WO2009119328A1 - 光学フィルムの製造方法及び光学フィルム - Google Patents
光学フィルムの製造方法及び光学フィルム Download PDFInfo
- Publication number
- WO2009119328A1 WO2009119328A1 PCT/JP2009/054754 JP2009054754W WO2009119328A1 WO 2009119328 A1 WO2009119328 A1 WO 2009119328A1 JP 2009054754 W JP2009054754 W JP 2009054754W WO 2009119328 A1 WO2009119328 A1 WO 2009119328A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- roll
- stretching
- temperature
- thermoplastic resin
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—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
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
-
- 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
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
Definitions
- the present invention relates to an optical film manufacturing method and an optical film.
- liquid crystal display devices have been developed to be thinner and lighter, larger screens and higher definition. Accordingly, demands for widening, thinning, and high quality of optical films (phase difference compensation films) used for improving the viewing angle and contrast of liquid crystal display devices are increasing rapidly.
- the retardation in the film plane and the film thickness direction, the uniformity of the orientation angle, the uniformity of the film thickness, etc. are controlled with high precision.
- sequential biaxial stretching consisting of longitudinal and lateral sequential stretching is generally used.
- the film 91 is heated and softened in the heating furnace 90, and the rotational speed of the take-off roll 92 at the outlet is increased with respect to the rotational speed of the feed-side drive roll 99 to stretch the film 91.
- the substantial stretch span between the low speed roller 93 and the high speed roller 94 (distance between the upstream end of the heater in the thermoplastic resin film transport direction and the position in contact with the downstream transport roll)
- a roll stretching method in which the film 91 is heated and softened by the heaters 95 and 96 and stretched within a substantially stretching span.
- necking when a film is stretched in the take-up direction, the film shrinks in the width direction (hereinafter referred to as necking).
- the heating medium of the film is due to air or radiation
- the heating zone is long
- the free state where the film is not bound to the roll is also long and necking is very large, but the film thickness is relatively uniform .
- the shrinkage of the width due to necking is large, and it has not been able to sufficiently meet the recent demand for widening.
- FIG. 12 schematically shows a change in thickness in the film width direction when the roll stretching method is used. This thick film portion at the end of the film is not preferable from the standpoint of product quality and is eliminated by trimming. However, the problem remains that the central portion is thin and both end portions are thick, and the quality of the optical film is lowered.
- a tenter method is used in which a clip holding the end of the film 91 spreads in the width direction while traveling along the endless rail 97 as shown in FIG.
- a so-called bowing phenomenon occurs in which the straight line (L1) drawn on the film before stretching is deformed into an arcuate curve (L2) after transverse stretching as shown in FIG. To do.
- L1 straight line drawn on the film before stretching
- L2 arcuate curve
- Patent Document 1 proposes a method of maintaining the process from stretching to the tenter outlet at a temperature equal to or lower than the glass transition temperature. According to Patent Document 1, bowing can be reduced and good optical characteristics can be obtained.
- An object of the present invention has been made in view of the above-mentioned problems of the prior art, and in successive biaxial stretching in which the thermoplastic resin film is stretched in the longitudinal direction and then in the transverse direction, there is little bowing and thickness unevenness is suppressed.
- An object of the present invention is to provide an optical film manufacturing method capable of manufacturing an optical film having good optical characteristics, and an optical film manufactured by the method.
- the present inventor has suppressed the decrease in film thickness at the center by changing the temperature in the width direction of the film in the longitudinal stretching step, and daredly after longitudinal stretching.
- the bowing generated in the transverse stretching process and the bowing generated in the longitudinal stretching process are offset, and the film thickness after biaxial stretching is made uniform. It has been found that both the suppression of bowing can be improved and an optical film having excellent optical properties can be produced, and the present invention has been completed.
- thermoplastic resin film in the longitudinal direction between two transport rolls; and a transverse stretching step of stretching the thermoplastic resin film in the width direction after the longitudinal stretching step.
- the temperature of both ends of the thermoplastic resin film in the width direction is higher than the temperature of the center portion of the thermoplastic resin film in the width direction.
- thermoplastic resin film is heated by an infrared heater disposed between the two transport rolls, An end on the upstream side in the transport direction of the thermoplastic resin film in the infrared heater; The distance from the position where the thermoplastic resin film is in contact with the roll on the downstream side in the conveyance direction of the thermoplastic resin film among the two conveyance rolls is 50 mm or more and 300 mm or less.
- thermoplastic resin film is heated by a hot air blower that blows hot air from the both end portions toward the central portion.
- thermoplastic resin film after the longitudinal stretching step is 20 ⁇ m or more and 150 ⁇ m or less.
- thermoplastic resin film is 1500 mm or more and 4000 mm or less.
- thermoplastic resin film is a heat-meltable film.
- thermoplastic resin film is a cellulose ester film.
- the film thickness after stretching can be uniform, bowing can be suppressed, and an optical film having excellent optical properties over the entire film surface can be produced.
- thermoplastic resin film in the width direction is higher than the temperature of the center portion of the thermoplastic resin film in the width direction.
- FIG. 1A and 1B show a side view and a cross-sectional view of a stretching apparatus which is an embodiment of a longitudinal stretching process and a lateral stretching process according to the present invention.
- the longitudinal stretching apparatus 10 is a roll stretching method performed between a first transport roll 11 and a second transport roll 13 that are close to each other.
- the nip rolls 12 and 14 and an infrared heater 15 disposed between the two transport rolls.
- the reflector 16 is provided.
- the long thermoplastic resin film 17 is nipped and transported by the transport rolls 11 and 13 and the nip rolls pressed against the transport rolls 11 and 13.
- the second transport roll 13 rotates at a higher speed than the first transport roll 11, and the film heated and softened by the infrared heater 15 between the transport rolls 11 and 13 is longitudinally stretched in the transport direction.
- the film 17 that has been stretched in the longitudinal direction is then stretched in the transverse direction by the transverse stretching apparatus 20.
- the distance between the infrared heater 15 and the thermoplastic resin film 17 is relative to the distance d1 from the film end in the film width direction.
- the distance d2 from the center is set to be long.
- the temperature of the width direction both ends of the film at the time of longitudinal stretching is higher than the temperature of a center part.
- the film thickness of the film after longitudinal stretching can be made uniform in the width direction because the temperature at both ends in the film width direction is higher than the temperature at the center.
- the both ends of a film show the area
- the temperature of the film end in the film width direction is increased by 1 ° C. to 20 ° C. from the center of the film and stretched in the longitudinal direction. Is preferred. By setting the temperature within this range, the film thickness after longitudinal stretching can be made more uniform. More preferably, the temperature is increased in the range of 5 ° C to 15 ° C. By increasing this range, not only the film thickness but also the optical properties (retardation) become uniform, which is more preferable.
- Fig. 2 shows the film thickness distribution in the film width direction after longitudinal stretching.
- the central portion is thinner than the both end portions by a thickness of h, but in the present invention, the effective width that can be used as a product excluding the thick film portions at both ends.
- a uniform film thickness can be obtained.
- the temperature at both ends in the width direction of the film during the longitudinal stretching of the present invention is higher than the temperature at the center, so that the bowing after the longitudinal stretching and the bowing that occurs during the next lateral stretching are offset.
- the amount of bowing after biaxial stretching can be suppressed, and an optical film with a uniform film thickness can be created.
- the amount of bowing after biaxial stretching is measured, and based on the measurement results, It is preferable to control the temperature distribution in the film width direction during stretching. By performing such control, it is possible to manufacture an optical film with a precisely uniform thickness and less bowing.
- thermoforming a hot air blower 80 shown in FIG.
- the temperature distribution in the film width direction can be smoothed by heating the film edge by the hot air blower 80.
- the difference between the temperature at both ends in the width direction of the thermoplastic resin film and the temperature at the center in the longitudinal stretching process is adjusted by the bowing amount of the film after biaxial stretching.
- the end portion on the upstream side in the transport direction of the thermoplastic resin film in the infrared heater and the downstream side in the transport direction of the thermoplastic resin film of the two transport rolls is preferably 50 mm or more and 300 mm or less.
- a substantially stretched span see FIG. 1A
- the installation space of a heating device such as a heater is limited, and since a small roll diameter is required, a large stretching stress cannot be produced, which hinders the production speed increase. It is not preferable.
- the substantial stretching span exceeds 300 mm the amount of width shrinkage accompanying longitudinal stretching becomes large, and the effective width that can be made in the product becomes narrow, which is not preferable.
- a solution casting film forming method for casting a resin solution or a molten resin is formed. It is preferable to form a film using the melt casting film forming method.
- the main materials of the optical film according to the present invention include preferable requirements such as easy manufacture, good adhesion to the polarizing film, and optical transparency.
- thermoplastic resin film having the above properties is not particularly limited.
- cellulose ester films such as cellulose diacetate film, cellulose triacetate film, cellulose acetate butyrate film, and cellulose acetate propionate film
- polyester Film polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyester film such as polyethylene terephthalate and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, polyvinylidene chloride film, polyvinyl alcohol film , Ethylene vinyl alcohol film, syndiotactic polystyrene film, poly -Bonate film, cycloolefin polymer film, ZEONEX (trade name, manufactured by ZEON CORPORATION), ZEONOR (trade name, manufactured by ZEON CORPORATION), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film , Fluororesin film, nylon film, polymethyl
- a cellulose ester film, a cycloolefin polymer film, a polycarbonate film, and a polysulfone (including polyethersulfone) film are preferable.
- a cellulose ester resin film or a cyclic olefin addition polymer is used.
- a resin film containing 80% or more is preferably used from the viewpoints of production, cost, transparency, adhesiveness, and the like.
- the materials constituting the optical film of the present invention include these resins, and if necessary, stabilizers, plasticizers, ultraviolet absorbers, matting agents as slip agents, and retardation control agents. These materials are appropriately selected depending on the required characteristics of the target optical film.
- the cellulose resin When a cellulose resin is used as the material of the optical film of the present invention, the cellulose resin has a cellulose ester structure, and includes at least one of a fatty acid acyl group and a substituted or unsubstituted aromatic acyl group.
- a single or mixed acid ester of cellulose hereinafter, simply referred to as “cellulose resin”), which is amorphous.
- cellulose resin A single or mixed acid ester of cellulose (hereinafter, simply referred to as “cellulose resin”), which is amorphous.
- “Amorphous” means a substance that is not a crystal but has a solid state in an irregular molecular arrangement, and represents a crystalline state at the time of the raw material.
- the cellulose resin constituting the optical film of the present invention has a cellulose ester structure and contains at least one of a fatty acyl group and a substituted or unsubstituted aromatic acyl group.
- An ester (hereinafter simply referred to as “cellulose resin”), which is amorphous. “Amorphous” means a substance that is not a crystal but has a solid state with an irregular molecular arrangement, and represents a crystalline state at the time of the raw material.
- examples of the substituent of the benzene ring include a halogen atom, cyano, alkyl group, alkoxy group, aryl group, aryloxy group, acyl group, Carboxamide group, sulfonamide group, ureido group, aralkyl group, nitro, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, carbamoyl group, sulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, aryl A sulfonyl group, an alkyloxysulfonyl group, an alkylsulfonyloxy group and an aryloxysulfonyl group, —SR, —NH—CO—OR, —PH—R,
- the number of substituents is 1 to 5, preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. Further, when the number of substituents substituted on the aromatic ring is 2 or more, they may be the same or different from each other, but they may be linked together to form a condensed polycyclic compound (eg, naphthalene, indene, indane, phenanthrene, quinoline) , Isoquinoline, chromene, chroman, phthalazine, acridine, indole, indoline, etc.).
- a condensed polycyclic compound eg, naphthalene, indene, indane, phenanthrene, quinoline
- Isoquinoline chromene, chroman, phthalazine, acridine, indole, indoline, etc.
