の範囲内であるジカルボン酸とジオールとの重縮合エステルを含有することを特徴とする第1項から第6項までのいずれか一項に記載の光学フィルムのロール体。
本発明の光学フィルムのロール体(以下、本発明の光学フィルムともいう。)は、セルロースエステルを含有し、膜厚が15~50μmの範囲内であり、23℃・55%RH下で測定したフィルム面内の弾性率の最大値の方向Aが長手方向に対して傾斜しており、当該最大値の方向Aの弾性率EAとそれに対して直交する方向Bの弾性率EBとの比の値が、1.4≦EA/EBである長尺の光学フィルムのロール体であって、
前記光学フィルムのロール体は、フィルム幅手方向の両端部からフィルム幅手長の5%以内の領域に、高さが1~20μmの範囲内であるエンボス部を有し、
当該エンボス部の表面上の直径5mmの円領域に、1kgの荷重を加えた状態で23℃・55%RH下において10分間保存した後の当該エンボス部の凸部の高さをDとし、前記荷重を加える前の当該エンボス部の凸部の高さをDoとしたとき、下記式1で定義されるつぶれ耐性率(%)が、両端のエンボス部とも50%以上であることを特徴とする。
本発明では、光学フィルムのロール体の保存時の巻きずれや光学品質の劣化を効果的に防止する観点から、請求項1で示すように、フィルムの両端部に特定の強度のエンボス部を形成することを特徴としている。
測定はエンボス部の場所を任意に変えて10回行い、つぶれ耐性率(%)の平均値を求める。
式(ii):Rt={(nx+ny)/2-nz}×d
式中、nx、ny及びnzは、23℃・55%RH、450nm、550nm、590nmの各々における屈折率nx(フィルムの面内の最大の屈折率、遅相軸方向の屈折率ともいう。)、ny(フィルム面内で遅相軸に直交する方向の屈折率)、nz(フィルム厚さ方向の屈折率)であり、dはフィルムの厚さ(nm)である。
本発明の光学フィルムは、セルロースエステルを含有し、更に光学特性及び物性向上のために添加剤を含有することが好ましい。
本発明の光学フィルムは、セルロースエステルを主成分として含有する。主成分とは、当該光学フィルム中のセルロースエステルの含有比率が55質量%以上、好ましくは70質量%以上であることをいう。
式(II) 0≦X≦2.5
中でも1.9≦X≦2.5、0.1≦Y≦0.9であることが好ましい。
カラム: Shodex K806、K805、K803G(昭和電工(株)製を3本接続して使用した)
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)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)製)Mw=1000000~500の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いる。
本発明の光学フィルムに含まれる添加剤の例には、可塑剤、酸化防止剤、光安定剤、紫外線吸収剤、リターデーション調整剤、帯電防止剤、及び剥離剤などが含まれ、好ましくは可塑剤である。
本発明の光学フィルムに含まれる添加剤として、下記一般式(A)で表される構造を有する化合物を用いることがリターデーションの調整の観点から好ましい。当該化合物は、1つの化合物で位相差上昇剤と波長分散調整剤の両方の機能を併せ持つ特徴を有していることから、斜め延伸適性が高く、かつセルロースエステルと組み合わせたときの吸湿による耐染みだし性にも優れていることから、ロール体の保管中及び輸送後の光学特性の均一性に優れた効果を有する。
前記一般式(1)において、A1、A2及びBは、ベンゼン環、ピロール環、ピラゾール環、イミダゾール環、1,2,3-トリアゾール環又は1,2,4-トリアゾール環を表すことが、光学特性の変動効果に優れ、かつ耐久性に優れた位相差フィルムが得られるために好ましい。
さらに、当該含窒素複素環化合物は、下記一般式(2)で表される構造を有する化合物であることが特に好ましい。
(式中Aはピラゾール環を表し、Ar1及びAr2はそれぞれ芳香族炭化水素環又は芳香族複素環を表し、置換基を有してもよい。R1は水素原子、アルキル基、アシル基、スルホニル基、アルキルオキシカルボニル基、又はアリールオキシカルボニル基を表し、qは1~2の整数を表し、n及びmは1~3の整数を表す。)
Ar1及びAr2で表される芳香族炭化水素環又は芳香族複素環は、それぞれ一般式(1)で挙げた5員若しくは6員の芳香族炭化水素環又は芳香族複素環であることが好ましい。また、Ar1及びAr2の置換基としては、前記一般式(1)で表される構造を有する化合物で示したのと同様な置換基が挙げられる。
可塑剤の例には、ポリエステル(本願では、重縮合エステルともいう。)、多価アルコールエステル、多価カルボン酸エステル(フタル酸エステルを含む)、グリコレート化合物、及び脂肪酸エステルやリン酸エステルなどが含まれる。これらは、単独で用いても、二種類以上を組み合わせて用いてもよい。
B-(G-A)n-G-B
一般式(II)
C-(A-G)n-A-C
一般式(I)及び(II)のAは、炭素原子数3~20(好ましくは4~12)のアルキレンジカルボン酸から誘導される2価の基、炭素原子数4~20(好ましくは4~12)のアルケニレンジカルボン酸から誘導される2価の基、又は炭素原子数8~20(好ましくは8~12)のアリールジカルボン酸から誘導される2価の基を表す。
P-2:コハク酸/フタル酸/エタンジオール/(1/1/2 モル比)からなる縮合物(重量平均分子量2500)の両末端のアセチルエステル化体
P-3:グルタル酸/イソフタル酸/1,3-プロパンジオール(1/1/2 モル比)からなる縮合物(重量平均分子量1300)の両末端のアセチルエステル化体
P-4: コハク酸/グルタル酸/アジピン酸/テレフタル酸/イソフタル酸/エタンジオール/1,2-プロパンジオール(1/1/1/1/1/3/2 モル比)からなる縮合物(数平均分子量3000)の両末端のプロピルエステル化体
P-5: コハク酸/フタル酸/エタンジオール/(1/1/2 モル比)からなる縮合物(重量平均分子量2100)の両末端のブチルエステル化体
P-6: アジピン酸/テレフタル酸/1,2-プロパンジオール(1/1/2 モル比)からなる縮合物(数平均分子量2500)の両末端の2-エチルヘキシルエステル化体
P-7: コハク酸/テレフタル酸/ポリ(平均重合度5)プロピレンエーテルグリコール/1,2-プロパンジオール(2/1/1/2モル比)からなる縮合物(重量平均分子量3500)の両末端の2-エチルヘキシルエステル化体
P-8:アジピン酸/フタル酸/1,2-プロパンジオール(3/1/3 モル比)からなる縮合物(重量平均分子量490)の両末端が安息香酸エステル化体
多価アルコールエステル化合物は、2価以上の脂肪族多価アルコールと、モノカルボン酸とのエステル化合物(アルコールエステル)であり、好ましくは2~20価の脂肪族多価アルコールエステルである。多価アルコールエステル化合物は、分子内に芳香環又はシクロアルキル環を有することが好ましい。
本発明の光学フィルムは、紫外線吸収剤を含有することが好ましい。紫外線吸収剤は400nm以下の紫外線を吸収することで、耐久性を向上させることを目的としており、特に波長370nmでの透過率が10%以下であることが好ましく、より好ましくは5%以下、更に好ましくは2%以下である。
酸化防止剤は劣化防止剤ともいわれる。高湿高温の状態に液晶画像表示装置などがおかれた場合には、光学フィルムの劣化が起こる場合がある。
光学フィルムは、表面の滑り性を高めるため、必要に応じて微粒子(マット剤)をさらに含有してもよい。
本発明の光学フィルムのロール体の製造方法は、(1)セルロースエステルと、添加剤とを溶剤に溶解させてドープを調製する工程、(2)ドープを無端の金属支持体上に流延する工程、(3)流延したドープから溶媒を蒸発させてウェブを得る工程、(4)ウェブを金属支持体から剥離する工程、(5)ウェブを乾燥後、斜め延伸してフィルムを得る工程、(6)フィルムの幅手方向の両端部にエンボス加工を施す工程、(7)フィルムを巻き取る工程、を経て製造することができる。(5)の工程は幅手方向又は長手方向への延伸(予備延伸)を含む工程である。
溶解釜において、セルロースエステルと、添加剤とを溶剤に溶解させてドープを調製する。
ドープを、加圧ダイのスリットから無端状の金属支持体(例えばステンレスベルトや回転する金属ドラムなど)上に流延させる。
ドープ膜を金属支持体上で加熱して溶剤を蒸発させて、ウェブを得る。