- a halogen atom, cyano, alkyl group, alkoxy group, aryl group, aryloxy group, acyl group, carbonamido group, sulfonamido group and ureido group are preferable, halogen atom, cyano, alkyl group, alkoxy group, An aryloxy group, an acyl group and a carbonamido group are more preferred, a halogen atom, cyano, an alkyl group, an alkoxy group and an aryloxy group are more preferred, and a halogen atom, an alkyl group and an alkoxy group are most preferred.
- the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- the alkyl group may have a cyclic structure or a branch.
- the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12, more preferably 1 to 6, and most preferably 1 to 4.
- alkyl group examples include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclohexyl, octyl and 2-ethylhexyl.
- the alkoxy group may have a cyclic structure or a branch.
- the number of carbon atoms of the alkoxy group is preferably 1-20, more preferably 1-12, still more preferably 1-6, and most preferably 1-4.
- the alkoxy group may be further substituted with another alkoxy group. Examples of the alkoxy group include methoxy, ethoxy, 2-methoxyethoxy, 2-methoxy-2-ethoxyethoxy, butyloxy, hexyloxy and octyloxy.
- the number of carbon atoms of the aryl group is preferably 6-20, and more preferably 6-12.
- Examples of the aryl group include phenyl and naphthyl.
- the number of carbon atoms of the aryloxy group is preferably 6-20, and more preferably 6-12.
- Examples of the aryloxy group include phenoxy and naphthoxy.
- the number of carbon atoms of the acyl group is preferably 1-20, and more preferably 1-12.
- Examples of the acyl group include formyl, acetyl and benzoyl.
- the number of carbon atoms in the carbonamide group is preferably 1-20, and more preferably 1-12.
- Examples of the carbonamido group include acetamide and benzamide.
- the number of carbon atoms of the sulfonamide group is preferably 1-20, and more preferably 1-12.
- Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and p-toluenesulfonamide.
- the number of carbon atoms in the ureido group is preferably 1-20, and more preferably 1-12.
- Examples of the ureido group include (unsubstituted) ureido.
- the number of carbon atoms in the aralkyl group is preferably 7-20, and more preferably 7-12.
- Examples of the aralkyl group include benzyl, phenethyl and naphthylmethyl.
- the number of carbon atoms of the alkoxycarbonyl group is preferably 1-20, and more preferably 2-12.
- Examples of the alkoxycarbonyl group include methoxycarbonyl.
- the number of carbon atoms of the aryloxycarbonyl group is preferably 7-20, and more preferably 7-12.
- Examples of the aryloxycarbonyl group include phenoxycarbonyl.
- the number of carbon atoms in the aralkyloxycarbonyl group is preferably 8-20, and more preferably 8-12.
- Examples of the aralkyloxycarbonyl group include benzyloxycarbonyl.
- the number of carbon atoms in the carbamoyl group is preferably 1-20, and more preferably 1-12.
- Examples of the carbamoyl group include (unsubstituted) carbamoyl and N-methylcarbamoyl.
- the number of carbon atoms in the sulfamoyl group is preferably 20 or less, and more preferably 12 or less.
- Examples of the sulfamoyl group include (unsubstituted) sulfamoyl and N-methylsulfamoyl.
- the acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms.
- acyloxy group examples include acetoxy and benzoyloxy.
- the number of carbon atoms of the alkenyl group is preferably 2-20, and more preferably 2-12.
- alkenyl groups include vinyl, allyl and isopropenyl.
- the number of carbon atoms of the alkynyl group is preferably 2-20, and more preferably 2-12.
- alkynyl groups include thienyl.
- the number of carbon atoms of the alkylsulfonyl group is preferably 1-20, and more preferably 1-12.
- the number of carbon atoms of the arylsulfonyl group is preferably 6-20, and more preferably 6-12.
- the number of carbon atoms of the alkyloxysulfonyl group is preferably 1-20, and more preferably 1-12.
- the number of carbon atoms of the aryloxysulfonyl group is preferably 6-20, and more preferably 6-12.
- the number of carbon atoms of the alkylsulfonyloxy group is preferably 1-20, and more preferably 1-12.
- the hydrogen atom of the hydroxyl group of cellulose is a fatty acid ester with an aliphatic acyl group
- the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetyl, propionyl, Examples include butyryl, isobutyryl, valeryl, pivaloyl, hexanoyl, octanoyl, lauroyl, stearoyl and the like.
- the aliphatic acyl group is meant to include those further having a substituent.
- the aromatic ring is a benzene ring in the above-described aromatic acyl group
- the substituent of the benzene ring are exemplified.
- the cellulose resin is at least one selected from cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose phthalate. It is preferred to use seeds.
- particularly preferable cellulose resins include cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.
- Cellulose acetate propionate and cellulose acetate butyrate which are mixed fatty acid esters, have 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 When Y represents Y, those satisfying the following formulas (I) and (II) are preferable.
- the degree of substitution is defined as a numerical value indicating the number of hydroxyl groups substituted by an acyl group in glucose units.
- Formula (II) 0 ⁇ X ⁇ 2.5 In particular, cellulose acetate propionate is preferably used. Among them, 1.9 ⁇ X ⁇ 2.5 and 0.1 ⁇ Y ⁇ 0.9 are preferable.
- the portion not substituted with the acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.
- the raw material cellulose of the cellulose resin 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.
- Cellulose resins made from these can be used in appropriate mixture or independently.
- the cellulose resin used in the present invention has few bright spot foreign substances when formed into a film.
- Bright spot foreign matter means that two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is arranged between them, and the slow axis of the polarizing plate protective film is placed on the transmission axis of the polarizing plate on one light source side.
- the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and a polarizing plate using a glass plate for protecting the polarizer is preferably used.
- the bright spot foreign matter is considered to be one of the reasons that the esterification part of the hydroxyl group contained in the cellulose resin is unreacted, and using a cellulose resin with few bright spot foreign substances and filtering the heated and melted cellulose resin Can remove foreign matter and reduce bright spot foreign matter. Moreover, the number of bright spot foreign matter per unit area decreases as the film thickness decreases, and the bright spot foreign matter tends to decrease as the content of the cellulose resin contained in the film decreases.
- bright spots with a size of 5 to 50 ⁇ m recognized in the polarization crossed Nicol state are 300 or less bright spots when observing the film, and 0 bright spots of 50 ⁇ m or more. Preferably there is. More preferably, the number of bright spots of 5 to 50 ⁇ m is 200 or less.
- the retardation film functions as a polarizing plate protective film, the presence of the bright spot is a factor of disturbance of birefringence, and the adverse effect on the image becomes large.
- a melt casting film forming step can be continuously performed including a bright spot foreign matter removing step.
- the melt casting film forming method including the filtration process of bright spot foreign matters by heat melting lowers the heat melting temperature when a plasticizer and a cellulose resin described later are used as a composition compared to a system in which no plasticizer is added. This is a preferable method from the viewpoint and from the viewpoint of improving the removal efficiency of bright spot foreign matter and avoiding thermal decomposition. Moreover, what mixed the ultraviolet absorber and the mat material suitably as another additive mentioned later can also be filtered similarly.
- the filter medium conventionally known materials such as glass fibers, cellulose fibers, filter paper, fluororesins such as tetrafluoroethylene resin are preferably used, and ceramics, metals and the like are particularly preferably used.
- the absolute filtration accuracy is 50 ⁇ m or less, preferably 30 ⁇ m or less, more preferably 10 ⁇ m or less, and still more preferably 5 ⁇ m or less. These can be used in combination as appropriate.
- the filter medium can be either a surface type or a depth type, but the depth type is preferable because it is relatively less clogged.
- the solution before heating and melting the film constituent material, at least in the cellulose resin of the constituent material, at least one of the late synthesis process and the precipitate obtaining process, the solution Similarly, the bright spot foreign matter can be removed through the filtration step as the state.
- a stabilizer is preferably present in the cellulose resin, and after dissolving in a solvent together with a UV absorber, a matting agent, etc. as a plasticizer or other additive described later, the solvent is removed and drying is performed. By doing so, you may make it obtain the solid content of the film constituent material which mainly has a cellulose resin.
- a process of cooling to ⁇ 20 ° C. or lower in the process of dissolving the constituent materials in a solvent can be performed.
- any one or more of stabilizers, plasticizers, and other additives are added to the cellulose resin, there is no particular limitation in the process of synthesizing (preparing) the cellulose resin used in the present invention. (Preparation) At least once by the latter stage of the process, filtration is performed to filter out bright spot foreign matter and insoluble matter in the solution state, and then other additives are added, and the solid content is separated by solvent removal or acid precipitation. It may be dried and a film constituent material mixed with powder when pelletized may be obtained.
- Mixing a constituent material other than the cellulose resin of the film constituent material uniformly with the resin can contribute to providing a uniform meltability in the meltability at the time of heating.
- Polymeric materials and oligomers other than cellulose resin may be appropriately selected and mixed with cellulose resin.
- a polymer material or oligomer preferably has excellent compatibility with the cellulose resin, and the transmittance is 80% or more, preferably 90% or more, more preferably over the entire visible region (400 nm to 800 nm) when formed into a film. Is 92% or more.
- the purpose of mixing at least one of polymer materials and oligomers other than the cellulose resin includes meanings for the purpose of improving viscosity control during heating and melting and improving film physical properties after film processing. This polymer material and oligomer may be regarded as other concepts as additives.
- the plasticizer is not particularly limited, but in the phosphate ester type, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc., phthalate ester type In diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, etc., in glycolic acid ester system, triacetin, tributyrin, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, It is preferable to use methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate or the like.
- the above plasticizers may be used in combination of two or more as required.
- the proportion of the phosphate ester plasticizer is more preferably smaller, and it is particularly preferable to use only a phthalate ester or glycolate ester plasticizer.
- the amount of the plasticizer to be added in order to make the water absorption rate and moisture content within a specific range is 3 to 30% by mass, more preferably 10 to 25% by mass, based on the cellulose ester resin. More preferably, it is 15 to 25% by mass.
- the addition amount of the plasticizer exceeds 30% by mass, the mechanical strength and dimensional stability of the cellulose ester-based resin film deteriorate, which is not preferable.
- hindered phenol compounds are suitable. Specific examples thereof include 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-tert-butyl-4-hydroxyphenyl) propionate], octade 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,
- 2,6-di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 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-t
- a phosphorus processing stabilizer such as -butylphenyl phosphite may be used in combination.
- the amount of these compounds added is preferably from 1 ppm to 1.0%, particularly preferably from 10 to 1000 ppm, by weight, based on the cellulose ester resin.
- an ultraviolet absorber it is preferable to add an ultraviolet absorber to the cellulose ester resin film.
- the ultraviolet absorber the absorption ability of ultraviolet rays having a wavelength of 370 nm or less is excellent from the viewpoint of preventing deterioration of the liquid crystal, and the absorption of visible light having a wavelength of 400 nm or more is as little as possible from the viewpoint of good liquid crystal display properties. Those are preferably used.
- the transmittance of ultraviolet rays at a wavelength of 370 nm is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less.
- ultraviolet absorber examples include, but are not limited to, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like.
- one or more of these ultraviolet absorbers are preferably used, and two or more different ultraviolet absorbers may be contained.
- Preferably used ultraviolet absorbers include benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers.
- An embodiment in which a benzotriazole-based ultraviolet absorber with less unnecessary coloring is added to the cellulose ester-based resin film is particularly preferable.
- the addition method of the ultraviolet absorber may be added to the dope after dissolving the ultraviolet absorber in an organic solvent such as alcohol, methylene chloride, dioxolane, or may be added directly to the dope composition.
- an organic solvent such as alcohol, methylene chloride, dioxolane
- a dissolver or a sand mill is used in the organic solvent and the cellulose ester resin to disperse and then added to the dope.