得られたウェブを、金属支持体上の剥離位置で剥離する。金属支持体上の剥離位置における温度は、好ましくは10~40℃の範囲であり、さらに好ましくは11~30℃の範囲である。
金属支持体から剥離して得られたウェブを乾燥させる。ウェブの乾燥は、ウェブを、上下に配置した多数のローラーにより搬送しながら乾燥させてもよいし、ウェブの両端部をクリップで固定して搬送しながら乾燥させてもよい。
本発明の光学フィルムのロール体は、フィルム長手方向に対して斜め延伸された光学フィルムであることを特徴とする。
本発明に用いられる斜め延伸テンターにおいて、把持具の軌跡を規制するレールには、しばしば大きい屈曲率が求められる。急激な屈曲による把持具同士の干渉、あるいは局所的な応力集中を避ける目的から、屈曲部では把持具の軌跡が円弧を描くようにすることが望ましい。
なお、Mはウェブ又はフィルムの延伸前の時点で採取した試料の質量で、NはMを115℃で1時間の加熱後の質量である。
延伸後に得られたフィルムの幅手方向両端部にエンボス加工を施す。図9は、エンボス加工装置20の一例を示す模式図である。図9に示されるように、エンボス加工装置は、エンボスローラー22と、フィルム14を介してエンボスローラー22と対向配置されたバックローラー24とを有する。
得られた長尺状の光学フィルムを、巻き取り機を用いて、フィルムの長さ方向(幅手方向に対して垂直方向)に巻き取る。
本発明の光学フィルムのロール体の製造方法は、前記溶液流延製膜法に限られるものではなく、溶融製膜法によって製膜しても良い。溶融製膜法は、樹脂及び可塑剤などの添加剤を含む組成物を、流動性を呈する温度まで加熱溶融し、その後、流動性のセルロースエステルを含む溶融物を流延する成形方法である。
本発明の光学フィルムのロール体は、樹脂フィルム、なかでも好ましくは樹脂フィルムにアルミ蒸着された防湿フィルムで包んだ後、巻き軸部分を紐若しくはゴムバンドで留めた保管形態にすることが好ましい。
側面の全体が、シート状の包装材料(203) により覆われており、包装材料(203) のロール周方向の両端部が互いに重ね合わせられ、これら包装材料(203) 端部同士の接合部分にガムテープ(204) が貼り付けられて、包装材料(203) 端部同士の接触部分に実質的に隙間がなく、内部へのゴミ等の侵入を防ぐようにするとともに、ロール状フィルムの左右両端部より外側に突出した巻芯(201) の両端部(201a)、(201a)の周面と包装材料(203) の左右両端部との接合部分は紐又はゴムバンド(205) で留められて、巻芯両端部(201a)、(201a)の周面と包装材料(203) の左右両端部との間に実質的にわずかな隙間があり、緩い密閉状態となされているものである形態が好ましい。従来のように、左右両端部をガムテープで何重にも留めて、実質的に隙間がなく内部を密閉状態とするよりも、巻き軸部分を紐若しくはゴムバンドで留めた形態であることが、保管中又は輸送中にロール体の適度な吸湿及び放湿が可能となり、光学フィルムの光学特性及び物性の均一性を高める上で好ましい態様である。
(表面粗さ)
本発明の光学フィルム表面の算術平均粗さRaとしては、おおむね1.3~4.0nmの範囲内であり、好ましくは1.6~3.5nmの範囲内である。
本発明の光学フィルムを、有機EL画像表示装置に具備した場合、使用する環境雰囲気、例えば、高湿環境下での吸湿による寸法変化により、ムラや位相差値の変化、及びコントラストの低下や色むらといった問題を発生させない為に、本発明の光学フィルムの寸法変化率(%)は、0.5%未満であることが好ましく、更に、0.3%未満であることが好ましく、最も好ましくは0.1%未満である。
本発明の光学フィルムでは、フィルム中の故障(以下、欠点ともいう)が少ないことが好ましく、ここでいう欠点とは、溶液流延法により製膜において、乾燥工程での溶媒の急激な蒸発に起因して発生するフィルム中の空洞(発泡欠点)や、製膜原液中の異物や製膜中に混入する異物に起因するフィルム中の異物(異物欠点)をいう。
また、本発明の光学フィルムは、JIS-K7127-1999に準拠した測定において、少なくとも一方向(TD方向又はMD方向)の破断伸度が、4%以上であることが好ましく、より好ましくは10%以上である。