- the amount of the ultraviolet absorber used is 0.1 to 2.5% by mass, preferably 0.5 to 2.0% by mass, more preferably 0.8 to 2.0% by mass, based on the cellulose ester resin. % By mass.
- the usage-amount of a ultraviolet absorber exceeds 2.5 mass%, there exists a tendency for the transparency of a cellulose-ester-type resin film to worsen, and it is unpreferable.
- fine particles may be added to the cellulose ester resin film as a matting agent in order to prevent the films from sticking to each other or to impart slipperiness to facilitate handling.
- the type of fine particles may be an inorganic compound or an organic compound.
- the fine particles of the inorganic compound include fine particles of silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, tin oxide and the like. In this, it is preferable that it is a compound containing a silicon atom, and especially a silicon dioxide fine particle is preferable.
- silicon dioxide fine particles for example, Aerosil manufactured by Aerosil Co., Ltd., 200V, 300, R972, R972V, R974, R976, R976S, R202, R812, R805, OX50, TT600, RY50, RX50, NY50, NAX50, NA50H, NA50Y, NX90, RY200S, RY200, RX200, R8200, RA200H, RA200HS, NA200Y, R816, R104, RY300, RX300, R106, and the like.
- AEROSIL-200V and R972V are preferable in terms of controlling dispersibility and particle size.
- the average particle size of the fine particles in the film is preferably 50 nm to 2 ⁇ m from the viewpoint of imparting slipperiness and ensuring transparency.
- the thickness is preferably 100 nm to 1000 nm, more preferably 100 nm to 500 nm.
- the average particle diameter in the film can be confirmed by taking and observing a cross-sectional photograph.
- the primary particle size, the particle size after being dispersed in a solvent, and the particle size after being added to a film often change. And controlling the particle size formed by aggregation and aggregation.
- the amount of fine particles added is 0.02 to 0.5% by mass, preferably 0.04 to 0.3% by mass, based on the cellulose ester resin film.
- FIG. 5 is a schematic flow sheet of a first embodiment of an apparatus for carrying out the method for producing an optical film of the present invention by using a melt casting film forming method, and FIG. It is an enlarged view.
- FIG. 6 shows that the film first contacts the surface of the first cooling roll (cooling first rotating body) 5 and the film contacts the surface of the touch roll (pressing second rotating body) 6.
- the point (P2) is different is shown, in some cases, the point (P1) where the film first contacts the surface of the first cooling roll (first cooling body) 5 and the film The point (P2) in contact with the surface of the touch roll (second pressing rotary body) 6 may be the same.
- the extruder 1 is used to melt and extrude from the casting die 4 onto the first cooling roll 5, While being circumscribed to the cooling roll 5, the film-like melt is pressed against the surface of the first cooling roll 5 with a predetermined pressure by the touch roll 6. Furthermore, the total of three cooling rolls of the second cooling roll 7 and the third cooling roll 8 are sequentially circumscribed and solidified by cooling, and are peeled off by the peeling roll 9. The peeled film 17 is stretched in the longitudinal (conveying direction) and lateral (lateral direction) of the film by the longitudinal stretching apparatus 10 and the lateral stretching apparatus 20 and then wound by the winding apparatus 60.
- a resin such as cellulose resin
- the film (resin mixture) extruded from the casting die 4 is cooled and surface-corrected by at least two rotating bodies having a cooling function.
- the rotating body that the film extruded from the casting die 4 first contacts is defined as the first rotating body
- the rotating body that contacts the film second is defined as the second rotating body. That is, the first cooling roll 5 corresponds to the first rotating body, and the touch roll 6 corresponds to the second rotating body.
- the first rotating body and the second rotating body are not limited to rolls, and may be drums or belts.
- the temperature of the first cooling roll 5 is preferably set to be equal to or lower than the glass transition temperature (Tg) of the resin mixture and equal to or higher than the melting point of the additive.
- the touch roll 6 is a rotating body for the purpose of sandwiching the film in the direction of the first cooling roll 5 from the opposite side of the first cooling roll (cooling first rotating body) 5 with respect to the film.
- the surface of the touch roll 6 is preferably a metal, and the thickness is 1 mm to 10 mm. It is preferably 2 mm to 6 mm.
- the surface of the second rotating body is subjected to a treatment such as chrome plating, and the surface roughness is preferably 0.2 S or less. The smoother the roll surface, the smoother the surface of the resulting film.
- the touch roll 6 is made of an elastic roll whose peripheral surface is coated with a thin metal plate.
- an elastic touch roll having a metal thin plate coated on the peripheral surface as described above is preferable.
- the metal material on the surface of the touch roll 6 is required to be smooth, moderately elastic, and durable. Carbon steel, stainless steel, titanium, nickel produced by electroforming, etc. can be preferably used. Further, in order to increase the hardness of the surface or improve the releasability from the resin, it is preferable to carry out a surface treatment such as hard chrome plating, nickel plating, amorphous chrome plating, or ceramic spraying. It is preferable that the surface processed is further polished to have the above-described surface roughness.
- the touch roll 6 has a double structure of a metal outer cylinder and an inner cylinder, and has a double cylinder configuration having a space so that a cooling fluid can flow between them.
- the inner cylinder is preferably a lightweight and rigid metallic inner cylinder such as carbon steel, stainless steel, aluminum, titanium or the like. By giving rigidity to the inner cylinder, it is possible to suppress the rotational shake of the roll. A sufficient rigidity can be obtained by setting the thickness of the inner cylinder to 2 to 10 times that of the outer cylinder.
- the inner cylinder may be further coated with a resin elastic material such as silicone or fluororubber.
- the structure of the space through which the cooling fluid flows can be any structure as long as the temperature of the roll surface can be uniformly controlled.
- the roll can be made to flow in a spiral direction by flowing alternately and back in the width direction. Temperature control with a small surface temperature distribution is possible.
- the cooling fluid is not particularly limited, and water or oil can be used according to the temperature range to be used.
- the touch roll 6 that is the second rotating body is set to a drum shape in which the outer diameter of the central part is larger than the outer diameters of both end parts.
- the touch roll generally presses both ends of the touch roll against the film with a pressurizing unit, but in this case, the touch roll is bent, so that there is a phenomenon that the touch roll is pressed more strongly toward the end. Highly uniform pressing is possible by making the roll into a drum shape.
- the diameter of the touch roll 6 that is the second rotating body is preferably in the range of 200 mm to 500 mm.
- the effective width of the touch roll 6 needs to be wider than the film width to be pinched. Due to the difference between the radius of the central portion of the touch roll 6 and the radius of the end portion (hereinafter referred to as the crowning amount), unevenness such as streaks generated in the central portion of the film can be prevented.
- the amount of crowning is preferably in the range of 50 to 300 ⁇ m.
- the first cooling roll 5 and the touch roll 6 are installed at positions opposite to the plane of the film so as to sandwich the film.
- the first cooling roll 5 and the touch roll 6 may be in contact with the film by a surface or by a line.
- the conditions for melt extrusion can be performed in the same manner as the conditions used for other thermoplastic resins such as polyester.
- the material is preferably dried beforehand. It is desirable to dry the moisture to 1000 ppm or less, preferably 200 ppm or less, using a vacuum or reduced pressure dryer or a dehumidifying hot air dryer.
- a cellulose ester resin dried under hot air, vacuum or reduced pressure is melted at an extrusion temperature of about 200 to 300 ° C. using an extruder 1 and filtered through a leaf disk type filter 2 to remove foreign matters.
- additives such as plasticizer are not mixed in advance, they 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 3.
- a resin such as a cellulose resin and other additives such as a stabilizer added as necessary are mixed before melting.
- Mixing may be performed by a mixer or the like, or as described above, mixing may be performed in a resin preparation process such as a cellulose resin.
- a general mixer such as a V-type mixer, a conical screw type mixer, a horizontal cylindrical type mixer, or the like can be used.
- the mixture may be melted directly using the extruder 1 to form a film.
- the pellets are extruded.
- the film may be melted by the machine 1 to form a film.
- a so-called braided semi-melt is once produced at a temperature at which only the material having a low melting point is melted, and the semi-melt is supplied to the extruder 1. It is also possible to form a film by introducing it.
- the film component contains a material that is easily pyrolyzed, in order to reduce the number of times of melting, a method of directly forming a film without producing pellets, or after making a paste-like semi-molten material as described above A method of forming a film is preferred.
- the extruder 1 can use various types of extruders available on the market, but is preferably a melt-kneading extruder, and may be a single-screw extruder or a twin-screw extruder.
- a twin-screw extruder When forming a film directly without producing pellets from film constituent materials, it is preferable to use a twin-screw extruder because an appropriate degree of kneading is necessary, but even with a single-screw extruder, the screw shape is a Maddock type. By changing to a kneading type screw such as a unimelt type or a dull mage, moderate kneading can be obtained, so that it can be used.
- a pellet or braided semi-melt When a pellet or braided semi-melt is once used as a film constituent material, it can be used in either a single screw extruder or a twin screw extruder.
- the cooling step is preferably performed by substituting with an inert gas such as nitrogen gas or reducing the pressure to reduce the oxygen concentration.
- the melting temperature of the film constituent material in the extruder 1 varies depending on the viscosity and discharge amount of the film constituent material, the thickness of the sheet to be produced, etc., but generally the glass transition temperature Tg of the film (resin mixture). On the other hand, it is Tg or more and Tg + 100 ° C. or less, preferably Tg + 10 ° C. or more and Tg + 90 ° C. or less.
- the melt viscosity at the time of extrusion is 10 to 100,000 poise, preferably 100 to 10,000 poise.
- the residence time of the film constituting material in the extruder 1 is preferably short, and is within 5 minutes, preferably within 3 minutes, more preferably within 2 minutes. The residence time depends on the type of the extruder 1 and the extrusion conditions, but can be shortened by adjusting the material supply amount, L / D, screw rotation speed, screw groove depth, and the like. is there.
- the shape of the screw and the number of revolutions of the extruder 1 are appropriately selected depending on the viscosity and the discharge amount of the film constituent material.
- the shear rate in the extruder 1 is 1 / second to 10,000 / second, preferably 5 / second to 1000 / second, more preferably 10 / second to 100 / second.
- an extruder generally marketed as a plastic molding machine can be used as the extruder 1.
- the film constituting material extruded from the extruder 1 is sent to the casting die 4 and extruded from the casting die 4 into a film shape.
- the melt discharged from the extruder 1 is supplied to the casting die 4.
- the casting die 4 is not particularly limited as long as it is used for producing a sheet or a film.
- the material of the casting die 4 is sprayed or plated with hard chromium, chromium carbide, chromium nitride, titanium carbide, titanium carbonitride, titanium nitride, super steel, ceramic (tungsten carbide, aluminum oxide, chromium oxide), etc.
- Processing includes buffing, lapping using a # 1000 or higher whetstone, flat cutting using a # 1000 or higher diamond whetstone (the cutting direction is perpendicular to the resin flow direction), electrolytic polishing, and electrolytic composite polishing. And so on.
- a preferable material of the lip portion of the casting die 4 is the same as that of the casting die 4.
- the surface accuracy of the lip is preferably 0.5S or less, and more preferably 0.2S or less.
- the temperature drop from when the film first contacts the surface of the first cooling roll 5 until it contacts the surface of the touch roll 6 is preferably within 20 ° C. If the temperature drop from the time when the film first contacts the surface of the first cooling roll 5 to the time when it contacts the surface of the touch roll 6 is too large, the unevenness of the film thickness increases due to uneven shrinkage. On the other hand, if the temperature when the film contacts the touch roll 6 is too low, the flatness of the film and the film thickness unevenness cannot be sufficiently corrected even if the film is pressed by the touch roll 6 due to the high viscosity of the film.
- Preferred materials for the first cooling roll 5 and the touch roll 6 include carbon steel and stainless steel.
- the surface accuracy is preferably high, and the surface roughness is 0.3 S or less, more preferably 0.1 S or less.