本発明の光学フィルムは、その全光線透過率が90%以上であることが好ましく、より好ましくは93%以上である。また、現実的な上限としては、99%程度である。かかる全光線透過率にて表される優れた透明性を達成するには、可視光を吸収する添加剤や共重合成分を導入しないようにすることや、ポリマー中の異物を高精度濾過により除去し、フィルム内部の光の拡散や吸収を低減させることが有効である。また、製膜時のフィルム接触部(冷却ローラー、カレンダーローラー、ドラム、ベルト、溶液製膜における塗布基材、搬送ローラーなど)の表面粗さを小さくしてフィルム表面の表面粗さを小さくすることによりフィルム表面の光の拡散や反射を低減させることが有効である。
本発明の光学フィルムのロール体から繰り出された長尺状の光学フィルムは、斜め延伸することによって遅相軸の角度(即ち配向角θ)が長手方向に対して好ましくは「実質的に45°」方向にあり、透過軸(又は吸収軸)が長手方向にある長尺状の偏光子とロール・トゥ・ロールで貼合することで、長尺状の円偏光板を形成することができる。
前処理工程では、光学フィルムの、偏光子との接着面に易接着処理を行う。偏光子の両面にそれぞれ光学フィルムを接着させる場合は、それぞれの光学フィルムの、偏光子との接着面に易接着処理を行う。易接着処理としては、コロナ処理、プラズマ処理等が挙げられる。
接着剤塗布工程では、偏光子と光学フィルムとの接着面のうち少なくとも一方に、上記光硬化性接着剤を塗布する。偏光子又は光学フィルムの表面に直接光硬化性接着剤を塗布する場合、その塗布方法に特別な限定はない。例えば、ドクターブレード、ワイヤーバー、ダイコーター、カンマコーター、グラビアコーター等、種々の塗工方式が利用できる。また、偏光子と光学フィルムの間に、光硬化性接着剤を流延させた後、ローラー等で加圧して均一に押し広げる方法も利用できる。
こうして光硬化性接着剤を塗布した後、貼合工程に供される。この貼合工程では、例えば、先の塗布工程で偏光子の表面に光硬化性接着剤を塗布した場合、そこに光学フィルムが重ね合わされる。先の塗布工程で光学フィルムの表面に光硬化性接着剤を塗布した場合は、そこに偏光子が重ね合わされる。また、偏光子と光学フィルムの間に光硬化性接着剤を流延させた場合は、その状態で偏光子と光学フィルムとが重ね合わされる。偏光子の両面に光学フィルムを接着する場合であって、両面とも光硬化性接着剤を用いる場合は、偏光子の両面にそれぞれ、光硬化性接着剤を介して光学フィルムが重ね合わされる。そして通常は、この状態で両面(偏光子の片面に光学フィルムを重ね合わせた場合は、偏光子側と光学フィルム側、また偏光子の両面に光学フィルムを重ね合わせた場合は、その両面の光学フィルム側)からロール等で挟んで加圧することになる。ロールの材質は、金属やゴム等を用いることが可能である。両面に配置されるローラーは、同じ材質であってもよいし、異なる材質であってもよい。
硬化工程では、未硬化の光硬化性接着剤に活性エネルギー線を照射して、エポキシ化合物やオキセタン化合物を含む接着剤層を硬化させる。それにより、光硬化性接着剤を介して重ね合わせた偏光子と光学フィルムとを接着させる。偏光子の片面に光学フィルムを貼合する場合、活性エネルギー線は、偏光子側又は光学フィルム側のいずれから照射してもよい。また、偏光子の両面に光学フィルムを貼合する場合、偏光子の両面にそれぞれ光硬化性接着剤を介して光学フィルムを重ね合わせた状態で、いずれか一方の光学フィルム側から活性エネルギー線を照射し、両面の光硬化性接着剤を同時に硬化させるのが有利である。
本発明の光学フィルムを具備した偏光板は、種々の表示装置に用いることができる。 液晶表示装置の場合は、TN(Twisted Nematic)方式、STN(Super Twisted Nematic)方式、IPS(In-Plane Switching)方式、OCB(Optically Compensated Birefringence)方式、VA(Vertical Alignment)方式(MVA;Multi-domain Vertical AlignmentやPVA;Patterned Vertical Alignmentも含む)、HAN(Hybrid Aligned Nematic)等に好ましく用いることができる。コントラストを高めるためには、VA(MVA、PVA)方式が好ましい。