- the touch roll 6 preferably presses the film against the first cooling roll 5 by pressing means.
- the linear pressure with which the touch roll 6 presses the film at this time can be adjusted by a hydraulic piston or the like, and is preferably 0.1 to 100 N / mm, more preferably 1 to 50 N / mm.
- first cooling roll 5 or the touch roll 6 can be made to have a narrow roll diameter or a flexible roll surface in order to improve the uniformity of adhesion with the film.
- the reduced pressure is preferably 50 kPa or more and 70 kPa or less.
- the method for maintaining the pressure of the portion from the lip of the casting die 4 to the first cooling roll 5 at 70 kPa or less is not particularly limited, but the method includes covering the periphery of the roll from the casting die 4 with a pressure-resistant member and reducing the pressure. There is.
- the suction device is preferably subjected to a treatment such as heating with a heater so that the device itself does not become a place where the sublimate is attached. If the suction pressure is too small, the sublimate cannot be sucked effectively, so it is necessary to set the suction pressure appropriately.
- a film-like cellulose ester resin in a molten state from the casting die 4 is brought into close contact with the first cooling roll 5, the second cooling roll 7, and the third cooling roll 8 in order to be cooled and solidified while being conveyed, and the cellulose ester series A resin film 17 is obtained.
- the cooled and solidified film 17 peeled from the third cooling roll (cooling fourth rotating body) 8 by the peeling roll 9 is introduced into the longitudinal stretching apparatus 10 and is conveyed in the transport direction. Roll-drawn in the (MD direction).
- FIG. 7 shows the details of the longitudinal stretching apparatus 10.
- the film 17 introduced into the longitudinal stretching apparatus 10 by the guide roll 41 includes a first pre-stretching preheating roll 21, a second pre-stretching preheating roll 22, a third pre-stretching preheating roll 23, and a fourth pre-stretching preheating. It passes through the roll 24 and reaches the stretching / preheating roll 25, is transported while being pressed from above by the nip roll 26, and is wound around the stretching / cooling roll 27.
- the stretching / preheating roll 25 and the stretching / cooling roll 27 Between the stretching / preheating roll 25 and the stretching / cooling roll 27, an upper heater 32 and a lower heater 33 are arranged.
- the film 17 wound around the stretching / cooling roll 27 is transferred while being pressed from above by the nip roll 28, where it is stretched longitudinally. Furthermore, the film 17 is carried out of the longitudinal stretching apparatus 10 by the guide roll 42 through the cooling roll 29 after the first stretching, the cooling roll 30 after the second stretching, and the cooling roll 31 after the third stretching.
- the unstretched film 17 after clamping is stretched 1.01 times or more and 3.0 times or less in the longitudinal direction of the film 17.
- the upper heater 32 and the lower heater 33 use infrared heaters, and air is blown by a hot air blower 80 from both ends of the film as shown in FIG.
- a hot air blower 80 By making the distance between the heaters 32 and 33 and the film surface constant and heating both ends of the film with the hot air blower 80, the temperature of the end can be set higher than the center of the film when longitudinally stretched.
- the hot air temperature and the air volume of the hot air blower 80 can be varied. By adjusting the hot air blower 80 at the time of longitudinal stretching based on the amount of bowing of the film after being stretched by the lateral stretching device 20 and the measured amount of film thickness unevenness of the film, the film thickness after lateral stretching is made uniform. In addition, the amount of bowing at the time of transverse stretching can be offset by the amount of bowing generated at the time of longitudinal stretching.
- the film stretching method in the longitudinal stretching step is a roll stretching method performed between two transport rolls 25 and 27 arranged close to each other, as shown in FIG. Then, the unstretched film that has been nipped and heated and softened by the heating of the heaters 32 and 33 is stretched longitudinally.
- the substantial stretching span S is set to 50 mm or more and 300 mm or less. In order to clear the substantial stretching span S, a roll that is longitudinally stretched between two adjacent rolls 25 and 27 instead of an oven heating method. The stretching method is advantageous.
- roll stretching is a method in which the film 17 is longitudinally stretched by a difference in peripheral speed between the low-speed roll group (21 to 25) and the high-speed roll group (27 to 31). Preheated by the heaters 32 and 33 provided between the low-speed roll group (21 to 25) and the high-speed roll group (27 to 31). It is cooled in 31) and conveyed to the next process.
- the number of preheating rolls in the low-speed roll group (21 to 25) is preferably small from the viewpoint of scratches, but the number may be selected according to the preheating temperature of the film 17, and is 1 or more, 20 or less, preferably Two or more and 15 or less rolls are used.
- the upper limit temperature of the preheating roll group is not more than the glass transition temperature (Tg) of the film 17, preferably (Tg-5) ° C. It is as follows.
- the temperature increase rate by the preheating roll group is set so that the film temperature difference between the entrance side and the exit side of each roll is 80 ° C. or less, preferably 50 ° C. or less, considering that wrinkles do not occur due to thermal expansion. Is preferred.
- the number of cooling rolls in the high-speed roll group may be selected according to the temperature to be cooled, and 1 or more, 15 or less, preferably 2 or more and 10 or less rolls are used. .
- the upper limit temperature of the chill roll group is not higher than the glass transition temperature (Tg), preferably not higher than (Tg-5) ° C., in consideration of not being overcooled.
- the cooling rate by the cooling roll group is such that wrinkles do not occur due to heat shrinkage, and the film temperature difference between the entrance side and the exit side of each roll is 100 ° C. or less.
- the roll diameters of the preheating roll group and the cooling roll group are 100 mm ⁇ or more and 400 mm ⁇ or less, preferably 150 mm ⁇ or more and 300 mm ⁇ or less from the viewpoint of roll strength and contact area (heat transfer / slip).
- the stretching rolls 25 and 27 are preferably 250 mm ⁇ or less in order to shorten the substantial stretching span S.
- Roll draw is 5% or less, preferably 1% or less, between adjacent rolls.
- the roll draw is the ratio of the peripheral speed V1 of the low-speed roll and the peripheral speed V2 of the high-speed roll, and is (V2 ⁇ V1) / V1 ⁇ 100 (%).
- each of the rolls in the preheating roll group and the cooling roll group is preferably a drive roll, but if it is a part, an auxiliary drive roll and a free roll are used. Also good.
- a planetary roller or roll gear is preferably used for the speed reducer.
- a direct drive system can also be used, and these may be selected as appropriate according to the system.
- the roll surface roughness in the preheating roll group and the cooling roll group may be changed depending on the purpose.
- a mirror surface roll having a surface roughness of 0.5 S or less, preferably 0.2 S or less is used to prevent rolls or slippage coming into contact with the film at high temperatures, and surface roughness is used to prevent tension cut or sticking. It is preferable to use a roll having a rough surface with a degree of 1.0 S or more.
- the roll surface material in the preheating roll group and the cooling roll group is, for example, hard chrome (H—Cr), aluminum oxide, titanium oxide, chromium oxide, etc., and rubbers such as ceramics, silicon, fluorine, chlorobrene, etc. surface-treated with these composites. Resin such as Teflon (registered trademark) is used.
- the roll arrangement / interval between the preheating roll group and the cooling roll group should be narrow to prevent longitudinal stretching between the rolls and to prevent the film from cooling. Between each roll, the distance from roll peeling to landing on the next roll is 200 mm or less, preferably 100 mm or less.
- the diameters of the nip rolls 26 and 28 are not particularly restricted, but are preferably smaller than the stretching roll group in order to secure the space for the heater installations 32 and 33.
- the material of the nip rolls 26 and 28 is preferably a rubber roll such as silicon rubber, fluorine rubber, or chlorobrene rubber, which is easily elastically deformed, or a resin roll such as fluororesin.
- the positions of the nip rolls 26 and 28 are preferably pressed at a position where the film is peeled / landed.
- the pressure of the nip rolls 26 and 28 is 0.1 to 50 N / mm, preferably 0.5 to 20 N / mm, from the viewpoints that the film can be pressure-bonded and the film is not scratched.
- the nip roll may nip only at the end of the film in order to prevent the film from being scratched, or the roll may be a drum shape from the viewpoint of suppressing the width shrinkage, or may be arranged at an angle with respect to the width direction of the film.
- a radiation type heat source such as an infrared heater, a halogen lamp heater, and a ceramic heater is desirable because it is clean, highly efficient, and space-saving. Just choose.
- the number of heaters 32 and 33 may be calculated from the heater capacity, the longitudinal stretching / preheating temperature, the conveyance speed, the film thickness, the thermal conductivity, and the like, and usually 1 to 12, preferably 1 to 8 are used.
- the height of the heaters 32 and 33 is preferably as close to the film as possible, as long as it is not in contact with the film, in order to increase efficiency. For example, it is 5 to 100 mm, preferably 10 to 50 mm.
- the output of the heaters 32 and 33 may be adjusted as appropriate in consideration of the stretching temperature, the heating rate, and the like.
- the temperature of the hot air blower from both ends and the air flow rate may be controlled.
- the distance between the heaters 32 and 33 and the film may be controlled to be wide at the center and narrow at both ends.
- the stretching temperature is a glass transition temperature Tg ⁇ 20 ° C. or higher and a melting point Tm or lower of the film, preferably Tg or higher, Tg + 100 ° C. or lower, more preferably Tg + 10 ° C. or higher, Tg + 80 ° C. or lower.
- the longitudinal stretching speed is 3000% / min or more and 75000% / min or less, preferably 5000% / min or more and 50000% / min or less.
- the longitudinal stretching speed (% / min) is defined as follows. That is, when the peripheral speed of the low-speed side stretching roll is V1, the peripheral speed of the high-speed side stretching roll is V2, and the substantial stretching span is S, it is expressed in the following initial stage.
- the cleaning device for the preheating / stretching / cooling roll in the longitudinal stretching apparatus 10 may be one or plural, and may be provided inline or offline, or may not be installed depending on circumstances.
- a known roll cleaning means such as a method of wiping off the dirt by pressing the nonwoven fabric is preferably used.
- the film after longitudinal stretching is guided to a lateral stretching apparatus (tenter) 20 where the film 17 is stretched in the lateral direction (width direction).
- a lateral stretching apparatus (tenter) 20 where the film 17 is stretched in the lateral direction (width direction).
- the molecules in the film are oriented.
- the cooled and solidified unpressed unstretched film 17 peeled from the third cooling roll 8 by the peeling roll 9 is continuously introduced into the longitudinal stretching apparatus 10 and is moved in the transport direction.
- the present invention is not limited to this, and the cooled and solidified unpressed unstretched film 17 is temporarily wound into a roll, and then so-called offline In some cases, the unstretched film 17 is fed out from the winding roll and guided to the longitudinal stretching apparatus 10 to be roll-stretched in the transport direction (MD direction).
- the thickness and optical distribution in the width direction are reduced by transverse stretching while sequentially raising the temperature difference in the range of 1 to 50 ° C in the stretched region divided into two or more. It is possible and preferable.
- a known tenter or the like can be preferably used as a method of stretching the film in the width direction.
- lamination with the polarizing film can be carried out in a roll form, which is preferable.
- stretching in the width direction the slow axis of the optical film made of the cellulose ester resin film becomes the width direction.
- the transmission axis of the polarizing film is also usually in the width direction.
- the display contrast of the liquid crystal display device can be increased and a good viewing angle can be obtained. Is obtained.
- an optical film having a center line average roughness (Ra) of 0.1 ⁇ m or less, further 0.05 ⁇ m or less is obtained.
- the film thickness variation in the width direction (the entire film width) is within ⁇ 3%, and further within ⁇ 2% with respect to the average film thickness.
- the “average film thickness” means the average value of the thickness of the entire film width excluding both end portions (mimi) that are thickened by necking.