本発明の光学フィルムを具備した偏光板(円偏光板)は、上記液晶表示装置の内部又は表面部位に配置されることで、視認性が向上する効果もあり好ましい。中でも、視認側の偏光板(円偏光板)として配置することで当該視認性向上の効果が発現しやすく、好ましい実施態様である。
<実施例に用いるセルロースエステル>
セルロースエステル1:アセチル基置換度(アシル基の総置換度)2.88、重量平均分子量Mw=220000、数平均分子量Mn=90000、Mw/Mn=2.4
セルロースエステル2:アセチル基置換度(アシル基の総置換度)2.35、重量平均分子量Mw=215000、数平均分子量Mn=100000、Mw/Mn=1.5
セルロースエステル3:アセチル基置換度1.50、プロピオニル基置換度0.90、総アシル基置換度2.40、重量平均分子量Mw=160000、数平均分子量Mn=100000、Mw/Mn=2.2
<光学フィルムのロール体101の作製>
〈インライン添加液の調製〉
10質量部のアエロジル972V(日本アエロジル社製、一次粒子の平均径16nm、見掛け比重90g/リットル)と、90質量部のメタノールとをディゾルバーで30分間撹拌混合した後、マントンゴーリンで分散させて、微粒子分散液を得た。
下記成分を密閉容器に投入し、加熱及び撹拌しながら完全に溶解させた。得られた溶液を安積濾紙(株)製の安積濾紙No.24で濾過して、主ドープを得た。
セルロースエステル1(アセチル基置換度(アシル基の総置換度)2.88、Mw=220000、Mn=90000、Mw/Mn=2.4)
100質量部
添加剤1:一般式(A)で表される構造を有する化合物(例示化合物A5)
5質量部
添加剤2:ポリエステル化合物(アジピン酸/テレフタル酸/エチレングリコール(モル比50/50/100)からなる重縮合エステルの末端アセチル基封止物:例示化合物(23)のm=1、n=1、重量平均分子量1000)
10質量部
ジクロロメタン 430質量部
メタノール 40質量部
100質量部の主ドープと、2.5質量部のインライン添加液とを、インラインミキサー(東レ静止型管内混合機 Hi-Mixer、SWJ)で十分に混合してドープを得た。
エンボスローラー:
材質:ステンレス製
ローラー径:30cm
表面温度:長手方向に対して右エンボスローラー 180℃
長手方向に対して左エンボスローラー 190℃
バックローラー:
材質:金属製(ステンレス製)
温度:60℃
フィルムの搬送速度:90m/分
搬送張力:120N/m
エンボスローラーとバックローラーとのクリアランス:27μm
エンボスローラーとバックローラーとによるニップ圧:1000Pa
このようにして得られた、幅2.4m、長さ4000m、膜厚15μmの長尺状の光学フィルムを、長さ方向に巻き取って光学フィルムのロール体101を得た。
光学フィルムのロール体101の作製において、表1に記載のように、斜め延伸を行うときの延伸率、フィルム長手方向に対する延伸の角度、光学フィルムの膜厚、エンボス部の凸部の高さ、及び左右のエンボスローラーの温度をそれぞれ変化させてエンボス部を形成した以外は同様にして、幅2.4m、長さ4000m、の長尺状の光学フィルムを、長手方向に巻き取って光学フィルムのロール体102~130を作製した。
〈耐エンボスつぶれ率(%)の測定〉
光学フィルム左右両端部のエンボス部凸部のつぶれ耐性率を、図3及び図4で示す測定方法で行った。下記符号は図3及び図4中の符号である。
測定はエンボス部の場所を任意に変えて10回行い、つぶれ耐性率(%)の平均値を求めた。
光学フィルム面内の弾性率の測定は、温度23℃、相対湿度55%RHの環境下で試料を24時間調湿し、JIS K7127に記載の方法に準じて、引っ張り試験器オリエンテック(株)製テンシロンRTA-100を使用して弾性率を求めた。試験片の形状は1号形試験片で、試験速度は10mm/分の条件で、任意方向に対し0°から15°毎の方向に測定し、求めた弾性率のうち最大値のものを最大弾性率及びその方向を最大値の方向Aとし、更にその方向Aに直交する方向Bの弾性率をそれぞれ求め、さらにその比(B/A)を計算した。
光学フィルム面内の遅相軸の角度測定は、作製した光学フィルムを23℃・55%RHで調湿し、その後遅相軸の方向を自動複屈折率計KOBRA-21AWR(王子計測機器(株)製)により求めた。遅相軸の方向は、フィルム長手方向を0°としてフィルム面内の遅相軸の角度を決定した。
式中、nx及びnyは、23℃・55%RH、450nm、550nm、590nmの各々における屈折率nx(フィルムの面内の最大の屈折率、遅相軸方向の屈折率ともいう。)、ny(フィルム面内で遅相軸に直交する方向の屈折率)であり、dはフィルムの厚さ(nm)である。
作製した光学フィルムのロール体を、厚さ30μmのポリエチレン樹脂フィルムにアルミニウムが蒸着されている防湿フィルムを用いて包装し、巻き芯端部を輪ゴム留めした。(図10参照。)
包装された光学フィルムのロール体を、30~40℃、65~85%RHの倉庫で、コア(巻芯)の長さ方向が水平になるように架台に乗せ1ヶ月間保管した。そして、1ヶ月経過後のロール体の巻きの状態を、目視観察し、下記のように評価した。
○:ロールの表面に僅かに皺が認められるが、巻きずれは認められない
△:ロールの表面に弱い皺が認められ、1cm未満の巻きずれが認められる
×:ロールの表面~内部に強い皺が有り、1cm以上の巻きずれが認められる
〈有機EL表示装置の表示むらの評価〉
(円偏光板の作製)
作製した光学フィルムのロール体を、厚さ30μmのポリエチレン樹脂フィルムにアルミニウムが蒸着されている防湿フィルムを用いて包装し、巻き芯端部を輪ゴム留めし、30~40℃、65~85%RHの倉庫で、コア(巻芯)の長さ方向が水平になるように架台に乗せ1ヶ月間保管した。
特許第4691205号実施例1を参考にして下記偏光子を作製した。
下記成分を混合した後、脱泡して、光硬化性接着剤を調製した。なお、トリアリールスルホニウムヘキサフルオロホスフェートは、50%プロピレンカーボネート溶液として配合し、下記にはトリアリールスルホニウムヘキサフルオロホスフェートの固形分量を表示した。
3,4-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート:45質量部
エポリードGT-301(ダイセル化学社製の脂環式エポキシ樹脂):40質量部
1,4-ブタンジオールジグリシジルエーテル:15質量部
トリアリールスルホニウムヘキサフルオロホスフェート:2.3質量部
9,10-ジブトキシアントラセン:0.1質量部
1,4-ジエトキシナフタレン:2.0質量部
(3)円偏光板及び有機EL画像表示装置の作製
保管した光学フィルムのロール体101から繰り出した光学フィルム上に、上記調製した光硬化性接着剤を、マイクログラビアコーターを用いて乾燥厚みが5μmになるように塗布して、光硬化性接着剤層を形成した。塗布は、グラビアローラ#300、回転速度140%/ライン速度の条件で行った。
○ :極く弱いむらが表示装置の端部に観察される
△ :弱いむら表示装置の端部に明らかに観察される
× :表示装置の端部から中央にかけてむらが観察される
××:全面で強度のむらが観察される
以上の評価結果を表1に示した。
実施例1の光学フィルムのロール体102の作製において、幅手方向(TD方向)への予備延伸の倍率を表2に記載の条件で行った以外は同様にして、光学フィルムのロール体201~206を作製した。
得られた光学フィルムを、23℃・55%RH下で5時間以上調湿した。次いで、得られた光学フィルムのヘイズを、JIS K-7136に準拠して、23℃・55%RHの条件下で、ヘイズメーター(濁度計)(型式:NDH 2000、日本電色(株)製)にて測定し、以下の基準で評価した。
△:ヘイズが0.5%~1.0%未満
×:ヘイズが1.0%以上
以上の評価結果を表2に示した。
実施例1の光学フィルムのロール体102の作製において、膜厚、及びエンボスローラーの温度を調整して左右エンボス部の平均つぶれ耐性率(%)を変化させて、表3記載の光学フィルムのロール体301~306を作製した。
実施例1の光学フィルムのロール体102の作製において、添加剤1として、一般式(A)で表される構造を有する化合物A36、下記位相差調整剤a、位相差調整剤b、位相差調整剤c、及びエチルセルロース(置換度2.8)、及び添加剤2としてジカルボン酸とジオールの重縮合エステルとして表4記載の組成の重縮合エステルを作製し、実施例1と同質量部用いた以外は同様にして、光学フィルムのロール体401~412を作製した。その際、光学フィルムのロール体の包装形態は、実施例1の包装形態を採用した。