- the film surface roughness and film thickness variation can be measured by known methods. For example, regarding the surface roughness of the film, there is a method in which the surface of the film is measured by a surface roughness meter by about 5 mm and compared as the center line average roughness (Ra). Further, the film thickness variation can be measured by a film thickness meter, and a standard deviation can be obtained or compared with a variation width with respect to the average film thickness.
- Tg glass transition temperature
- Tg can be controlled by varying the kind of material constituting the film and the ratio of the constituting material.
- Tg is preferably 120 ° C. or higher, preferably 135 ° C. or higher.
- the temperature environment of the film changes due to the temperature rise of the device itself, for example, the temperature rise derived from the light source.
- the retardation value derived from the orientation state of the molecules fixed inside the film by stretching and the dimensional shape as the film are greatly changed.
- Tg is preferably 250 ° C. or less.
- known heat setting treatment, cooling and relaxation treatment may be performed, and it may be appropriately adjusted so as to have the characteristics required for the target optical film.
- the transverse stretching step and the heat setting treatment are appropriately selected and performed in order to provide functions and physical properties necessary for widening the viewing angle of the liquid crystal display device. That is, when producing a retardation film as an optical film and further combining the functions of a polarizing plate protective film, it is necessary to control the refractive index, but the refractive index control can be performed by a transverse stretching operation, A transverse stretching operation is a preferred method. Hereinafter, the lateral stretching method will be described.
- Ro represents in-plane retardation, and is obtained by multiplying the difference between the refractive index in the longitudinal direction (MD) and the refractive index in the width direction (TD) by the thickness, and Rt is the thickness direction retardation.
- the difference between the in-plane refractive index (average in the longitudinal direction (MD) and the width direction (TD)) and the refractive index in the thickness direction is multiplied by the thickness.
- the transverse stretching can be performed, for example, sequentially or simultaneously in the longitudinal direction of the film (the direction of casting / conveying) and the direction orthogonal to the longitudinal direction of the film, that is, the width direction. At this time, if the stretching ratio in at least one direction is too small, a sufficient phase difference cannot be obtained, and if it is too large, transverse stretching becomes difficult and film breakage may occur.
- nx is the refractive index in the longitudinal (MD) direction
- ny is the refractive index in the width (TD) direction
- nz is the refractive index in the thickness direction.
- the refractive index When stretching in the width direction, the refractive index may be distributed in the width direction. This distribution may appear when the tenter method is used. By stretching the film in the width direction, a shrinkage force is generated at the center of the film, and the phenomenon is caused by the end being fixed. It is thought to be called the Boeing phenomenon.
- the temperature in the film width direction can be changed during longitudinal stretching, and the temperature at both ends is made higher than the central portion, thereby generating a uniform film thickness and bowing during longitudinal stretching. Can do. This bowing at the time of longitudinal stretching cancels out the bowing that occurs at the time of lateral stretching, and an optical film in which substantial bowing is suppressed can be created.
- the film thickness fluctuation of the obtained film can be further reduced by stretching in the biaxial directions perpendicular to each other.
- the retardation becomes uneven, and unevenness such as coloring may be a problem when used in a liquid crystal display.
- the film thickness variation of the cellulose resin film is preferably in the range of ⁇ 3%, more preferably ⁇ 1%.
- a method of stretching in the biaxial directions perpendicular to each other is effective, and the stretching ratios in the biaxial directions perpendicular to each other are finally 1.0 to 3.0 times in the longitudinal direction, It is preferable to set the width in the range of 1.01 to 3.1 times in the width direction, and it is necessary to perform in the range of 1.01 to 2.7 times in the longitudinal direction and 1.05 to 2.8 times in the width direction. Is more preferable for obtaining a retardation value.
- the transmission axis of the polarizer coincides with the width direction.
- the retardation film is preferably stretched so as to obtain a slow axis in the width direction.
- the slow axis of the retardation film can be imparted in the width direction by stretching in the width direction from the above-described configuration.
- the slow axis of the retardation film is preferably in the width direction, and in order to obtain the target retardation value, (Stretch ratio in width direction)> (Stretch ratio in longitudinal direction) It is necessary to satisfy the following conditions.
- the end of the film 17 is slit to a product width by the slitter 19 and cut off, and then knurled (embossing) is applied to both ends of the film by a knurling apparatus comprising an embossing ring 53 and a back roll 52.
- a knurling apparatus comprising an embossing ring 53 and a back roll 52.
- the knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing.
- the grip part of the clip of the both ends of a film is deform
- FIG. 9 shows a second embodiment of an optical film manufacturing apparatus using the optical film manufacturing method according to the present invention, but the present invention is not limited to this.
- a preliminarily prepared thermoplastic resin solution is cast from a casting die 50 onto a casting belt 51, and a web (a film containing a residual solvent after casting a dope on a metal support is referred to as a web).
- the film is longitudinally stretched by the longitudinal stretching apparatus 10.
- the film 17 stretched in the longitudinal direction is stretched in the transverse direction by a transverse stretching apparatus 20 (tenter).
- the film stretched biaxially and vertically is dried by a drying device 40 and wound by a take-up roll 60.
- the longitudinal stretching apparatus 10 the temperature of the film is changed in the film width direction.
- the same materials as the above-mentioned additives such as a cellulose ester resin, a plasticizer, an ultraviolet absorber, and a matting agent can be used.
- the solvent for the cellulose ester resin for example, lower alcohols such as methanol, ethanol, n-propyl alcohol, iso-propyl alcohol and n-butanol, lower aliphatics such as cyclohexanedioxanes and methylene chloride. Hydrocarbon chlorides can be used.
- methylene chloride is preferably 70 to 95% by mass, and other solvents are preferably 30 to 5% by mass.
- concentration of the cellulose ester resin in the dope is preferably 10 to 50% by mass.
- the heating temperature with the addition of the solvent is preferably a temperature that is not lower than the boiling point of the solvent used and does not boil, and is preferably set in the range of 60 ° C. or higher and 80 to 110 ° C., for example.
- the pressure is determined so that the solvent does not boil at the set temperature.
- the dope of the cellulose ester resin is taken out from the container (dissolution kettle) while cooling, or is taken out from the container with a pump or the like, cooled with a heat exchanger or the like, and used for film formation.
- the manufacturing method of the optical film of this embodiment comprises a dope preparation process, a casting process, a drying process, and a winding process.
- the cellulose ester resin is dissolved in an organic solvent mainly composed of a good solvent for the cellulose ester resin in a dissolution vessel while stirring to form a dope.
- a method carried out at normal pressure a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544 and JP-A-9-95557.
- Various dissolution methods such as a method using a cooling dissolution method as described in JP-A-9-95538 and a method using a high pressure as described in JP-A-11-21379 can be used.
- a method of pressurizing at a temperature equal to or higher than the boiling point of the main solvent is preferable.
- the heating temperature after adding the solvent is preferably a temperature that is not lower than the boiling point of the solvent used and does not boil, and is preferably set in the range of 60 ° C. or higher and 80 to 110 ° C., for example.
- the pressure is determined so that the solvent does not boil at the set temperature.
- the concentration of the cellulose ester resin in the dope is preferably 10 to 35% by mass.
- the necessary additives such as plasticizers, UV absorbers, and matting agents are mixed with the solvent in advance, dissolved or dispersed, and then added to the solvent before dissolution of the cellulose ester resin. Alternatively, it may be added to the dope after dissolving the cellulose ester resin.
- the type of the melting pot is not particularly limited as long as it can withstand a predetermined pressure and can be heated and stirred under pressure.
- instruments such as a pressure gauge and a thermometer are appropriately disposed in the pressurized container.
- the pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside.
- a jacket type is preferable because temperature control is easy.
- Foreign materials include foreign materials that are recognized in the polarization crossed Nicol state, and foreign materials due to aggregates of fine particles protruding on the film surface.
- the foreign substance recognized in the polarization crossed Nicol state refers to a substance measured by placing two polarizing plates in a direct (crossed Nicol) state and placing a cellulose ester resin film between them. In the polarization crossed Nicol state, such a foreign substance is observed by shining only the part of the foreign substance in the dark field, so that the size and number can be easily identified.
- any means can be used, but it can be achieved by filtering a dope composition obtained by dissolving a cellulose ester-based resin in a solvent using the following filter paper.
- a filter paper having a filtering time of 20 sec or more as a kind of filter paper and to form a film by filtering at a filtration pressure of 16 kg / cm 2 or less. More preferably, filtering is performed using a filter paper of 30 sec or more and a filtration pressure of 12 kg / cm 2 or less, more preferably using a filter paper of 40 sec or more and a filtration pressure of 10 kg / cm 2 or less.
- the filtration pressure can be controlled by appropriately selecting the filtration flow rate and the filtration area.
- the casting dope produced as described above is cast on the support 51 by the casting die 50.
- a pressure die that can adjust the slit shape of the die base and easily make the film thickness uniform is preferable.
- the pressure die include a coat hanger die and a T die, and any of them is preferably used.
- the support 51 in the casting step a stainless steel rotary drive belt or a support having a mirror-finished drum is used.
- the temperature of the support in the casting step can be cast in a general temperature range of 0 ° C. to a temperature lower than the boiling point of the solvent, but the dope is more easily cast on the support at 5 to 30 ° C. It is preferable to cast on a support at 5 to 15 ° C. because gelation can increase the peeling limit time.
- the peeling limit time refers to the time during which the cast dope is on the support at the limit of the casting speed at which a transparent and flat film can be continuously obtained. A shorter peeling limit time is preferable because of excellent productivity.
- the dope temperature is set within 30% from casting. By setting the temperature to ⁇ 70 ° C., the evaporation of the solvent is promoted, and it can be peeled off from the support as soon as possible. Further, the peeling strength is increased, and the dope temperature is preferably set to 55 to 70 ° C. within 30%. More preferred. Thereafter, this temperature is preferably maintained at 20% or more, and further preferably maintained at 40% or more.
- the residual solvent amount is 60 to 150% by mass with a peeling roll because the peeling strength from the support is small, and 80 to 120% by mass is more preferable.
- the temperature of the dope at the time of peeling is preferably 0 to 30 ° C., since the base strength at the time of peeling can be increased and the base breakage at the time of peeling can be prevented, and 5 ° C. to 20 ° C. is more preferable.
- the amount of residual solvent is represented by the following formula.
- Residual solvent amount (% by mass) ⁇ (MN) / N ⁇ ⁇ 100
- M is the mass of the web (film) at an arbitrary time point
- N is the mass of the film when the mass M is heat-treated at 115 ° C. for 1 hour.
- the film 17 peeled from the support 51 by the peeling roll 52 is longitudinally stretched by the longitudinal stretching apparatus 10 as a longitudinal stretching step.
- the temperature of the film during this longitudinal stretching is changed in the width direction of the film.
- the film end is 1 to 20 ° C. higher than the film center.
- the means for drying the film in the drying device 40 is not particularly limited, and is generally performed by hot air, infrared rays, a heating roll, microwaves, or the like. It is preferable to carry out with hot air in terms of simplicity.
- the drying temperature is preferably in the range of 40 to 150 ° C. and gradually increased to 3 to 5 stages, and more preferably in the range of 80 to 140 ° C. in order to improve dimensional stability. .
- the cellulose ester resin film is wound into a roll by a winder, and the residual solvent amount is 0.5 mass.
- the ratio is set to not more than%, a film having good dimensional stability can be obtained.
- the winding machine to be used may be a commonly used winding machine, and can be wound by a winding method such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress.
- a winding method such as a constant tension method, a constant torque method, a taper tension method, or a program tension control method with a constant internal stress.
- the thickness of the protective film is preferably 10 to 500 ⁇ m. .
- the lower limit is 20 ⁇ m or more, preferably 35 ⁇ m or more.
- the upper limit is 150 ⁇ m or less, preferably 120 ⁇ m or less.
- a particularly preferred range is 35 to 90 ⁇ m.
- the retardation film is thick, the polarizing plate after polarizing plate processing becomes too thick, and is not suitable for the purpose of thin and light in liquid crystal displays used for notebook personal computers and mobile electronic devices.
- the retardation film is thin, it is difficult to develop retardation as a retardation film, and the moisture permeability of the film is increased, and the ability to protect the polarizer from humidity is reduced, which is not preferable.
- the optical film targeted by the present invention is a functional film used for various displays such as a liquid crystal display, a plasma display, and an organic EL display, particularly a liquid crystal display.
- a polarizing plate protective film, a retardation film, and an antireflection film in addition, it includes a retardation film, such as a brightness enhancement film, an optical compensation film for expanding the viewing angle and the like.
- the polarizing plate including the retardation film constituted by the optical film of the present invention can exhibit high display quality as compared with a normal polarizing plate, particularly a multi-domain liquid crystal display device, more preferably birefringence. Suitable for use in multi-domain liquid crystal display devices in mode.
- Multi-domainization is also suitable for improving the symmetry of image display, and various methods have been reported “Okita, Yamauchi: Liquid Crystal, 6 (3), 303 (2002)”.
- the liquid crystal display cell is also shown in “Yamada, Yamabara: Liquid Crystal, 7 (2), 184 (2003)”, but is not limited thereto.
- the polarizing plate using the optical film of the present invention is an MVA (Multi-domain Vertical Alignment) mode typified by a vertical alignment mode, particularly a MVA mode divided into four, and a known PVA (Patterned) multi-domained by electrode arrangement. It can be effectively used for a Vertical Alignment (CPA) mode and a CPA (Continuous Pinsed Alignment Alignment) mode that combines electrode arrangement and chirality.
- CPA Vertical Alignment
- CPA Continuous Pinsed Alignment Alignment
- a proposal of an optically biaxial film is also disclosed in conformity with the OCB (Optical Compensated Bend) mode, and “T. Miyashita, T. Uchida: J. SID, 3 (1), 29 ( 1995) ”, a display quality effect can be exhibited by the polarizing plate using the optical film of the present invention.
- the arrangement of the liquid crystal mode and the polarizing plate is not limited.
- the display quality of the display cell is preferably symmetrical in human observation. Therefore, when the display cell is a liquid crystal display cell, it is possible to multiplex domains by giving priority to the symmetry on the observation side.
- a known method can be used to divide the domain, and can be determined in consideration of the properties of a known liquid crystal mode by a two-part dividing method, more preferably a four-part dividing method.
- Liquid crystal display devices are also being applied as devices for colorization and moving image display, and the display quality is improved by the optical film of the present invention, and the improvement in contrast and the resistance of the polarizing plate are improved. A moving image can be displayed.
- one polarizing plate including a retardation film constituted by the optical film of the present invention is arranged for the liquid crystal cell, or two polarizing plates are arranged on both sides of the liquid crystal cell. At this time, it can contribute to the improvement of display quality by using it so that the phase difference film side contained in a polarizing plate may face the liquid crystal cell of a liquid crystal display device.
- a polarizing plate protective film of a cellulose derivative is used on the surface opposite to the retardation film as viewed from the polarizer, and a general-purpose TAC film or the like can be used.
- the polarizing plate protective film located on the side far from the liquid crystal cell can be provided with another functional layer in order to improve the quality of the display device.
- the optical film according to the present invention may have functions such as antireflection, antiglare, abrasion resistance, dust adhesion prevention, and brightness enhancement. Although you may affix on the polarizing plate surface, it is not limited to these.
- a retardation film is required to have a small variation in Ro and Rt as the retardation value in order to obtain stable optical characteristics.
- these fluctuations may cause image unevenness.
- the retardation value of a film produced by a method by the solution casting method may vary depending on the volatilization of the amount of organic solvent remaining in a very small amount in the film.
- This film is manufactured, stored and transported in the form of a long roll, and processed into a polarizing plate by a polarizing plate manufacturer or the like.
- the residual solvent may be present and the volatility may slow down. For this reason, a slight difference in the concentration of residual solvent occurs from both ends to the center in the winding direction and in the width direction, which may trigger the change and fluctuation of the retardation value over time.
- the film produced by the melt casting method is mainly composed of a resin such as a cellulose resin
- an alkali treatment process can be utilized by utilizing saponification inherent to a resin such as a cellulose resin.
- the resin which comprises a polarizer is polyvinyl alcohol
- it can be bonded with a phase difference film using the completely saponified polyvinyl alcohol aqueous solution similarly to the conventional polarizing plate protective film. For this reason, it is more excellent in the point which can apply the conventional polarizing plate processing method, and it is excellent especially in the point from which the roll polarizing plate which is elongate is obtained.
- a film with high planarity can be produced particularly when a film is produced using a wide casting die 4 having a film (web) width of 1500 mm or more and 4000 mm or less at the exit of the casting die. Get the effect.
- the film (web) width at the casting die exit is 1500 mm or more, it is possible to take a product with a width exceeding 2000 mm as an optical film after stretching. It is in the range of 1500 mm to 4000 mm, particularly in the range of 1700 mm to 4000 mm, that the film (web) width at the exit of the casting die exhibits the effect of obtaining a film having particularly high flatness.
- a film having a casting width exceeding 4000 mm is not practical because it is assumed that stability in a subsequent transport process or the like is lowered.
- functional layers such as an antistatic layer, a hard coat layer, a slippery layer, an adhesive layer, an antiglare layer, and a barrier layer may be coated before and / or after stretching.
- various surface treatments such as corona discharge treatment, plasma treatment, and chemical treatment can be performed as necessary.
- the clip gripping portions at both ends of the cut film are pulverized or granulated as necessary, and then used as film raw materials of the same type or as film raw materials of different types. It may be reused.
- an optical film having a laminated structure by co-casting a composition containing a resin such as a cellulose resin having different additive concentrations such as the above-mentioned plasticizer, ultraviolet absorber and matting agent.
- a resin such as a cellulose resin having different additive concentrations
- the above-mentioned plasticizer, ultraviolet absorber and matting agent can be produced.
- the matting agent can be contained in the skin layer in a large amount or only in the skin layer.
- the plasticizer and the ultraviolet absorber can be contained in the core layer more than the skin layer, and may be contained only in the core layer.
- the kind of plasticizer and ultraviolet absorber can be changed between the core layer and the skin layer.
- the skin layer contains a low-volatile plasticizer and / or an ultraviolet absorber, and the core layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption.
- the glass transition temperature of the skin layer and the core layer may be different, and the glass transition temperature of the core layer is preferably lower than the glass transition temperature of the skin layer. At this time, the glass transition temperatures of both the skin and the core can be measured, and an average value calculated from these volume fractions can be defined as the glass transition temperature Tg and similarly handled.
- the viscosity of the melt containing the cellulose ester during melt casting may be different between the skin layer and the core layer, and the viscosity of the skin layer> the viscosity of the core layer or the viscosity of the core layer ⁇ the viscosity of the skin layer may be used.
- the dimensional stability of the optical film of the present invention is such that the dimensional stability value at a temperature of 80 ° C. and a humidity of 90% RH is ⁇ on the basis of the dimensions of the film left at a temperature of 23 ° C. and a humidity of 55% RH for 24 hours. It is less than 2.0%, preferably less than 1.0%, more preferably less than 0.5%.
- the optical film of the present invention As a retardation film for a protective film of a polarizing plate, if the retardation film itself has a variation beyond the above range, the absolute value of the retardation as a polarizing plate and the orientation angle are initially set. Therefore, the display quality improvement ability may be reduced or the display quality may be deteriorated.
- the method for producing the polarizing plate is not particularly limited, and can be produced by a general method.
- the obtained retardation film was treated with an alkali, and a polyvinyl alcohol film was immersed and drawn in an iodine solution, and a polarizer protective film was formed on both sides of the polarizer using a completely saponified polyvinyl alcohol aqueous solution on both sides of the polarizer.
- polarizing plate processing may be performed by applying an easy adhesion process as described in JP-A-6-94915 and JP-A-6-118232.
- the polarizing plate is composed of a polarizer and a protective film that protects both surfaces of the polarizer, and can further be constructed by laminating a protective film on one surface of the polarizing plate and a separate film on the opposite surface.
- the protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection.
- the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate.
- a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal board, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell.
- Examples and comparative examples in the case of using the melt casting method as a method for producing an optical film are shown below.
- Examples 1-7, Comparative Example 1 (Resin mixture) Cellulose acetate propionate 89% by mass (Acetyl group substitution degree 1.4, propionyl group substitution degree 1.35, Number average molecular weight 60000) 9% by mass of trimethylolpropane tribenzoate (Plasticizer, melting point 85 ° C)
- Antioxidant IRGANOX XP 420 / FD
- UV absorber 1.6% by mass TINUVIN 928, manufactured by Ciba Japan, melting point 115 ° C.
- Matting agent (silica fine particles) 0.15% by mass (Seahoster KEP-30: Nippon Shokubai Co., Ltd., average particle size 0.3 ⁇ m)
- the degree of substitution of acyl groups such as acetyl group, propionyl group and butyryl group of cellulose acetate propionate was
- the above materials were mixed in a V-type mixer for 30 minutes, and then melted at 230 ° C. under a nitrogen atmosphere using a twin screw extruder equipped with a strand die to prepare cylindrical pellets having a length of 4 mm and a diameter of 3 mm. .
- the obtained pellet had a glass transition point (Tg) of 135 ° C.
- the pellets were dried at 100 ° C. for 5 hours to a moisture content of 100 ppm, and the pellets were supplied to the single-screw extruder 1 equipped with the T-die 4 shown in FIG.
- the melt contained 11% by mass of additives other than resin.
- Nitrogen gas was sealed from the vicinity of the material supply port, and the inside of the extruder 1 was kept in a nitrogen atmosphere.
- the extruder 1 and the T die 4 were set to a temperature of 240 ° C.
- the T die 4 is a coat hanger type, has a width of 1900 mm, has an inner wall plated with hard chrome, and is finished to a mirror surface with a surface roughness of 0.1S.
- the lip gap of the T die 4 was set to 2 mm.
- the film from the T-die 4 was dropped onto a first cooling roll (cooling first rotating body) 5 having a roll-plated 2400 mm chrome-plated mirror surface, and the temperature was adjusted to 100 ° C. at the same time.
- the film was pressed by a touch roll (second rotating body for pressing) 6 having a roll width of 2400 mm.
- the melting point was set to 120 ° C., which is not less than 115 ° C.).
- the touch roll (second rotating body for pressing) 6 pressed the film with a linear pressure of 5 N / mm.
- the film pressed by the first cooling roll (cooling first rotating body) 5 and the touch roll (pressing second rotating body) 6 continues to the second cooling roll (cooling third rotating body) 7, and the second A total of three cooling rolls (fourth rotating body for cooling) 8 are sequentially circumscribed and solidified by cooling, and are peeled off by a peeling roll 9.
- the film thickness of the unstretched film 17 that has been narrowed by the touch roll 6 is such that the average film thickness of the product equivalent width of 1500 mm excluding 100 mm each of the end thick film portions accompanying necking is 200 ⁇ m, and the lip gap is set with a casting die bolt. It was adjusted. This unstretched film 17 was once wound up into a roll.
- the unstretched film 17 had a width of 1700 mm.
- the non-clamped unstretched film 17 introduced into the longitudinal stretching apparatus 10 by the guide roll 41 includes a first pre-stretching preheating roll 21, a second pre-stretching preheating roll 22, a third pre-stretching preheating roll 23, and a first 4 It passes through the preheating roll 24 before extending
- An upper heater 32 and a lower heater 33 are disposed between the stretching / preheating roll 25 and the stretching / cooling roll 27.
- Hot air was blown by 80.
- Comparative Example 1 the same settings as in Examples 1 to 7 were made except that the hot air blower 80 in Examples 1 to 7 was not provided.