(光学フィルム401に使う重縮合エステルの合成)
エチレングリコール310g、テレフタル酸415g、アジピン酸365g、酢酸300g、エステル化触媒としてテトライソプロピルチタネート0.21g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する。15時間脱水縮合反応させ、反応終了後200℃で未反応のエチレングリコールを減圧留去することにより、重縮合エステルを得た。酸価0.10、数平均分子量1000であった。
(光学フィルム402に使う重縮合エステルの合成)
エチレングリコール310g、アジピン酸730g、酢酸300g、エステル化触媒としてテトライソプロピルチタネート0.21g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する。15時間脱水縮合反応させ、反応終了後200℃で未反応のエチレングリコールを減圧留去することにより、重縮合エステルを得た。酸価0.10、数平均分子量1000であった。
実施例1の光学フィルムのロール体102の作製において、セルロースエステルとして、セルロースエステル1、3及び下記セルロースエステル4、添加剤1として、下記化合物1及び2、一般式(1)又は(2)で表される構造を有する下記化合物3~10、及び添加剤2としてジカルボン酸とジオールの重縮合エステルとして例示化合物P-8を、実施例1と同質量部用い、膜厚30μm、巻き長を6000mとした以外は同様にして、光学フィルムのロール体501~514を作製した。その際、光学フィルムのロール体の包装形態は、実施例1の包装形態を採用した。
上記作製した6000m巻のロールの外観を目視観察し、光学フィルムロールの巻き取り品質(ゆる巻きに起因する馬の背状故障、凹凸状の変形故障)について目視観察を行い、下記の基準に従って、巻き取り品質の評価を行った。
○:光学フィルムロールに、ゆる巻きに起因する馬の背状故障、凹凸状の変形故障の発生はほぼ認められない
△:光学フィルムロールに、ゆる巻きに起因する馬の背状故障又は凹凸状の変形故障の発生がごく弱く見られるが、実用上問題の無い品質である
×:光学フィルムロールに、ゆる巻きに起因する馬の背状故障又は凹凸状の変形故障の発生が見られ、実用上懸念される品質である
上記評価の結果を、下記表5に示す。
12 巻芯
14 光学フィルム
14A サンプルフィルム
15 ステージ
16 エンボス部
18A 円筒棒
18B 分銅
18 重り
20 エンボス加工装置
22 エンボスローラー
24 バックローラー
100 未延伸フィルム
102-1 右側のフィルム保持開始点
102-2 左側のフィルム保持開始点
103-1 右側のフィルム保持手段の軌跡
103-2 左側のフィルム保持手段の軌跡
104 テンター
105-1 右側のフィルム保持終了点
105-2 左側のフィルム保持終了点
106 斜め延伸フィルム
107 フィルムの送り方向
108-1 テンター入り口側のガイドローラー
108-2 テンター出口側のガイドローラー
109 フィルムの延伸方向
DR1 繰出し方向
DR2 巻取り方向
θi 繰出し角度(繰出し方向と巻取り方向のなす角度)
CR、CL 把持具
Wo 延伸前のフィルムの幅
W 延伸後のフィルムの幅
110 フィルム繰り出し装置
111 搬送方向変更装置
112 巻き取り装置
113 製膜装置
201 巻芯
201a 巻芯の両端部
203 包装材料
204 ガムテープ
205 紐又はゴムバンド
210 光学フィルムのロール体の包装形態
Claims (13)
- セルロースエステルを含有し、膜厚が15~50μmの範囲内であり、23℃・55%RH下で測定したフィルム面内の弾性率の最大値の方向Aが長手方向に対して傾斜しており、当該最大値の方向Aの弾性率EAとそれに対して直交する方向Bの弾性率EBとの比の値が、1.4≦EA/EBである長尺の光学フィルムのロール体であって、
前記光学フィルムのロール体は、フィルム幅手方向の両端部からフィルム幅手長の5%以内の領域に、高さが1~20μmの範囲内であるエンボス部を有し、