- the film 17 wound around the stretching / cooling roll 27 is transported while being pressed from above by the nip roll 28 and stretched longitudinally. Furthermore, the film 17 was carried out of the longitudinal stretching apparatus 10 by the guide roll 42 through the cooling roll 29 after the first stretching, the cooling roll 30 after the second stretching, and the cooling roll 31 after the third stretching.
- halogen heaters were used as the heaters 32 and 33, the capacity was 50 kW, and the output was adjusted to the set stretching temperature.
- the height of the heaters 32 and 33 was set to be 30 mm from the film surface and was set uniformly in the film width direction, and the pressure of the nip rolls 26 and 28 was 2 N / mm.
- the air volume and the hot air temperature were adjusted, and the temperature difference between the both end portions and the central portion in the film width direction was as shown in Table 2, and Examples 1 to 7 were obtained.
- the temperature at both ends and the center of the film was measured by using an infrared thermography FSV-7000S manufactured by Apiste, and installed near the infrared heater 15 in FIG. The center position of was measured. Further, the central part was also divided into five equal parts, and the position of each central part was measured. The difference between the temperature at both ends and the temperature at the center was calculated as the temperature difference, with the average of the measured values at both ends as the temperature at both ends and the average of the measured values at the center as the temperature at the center.
- the unstretched film 17 after the clamping was stretched 2.0 times in the longitudinal direction.
- the effective span was 100 mm.
- the thickness deviation ( ⁇ m) after stretching was measured using a contact-type film thickness meter.
- the film was measured at intervals of 10 mm over the entire width of the film, and the deviation between the maximum film thickness and the minimum film thickness was evaluated within the range excluding the abrupt film thickness change at the end.
- the deviation is 2 ⁇ m or less, ⁇ , when 2 ⁇ m is exceeded and 5 ⁇ m or less is ⁇ , and when 5 ⁇ m or more is exceeded, ⁇ . If the film thickness deviation exceeds 5 ⁇ m, the viewing angle and contrast change, and cannot be used as a product quality level.
- a reference line La is drawn on the film before longitudinal stretching as shown in FIG. 3, and the bowing amount B after lateral stretching is measured, and ⁇ is 50 mm or less, ⁇ is 50 mm and 80 mm or less, and x is 80 mm or more. As evaluated. If the bowing amount exceeds 80 mm, the retardation and orientation angle of the film become non-uniform and cannot be used as the quality level of the product.
- the retardation was measured at intervals of 100 mm in the width direction, and the deviation was evaluated as ⁇ ⁇ ⁇ , 2 nm exceeding ⁇ , 2 nm exceeding 5 nm and ⁇ exceeding 5 nm as x.
- the retardation deviation exceeds 5 nm, a bright and dark pattern is seen when observed with crossed Nicols and cannot be used as the quality level of the product.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
長尺状の熱可塑性樹脂フィルムを2本の搬送ロール間で長手方向に延伸する縦延伸工程と、該縦延伸工程の後に前記熱可塑性樹脂フィルムを幅方向に延伸する横延伸工程と、を有する光学フィルムの製造方法において、
前記縦延伸工程において、幅方向における前記熱可塑性樹脂フィルムの両端部の温度が、幅方向における前記熱可塑性樹脂フィルムの中央部の温度よりも高いことを特徴とする光学フィルムの製造方法。
前記縦延伸工程において、前記両端部の温度が、前記中央部の温度よりも1℃~20℃高いことを特徴とする前記1に記載の光学フィルムの製造方法。
前記縦延伸工程において、前記両端部の温度が、前記中央部の温度よりも5℃~15℃高いことを特徴とする前記1または2に記載の光学フィルムの製造方法。
前記縦延伸工程において、前記熱可塑性樹脂フィルムが、前記2本の搬送ロール間に配置された赤外線ヒータにより加温され、
該赤外線ヒータにおける前記熱可塑性樹脂フィルムの搬送方向上流側の端部と、
前記2本の搬送ロールのうち前記熱可塑性樹脂フィルムの搬送方向下流側のロールに前記熱可塑性樹脂フィルムが接する位置との距離が、50mm以上300mm以下であることを特徴とする前記1から3の何れか1項に記載の光学フィルムの製造方法。
前記両端部と前記赤外線ヒータとの距離が、前記中央部と前記赤外線ヒータとの距離より短いことを特徴とする前記4に記載の光学フィルムの製造方法。
前記縦延伸工程において、前記熱可塑性樹脂フィルムが、前記両端部から前記中央部に向けて熱風を吹き付ける熱風送風機により加温されることを特徴とする前記4又は5に記載の光学フィルムの製造方法。
前記縦延伸工程における前記両端部の温度と前記中央部の温度との差は、前記縦延伸工程及び前記横延伸工程を経た後の熱可塑性樹脂フィルムのボーイング量により調整されることを特徴とする前記6に記載の光学フィルムの製造方法。
前記縦延伸工程の後の前記熱可塑性樹脂フィルムの膜厚が20μm以上150μm以下であることを特徴とする前記4から7の何れか1項に記載の光学フィルムの製造方法。
前記縦延伸工程において、前記熱可塑性樹脂フィルムの幅が1500mm以上4000mm以下であることを特徴とする前記4から8の何れか1項に記載の光学フィルムの製造方法。
前記熱可塑性樹脂フィルムが、熱溶融性フィルムであることを特徴とする前記4から9の何れか1項に記載の光学フィルムの製造方法。
前記熱可塑性樹脂フィルムが、セルロースエステルフィルムであることを特徴とする前記1から10の何れか1項に記載の光学フィルムの製造方法。
前記1から11の何れか1項に記載の光学フィルムの製造方法によって製造されたことを特徴とする光学フィルム。
2 フィルター
3 スタチックミキサー
4、50 流延ダイ
5 第1冷却ロール(冷却用第1回転体)
6 タッチロール(押圧用第2回転体)
7 第2冷却ロール(冷却用第3回転体)
8 第3冷却ロール(冷却用第4回転体)
P1 フィルムが最初に第1冷却ロール表面に接触した点
P2 フィルムがタッチロール表面に接触した点
9、52 剥離ロール
10 縦延伸装置
11、13 搬送ロール
15 赤外線ヒータ
16 反射板
17 フィルム
19 スリッター
20 横延伸装置
21 第1延伸前予熱ロール
22 第2延伸前予熱ロール
23 第3延伸前予熱ロール
24 第4延伸前予熱ロール
25 延伸・予熱ロール
26 ニップロール
27 延伸・冷却ロール
28 ニップロール
29 第1延伸後冷却ロール
30 第2延伸後冷却ロール
31 第3延伸後冷却ロール
32 上部加熱ヒータ
33 下部加熱ヒータ
41 ガイドロール
42 ガイドロール
51 流延用ベルト
40 乾燥装置
52 バックロール
53 エンボスリング
60 巻取り装置
S 実質延伸スパン
F 光学フィルム(元巻き)
式(II) 0≦X≦2.5
特にセルロースアセテートプロピオネートが好ましく用いられ、中でも1.9≦X≦2.5であり、0.1≦Y≦0.9であることが好ましい。上記アシル基で置換されていない部分は通常水酸基として存在している。これらは公知の方法で合成することができる。
また、縦延伸ロールの間隔は、フィルムがロールに保持されていない区間は短いほど幅収縮が抑えられる。ここで、ロールの中心同士の間の距離が、400mm以下、好ましくは300mm以下である。
(幅方向の延伸倍率)>(長手方向の延伸倍率)
の条件を満たすことが必要である。
ここで、Mはウェブ(フィルム)の任意時点での質量、Nは質量Mのものを115℃で1時間加熱処理したときのフィルム質量である。
本発明の光学フィルムによって構成される位相差フィルムを含む偏光板は、通常の偏光板と比較して高い表示品質を発現させることができ、特にマルチドメイン型の液晶表示装置、より好ましくは複屈折モードにるマルチドメイン型の液晶表示装置への使用に適している。
実施例1~7、比較例1
(樹脂混合物)
セルロースアセテートプロピオネート 89質量%
(アセチル基置換度1.4、プロピオニル基置換度1.35、
数平均分子量60000)
トリメチロールプロパントリベンゾエート 9質量%
(可塑剤、融点85℃)
酸化防止剤(IRGANOX XP 420/FD) 0.25質量%
(チバ・ジャパン社製)
紫外線吸収剤 1.6質量%
(TINUVIN 928、チバ・ジャパン社製、融点115℃)
マット剤(シリカ微粒子) 0.15質量%
(シーホスターKEP-30:日本触媒株式会社製、平均粒径0.3μm)
なお、セルロースアセテートプロピオネートのアセチル基、プロピオニル基、ブチリル基等のアシル基の置換度の測定は、ASTM-D817-96に規定の方法に準じて測定した。
つぎに、実施例1~7及び比較例1において延伸したセルロースアセテートプロピオネートフィルムについて、延伸後の膜厚偏差(μm)を接触式膜厚計を用い、フィルムの全幅において10mm間隔で測定し、端部の急激な膜厚変化を除いた範囲で、最大膜厚と最小膜厚の偏差を評価した。偏差が2μm以下を◎、2μmを越えて5μm以下を○、5μmを越えるものを×とした。膜厚偏差が、5μmを越えると、視野角やコントラストが変化し、製品の品質レベルとして用いることができない。
Claims (12)
- 長尺状の熱可塑性樹脂フィルムを2本の搬送ロール間で長手方向に延伸する縦延伸工程と、該縦延伸工程の後に前記熱可塑性樹脂フィルムを幅方向に延伸する横延伸工程と、を有する光学フィルムの製造方法において、
前記縦延伸工程において、幅方向における前記熱可塑性樹脂フィルムの両端部の温度が、幅方向における前記熱可塑性樹脂フィルムの中央部の温度よりも高いことを特徴とする光学フィルムの製造方法。 - 前記縦延伸工程において、前記両端部の温度が、前記中央部の温度よりも1℃~20℃高いことを特徴とする請求の範囲第1項に記載の光学フィルムの製造方法。
- 前記縦延伸工程において、前記両端部の温度が、前記中央部の温度よりも5℃~15℃高いことを特徴とする請求の範囲第1項又は第2項に記載の光学フィルムの製造方法。
- 前記縦延伸工程において、前記熱可塑性樹脂フィルムが、前記2本の搬送ロール間に配置された赤外線ヒータにより加温され、
該赤外線ヒータにおける前記熱可塑性樹脂フィルムの搬送方向上流側の端部と、
前記2本の搬送ロールのうち前記熱可塑性樹脂フィルムの搬送方向下流側のロールに前記熱可塑性樹脂フィルムが接する位置との距離が、50mm以上300mm以下であることを特徴とする請求の範囲第1項から第3項の何れか1項に記載の光学フィルムの製造方法。 - 前記両端部と前記赤外線ヒータとの距離が、前記中央部と前記赤外線ヒータとの距離より短いことを特徴とする請求の範囲第4項に記載の光学フィルムの製造方法。
- 前記縦延伸工程において、前記熱可塑性樹脂フィルムが、前記両端部から前記中央部に向けて熱風を吹き付ける熱風送風機により加温されることを特徴とする請求の範囲第4項又は第5項に記載の光学フィルムの製造方法。
- 前記縦延伸工程における前記両端部の温度と前記中央部の温度との差は、前記縦延伸工程及び前記横延伸工程を経た後の熱可塑性樹脂フィルムのボーイング量により調整されることを特徴とする請求の範囲第6項に記載の光学フィルムの製造方法。
- 前記縦延伸工程の後の前記熱可塑性樹脂フィルムの膜厚が20μm以上150μm以下であることを特徴とする請求の範囲第4項から第7項の何れか1項に記載の光学フィルムの製造方法。
- 前記縦延伸工程において、前記熱可塑性樹脂フィルムの幅が1500mm以上4000mm以下であることを特徴とする請求の範囲第4項から第8項の何れか1項に記載の光学フィルムの製造方法。
- 前記熱可塑性樹脂フィルムが、熱溶融性フィルムであることを特徴とする請求の範囲第4項から第9項の何れか1項に記載の光学フィルムの製造方法。
- 前記熱可塑性樹脂フィルムが、セルロースエステルフィルムであることを特徴とする請求の範囲第1項から第10項の何れか1項に記載の光学フィルムの製造方法。
- 請求の範囲第1項から第11項の何れか1項に記載の光学フィルムの製造方法によって製造されたことを特徴とする光学フィルム。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010505527A JPWO2009119328A1 (ja) | 2008-03-27 | 2009-03-12 | 光学フィルムの製造方法及び光学フィルム |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008-083151 | 2008-03-27 | ||
JP2008083151 | 2008-03-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009119328A1 true WO2009119328A1 (ja) | 2009-10-01 |
Family
ID=41113526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2009/054754 WO2009119328A1 (ja) | 2008-03-27 | 2009-03-12 | 光学フィルムの製造方法及び光学フィルム |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPWO2009119328A1 (ja) |
KR (1) | KR20110005790A (ja) |
WO (1) | WO2009119328A1 (ja) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010234715A (ja) * | 2009-03-31 | 2010-10-21 | Konica Minolta Opto Inc | 光学フィルムの製造方法、光学フィルム及び光学フィルムの製造装置 |
CN102267230A (zh) * | 2011-07-30 | 2011-12-07 | 江阴中绿化纤工艺技术有限公司 | 横拉机 |
WO2012153612A1 (ja) * | 2011-05-06 | 2012-11-15 | コニカミノルタアドバンストレイヤー株式会社 | 延伸セルロースエステルフィルム、及びその製造方法 |
WO2013191102A1 (ja) * | 2012-06-21 | 2013-12-27 | コニカミノルタ株式会社 | 光学フィルム積層体の製造方法、薄型偏光膜、偏光板及び液晶表示装置 |
JPWO2013140728A1 (ja) * | 2012-03-21 | 2015-08-03 | コニカミノルタ株式会社 | 長尺延伸フィルムの製造方法 |
JP2016221809A (ja) * | 2015-05-29 | 2016-12-28 | 株式会社カネカ | フィルムの製造方法、フィルムの製造装置、及び一軸延伸フィルム |
JP2017177686A (ja) * | 2016-03-31 | 2017-10-05 | 株式会社カネカ | 光学フィルムの製造方法 |
CN112406146A (zh) * | 2020-10-26 | 2021-02-26 | 安徽铜峰电子股份有限公司 | 一种双向拉伸聚4-甲基1-戊烯薄膜及其制备方法 |
CN112533755A (zh) * | 2018-05-18 | 2021-03-19 | 3M创新有限公司 | 成型光学膜 |
CN114536726A (zh) * | 2022-02-24 | 2022-05-27 | 宁波长阳科技股份有限公司 | 薄膜纵向拉伸装置及薄膜纵向拉伸方法 |
CN114643703A (zh) * | 2022-03-24 | 2022-06-21 | 江苏集萃功能材料研究所有限公司 | 一种薄膜拉伸系统及其应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003057444A (ja) * | 2001-08-20 | 2003-02-26 | Fuji Photo Film Co Ltd | 光学異方性延伸フイルム、光学異方性延伸フイルムの製造方法、位相差板、円偏光板および液晶表示装置 |
JP2003322722A (ja) * | 2002-05-01 | 2003-11-14 | Fuji Photo Film Co Ltd | 光学フィルム |
JP2004018784A (ja) * | 2002-06-19 | 2004-01-22 | Toray Ind Inc | ポリエステルフィルム及びその製造方法 |
JP2005111919A (ja) * | 2003-10-10 | 2005-04-28 | Toray Ind Inc | 離型用二軸延伸ポリエステルフィルム |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60262624A (ja) * | 1984-06-08 | 1985-12-26 | Unitika Ltd | ポリエステルフイルムの延伸方法 |
JPH10244586A (ja) * | 1997-03-06 | 1998-09-14 | Fuji Photo Film Co Ltd | 縦延伸熱可塑性ポリマーフィルムの製造方法 |
JPH10332936A (ja) * | 1997-05-29 | 1998-12-18 | Nippon Synthetic Chem Ind Co Ltd:The | ポリビニルアルコール系位相差フィルムの製造法 |
JP3852671B2 (ja) * | 2000-12-05 | 2006-12-06 | 東洋紡績株式会社 | 二軸延伸ポリエステルフィルムの製造方法 |
JP2002192609A (ja) * | 2000-12-22 | 2002-07-10 | Toyobo Co Ltd | 二軸延伸ポリエステルフィルムの製造方法 |
JP4721655B2 (ja) * | 2004-05-21 | 2011-07-13 | 富士フイルム株式会社 | 飽和ノルボルネンフィルムおよびその製造方法 |
JP5184806B2 (ja) * | 2006-04-11 | 2013-04-17 | 富士フイルム株式会社 | 透明熱可塑性フィルムの製造方法および透明熱可塑性フィルム |
JP4975504B2 (ja) * | 2006-04-13 | 2012-07-11 | 富士フイルム株式会社 | 透明熱可塑性フィルムおよびその製造方法 |
JP5038777B2 (ja) * | 2006-05-18 | 2012-10-03 | 富士フイルム株式会社 | セルロースアシレートフィルムおよびその製造方法、並びに、それを用いた位相差フィルム、偏光板および液晶表示装置 |
-
2009
- 2009-03-12 WO PCT/JP2009/054754 patent/WO2009119328A1/ja active Application Filing
- 2009-03-12 KR KR1020107021137A patent/KR20110005790A/ko not_active Application Discontinuation
- 2009-03-12 JP JP2010505527A patent/JPWO2009119328A1/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003057444A (ja) * | 2001-08-20 | 2003-02-26 | Fuji Photo Film Co Ltd | 光学異方性延伸フイルム、光学異方性延伸フイルムの製造方法、位相差板、円偏光板および液晶表示装置 |
JP2003322722A (ja) * | 2002-05-01 | 2003-11-14 | Fuji Photo Film Co Ltd | 光学フィルム |
JP2004018784A (ja) * | 2002-06-19 | 2004-01-22 | Toray Ind Inc | ポリエステルフィルム及びその製造方法 |
JP2005111919A (ja) * | 2003-10-10 | 2005-04-28 | Toray Ind Inc | 離型用二軸延伸ポリエステルフィルム |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010234715A (ja) * | 2009-03-31 | 2010-10-21 | Konica Minolta Opto Inc | 光学フィルムの製造方法、光学フィルム及び光学フィルムの製造装置 |
JP5861700B2 (ja) * | 2011-05-06 | 2016-02-16 | コニカミノルタ株式会社 | 延伸セルロースエステルフィルム、及びその製造方法 |
WO2012153612A1 (ja) * | 2011-05-06 | 2012-11-15 | コニカミノルタアドバンストレイヤー株式会社 | 延伸セルロースエステルフィルム、及びその製造方法 |
TWI499496B (zh) * | 2011-05-06 | 2015-09-11 | Konica Minolta Opto Inc | A stretched cellulose ester film, and a method for producing the same |
CN102267230A (zh) * | 2011-07-30 | 2011-12-07 | 江阴中绿化纤工艺技术有限公司 | 横拉机 |
CN102267230B (zh) * | 2011-07-30 | 2013-05-01 | 江阴中绿化纤工艺技术有限公司 | 横拉机 |
JPWO2013140728A1 (ja) * | 2012-03-21 | 2015-08-03 | コニカミノルタ株式会社 | 長尺延伸フィルムの製造方法 |
WO2013191102A1 (ja) * | 2012-06-21 | 2013-12-27 | コニカミノルタ株式会社 | 光学フィルム積層体の製造方法、薄型偏光膜、偏光板及び液晶表示装置 |
TWI512342B (zh) * | 2012-06-21 | 2015-12-11 | Konica Minolta Inc | A method for producing an optical film laminate, a thin polarizing film, a polarizing plate, and a liquid crystal display device |
JPWO2013191102A1 (ja) * | 2012-06-21 | 2016-05-26 | コニカミノルタ株式会社 | 光学フィルム積層体の製造方法、薄型偏光膜、偏光板及び液晶表示装置 |
JP2016221809A (ja) * | 2015-05-29 | 2016-12-28 | 株式会社カネカ | フィルムの製造方法、フィルムの製造装置、及び一軸延伸フィルム |
JP2017177686A (ja) * | 2016-03-31 | 2017-10-05 | 株式会社カネカ | 光学フィルムの製造方法 |
CN112533755A (zh) * | 2018-05-18 | 2021-03-19 | 3M创新有限公司 | 成型光学膜 |
CN112533755B (zh) * | 2018-05-18 | 2022-11-18 | 3M创新有限公司 | 成型光学膜 |
CN112406146A (zh) * | 2020-10-26 | 2021-02-26 | 安徽铜峰电子股份有限公司 | 一种双向拉伸聚4-甲基1-戊烯薄膜及其制备方法 |
CN114536726A (zh) * | 2022-02-24 | 2022-05-27 | 宁波长阳科技股份有限公司 | 薄膜纵向拉伸装置及薄膜纵向拉伸方法 |
CN114536726B (zh) * | 2022-02-24 | 2023-11-07 | 宁波长阳科技股份有限公司 | 薄膜纵向拉伸装置及薄膜纵向拉伸方法 |
CN114643703A (zh) * | 2022-03-24 | 2022-06-21 | 江苏集萃功能材料研究所有限公司 | 一种薄膜拉伸系统及其应用 |
Also Published As
Publication number | Publication date |
---|---|
KR20110005790A (ko) | 2011-01-19 |
JPWO2009119328A1 (ja) | 2011-07-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2009119328A1 (ja) | 光学フィルムの製造方法及び光学フィルム | |
JP4888395B2 (ja) | セルロースフィルムの製造方法 | |
KR101216903B1 (ko) | 광학 필름 | |
JP5560710B2 (ja) | 光学フィルムの製造方法 | |
JPWO2009044673A1 (ja) | 光学フィルム、その製造方法、偏光板、及び表示装置 | |
JP2008044336A (ja) | タッチロール、光学フィルムの製造装置、及び、光学フィルムの製造方法 | |
JP4883087B2 (ja) | 光学フィルムとその製造方法 | |
JP2009096051A (ja) | 光学フィルム、及びその製造方法 | |
JP2010058386A (ja) | 光学フィルムの製造方法及び光学フィルム | |
JP2007098917A (ja) | 光学フィルム、及びその製造方法 | |
JP2013208717A (ja) | 光学フィルムの製造方法、偏光板及び液晶表示装置 | |
JP2010076279A (ja) | 光学フィルムの製造方法、光学フィルム、偏光板および液晶表示装置 | |
JP2008265167A (ja) | 熱可塑性フイルム及びその製造方法、並びに、偏光板、液晶表示板用光学補償フイルム、反射防止フイルム及び液晶表示装置 | |
JP2010214863A (ja) | テンター用クリップ及び光学フィルムの製造方法 | |
JP5907178B2 (ja) | 光学フィルムの製造方法 | |
JP5673526B2 (ja) | 光学フィルムの製造方法 | |
JP5104154B2 (ja) | 位相差フィルムの製造方法 | |
JP4882566B2 (ja) | 光学フィルムの製造方法 | |
JP4453631B2 (ja) | ディスプレイ用光学フィルムの製造方法 | |
JP2008023745A (ja) | キャストロール、光学フィルムの製造装置、及び、光学フィルムの製造方法 | |
JP2008023762A (ja) | 光学フィルムとその製造方法 | |
JP5682522B2 (ja) | 液晶表示装置用光学フィルムの製造方法 | |
WO2011027681A1 (ja) | フィルムの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09724583 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010505527 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20107021137 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 09724583 Country of ref document: EP Kind code of ref document: A1 |