当該エンボス部の表面上の直径5mmの円領域に、1kgの荷重を加えた状態で23℃・55%RH下において10分間保存した後の当該エンボス部の凸部の高さをDとし、前記荷重を加える前の当該エンボス部の凸部の高さをDoとしたとき、下記式1で定義されるつぶれ耐性率(%)が、両端のエンボス部とも50%以上であることを特徴とする光学フィルムのロール体。
(式1) つぶれ耐性率(%)=D/Do×100(%) - 前記つぶれ耐性率(%)が、70%以上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ロール体。
- 前記フィルム幅手方向の両端部のエンボス部をa及びa'としたときに、当該エンボス部a及びa'の前記つぶれ耐性率の差が、10%以内であることを特徴とする請求項1又は請求項2に記載の光学フィルムのロール体。
- 前記フィルム面内の弾性率の最大値の方向Aが、長手方向に対して、30~60°方向の範囲内にあることを特徴とする請求項1から請求項3までのいずれか一項に記載の光学フィルムのロール体。
- 前記フィルム面内の遅相軸が、長手方向に対して、30~60°方向の範囲内にあることを特徴とする請求項1から請求項4までのいずれか一項に記載の光学フィルムのロール体。
- 添加剤として、下記一般式(A)で表される構造を有する化合物を含有することを特徴とする請求項1から請求項5までのいずれか一項に記載の光学フィルムのロール体。
〔上記一般式(A)において、Qは、芳香族炭化水素環、非芳香族炭化水素環、芳香族複素環又は非芳香族複素環を表す。Wa及びWbは、それぞれ独立に、Qを構成する原子に結合する水素原子又は置換基であり、WaとWbとは互いに同じでも異なっていてもよく、WaとWbは互いに結合して環を形成してもよい。R3は、水素原子又は置換基を表す。mは、0~2の整数を表し、mが2の場合、2つのR3は互いに同じでも異なっていてもよい。nは、1~10の整数を表し、nが2以上である場合、2以上のQ、L2、Wa、Wb、R3及びmのそれぞれは、互いに同一であっても異なっていてもよい。L1及びL2は、それぞれ独立に、アルキレン基、アルケニレン基、アルキニレン基、O、(C=O)、(C=O)-O、NRL、S、(O=S=O)及び(C=O)-NRLからなる群より選ばれる2価の連結基であるか、それらの組合せか又は単結合を表す。RLは、水素原子又は置換基を表す。R1及びR2は、それぞれ独立に、置換基を表す。〕 - 添加剤として、重量平均分子量(Mw)が350~3000の範囲内であるジカルボン酸とジオールとの重縮合エステルを含有することを特徴とする請求項1から請求項6までのいずれか一項に記載の光学フィルムのロール体。
- 光学フィルムの巻き長が、1500~8000mの範囲内であることを特徴とする請求項1から請求項7までのいずれか一項に記載の光学フィルムのロール体。
- 請求項1から請求項8までのいずれか一項に記載の光学フィルムのロール体を樹脂フィルムにアルミ蒸着された防湿フィルムで包んだ後、巻き軸部分を紐又はゴムバンドで留めたことを特徴とする光学フィルムのロール体。
- 請求項1から請求項9までのいずれか一項に記載の光学フィルムのロール体を製造する光学フィルムのロール体の製造方法であって、当該光学フィルムをフィルム幅手方向に延伸率として1~50%の範囲内で予備延伸した後、フィルム長手方向に対して斜め方向に延伸し、その後フィルム幅手方向の両端部にエンボス部を形成することを特徴とする光学フィルムのロール体の製造方法。
- フィルム幅手方向の両端部にエンボスローラーによって前記エンボス部を形成するときに、両側のエンボスローラーの表面温度に5~20℃の範囲内の温度差をつけて当該エンボス部を形成することを特徴とする請求項10に記載の光学フィルムのロール体の製造方法。
- 請求項1から請求項9までのいずれか一項に記載の光学フィルムのロール体から繰り出され光学フィルムを、偏光子の少なくとも一方の面に具備したことを特徴とする偏光板。
- 請求項12に記載の偏光板を具備することを特徴とする表示装置。
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