WO2007125729A1 - 光学フィルムの製造方法 - Google Patents
光学フィルムの製造方法 Download PDFInfo
- Publication number
- WO2007125729A1 WO2007125729A1 PCT/JP2007/057388 JP2007057388W WO2007125729A1 WO 2007125729 A1 WO2007125729 A1 WO 2007125729A1 JP 2007057388 W JP2007057388 W JP 2007057388W WO 2007125729 A1 WO2007125729 A1 WO 2007125729A1
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- WIPO (PCT)
- Prior art keywords
- belt support
- width
- film
- belt
- optical film
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/38—Moulds, cores or other substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
Definitions
- the present invention relates to an optical film used in various display devices such as a liquid crystal display device (LCD) or an organic EL (electric mouth luminescence) display, in particular, a protective film for a polarizing plate used in these display devices, and a film.
- the present invention relates to a method for producing an optical film having birefringence that can be used as a phase difference film.
- the basic configuration of a liquid crystal display device is one in which polarizing plates are provided on both sides of a liquid crystal cell. Since a polarizing plate allows only light with a polarization plane in a certain direction to pass, it plays an important role in visualizing changes in the orientation of liquid crystal due to an electric field in a liquid crystal display device. The performance of a liquid crystal display device depends on the performance of the polarizing plate. Is greatly affected.
- a resin solution having a desired component is cast on an endless belt (belt support) made of a rotationally driven metal until it can be conveyed. After drying, the film is peeled off from the belt support, then dried and wound up to produce a film.
- meandering adjustment during film (web) conveyance by the belt support is performed by changing the angle formed by the rotation shafts of the pair of front and rear rotating drums that rotationally drive the metal endless belt.
- a method is adopted in which the rotational axis of one of the rotating drums is slightly shifted from the direction perpendicular to the traveling direction of the belt support.
- a strong force is applied to the belt end, so that the belt end is deformed by repeated control. In particular, this deformation becomes significant when the width of the belt support exceeds 1.8 m.
- patent literature relating to a method for producing an optical film by a solution casting film forming method using a wide belt support includes the following.
- Patent Document 1 discloses a solution casting method.
- a belt having a width of 1.6 m or more is used as a support for supporting a film of polymer solution cast by Daika, and the belt.
- the meandering amount of the belt is ⁇ 0.5% or less of the belt width
- the casting width of the film from the die is 70% or more of the belt width and the belt width (meandering amount X 4) or less. ing.
- Patent Document 1 JP 2002-127169 A
- Patent Document 1 for the wide belt support, the force for defining the casting width of the film with respect to the belt width and suppressing the amount of meandering is small.
- the problem is that the belt end is deformed during long-term operation.
- An object of the present invention is to solve the above-mentioned problems of the prior art, and to maintain a stable conveying state with less meandering even when a wide belt support is used for film production, Ev) An object of the present invention is to provide a method for producing an optical film capable of obtaining a stable and high productivity without poor drying at the edge and deterioration of the flatness of the film.
- the present inventor has adopted the following means in the solution casting film forming method, thereby enabling the bell during the meander control. It was found that the stress applied to the belt support is reduced, and deformation of both ends of the belt support after a long operation is suppressed, and the present invention has been completed.
- the invention of claim 1 is characterized in that a dope (solution) obtained by dissolving a thermoplastic resin film raw material in a solvent has a width of 1.8 m or more from a casting die.
- the thickness (Te) of the left and right end portions, each having a width (We) of 2 to 25% of the total width (W) of the belt support, is greater than the thickness (T) of the other portions including the width center of the belt support. 5-20% thin.
- the invention of claim 2 is the method for producing an optical film of claim 1, wherein the belt support has a belt support full width from the left and right side edges of the belt support, respectively.
- the invention of claim 3 is the method for producing an optical film of claim 1, wherein the belt support is formed from the left and right side edges of the belt support, respectively.
- W 10-20% width
- We thickness of left and right ends
- T thickness of other parts including the width center of belt support It is characterized by this.
- the invention of claim 4 is the method of manufacturing an optical film according to claim 1, wherein the belt support is respectively wider than the left and right side edges of the belt support.
- W 10-20% width
- We thickness of both left and right ends
- T thickness of other parts including the width center of the belt support It is characterized by this.
- the invention of claim 5 is the method of manufacturing an optical film according to any one of claims 1 to 4, wherein the belt support is a belt support.
- the thin left and right end portions and other thick portions including the width central portion are integrally formed by welding.
- the invention of claim 6 relates to a belt in which a dope (solution) in which a thermoplastic resin film raw material is dissolved in a solvent is cast on a belt support having a casting die force width of 1.8 m or more.
- a method of producing an optical film by drying a web (film) that has been peeled off from a support, wherein the belt support has a total width (W) of the belt support from the left and right side edges of the belt support.
- the invention of claim 7 is the method of manufacturing an optical film according to claim 6, wherein the belt support is formed from the left and right side edges of the belt support, respectively.
- the longitudinal elastic modulus (Ee) force of the left and right ends having a width (We) of 2 to 25% of (W)
- the longitudinal elastic modulus (E) of other parts including the center of the width of the belt support 8 It is characterized by ⁇ 15% smaller.
- the invention of claim 8 is the method of manufacturing an optical film according to claim 6, wherein the belt support has a full width of the belt support from both left and right side edges of the belt support.
- the longitudinal elastic modulus (Ee) of the left and right end portions having a width (We) of 10 to 20% of (W) is more than the longitudinal elastic modulus (E) of other portions including the width central portion of the belt support. It is characterized by being ⁇ 20% smaller.
- the invention according to claim 9 is the method for producing an optical film according to claim 6, wherein the belt support has a full width of the belt support from both left and right side edges of the belt support.
- the longitudinal elastic modulus (Ee) of the left and right end portions having a width (We) of 10 to 20% of (W) is more than the longitudinal elastic modulus (E) of other portions including the width center portion of the belt support. It is characterized by being ⁇ 15% smaller.
- the invention of claim 10 is the method for producing an optical film according to any one of claims 6 to 9, wherein the belt support is a belt support. It is characterized in that both left and right end portions having a small longitudinal elastic modulus and other portions having a large longitudinal elastic modulus including the central portion of the width are joined together by welding.
- the invention of claim 11 is the method of manufacturing an optical film according to any one of claims 1 to 10, wherein the width of the optical film is 1.7 m or more. Be It is characterized by.
- the invention of claim 12 is the method for producing an optical film according to any one of claims 1 to 10, wherein the thermoplastic resin film raw material is a cellulose ester. It is characterized by including. The invention's effect
- the invention of claim 1 is a method for producing an optical film by a solution casting film forming method, wherein the full width of the belt support (W ) Of the belt support having a width (We) of 2 to 25%, the thickness (Te) of the left and right ends of the belt support is 5 to 20 than the thickness (T) of the other portions including the width center of the belt support.
- the belt end portions on both the left and right sides of the belt support By reducing the thickness of the edge portion, the stress applied to the belt support during meander control is reduced, and deformation at both ends of the belt support after long-time operation is suppressed, resulting in less meandering and stable conveyance.
- the cast film (web) edge dry and the film To be able to flat surface deterioration obtain a stable high productivity Nag, when it is possible to manufacture an optical film having a good quality, it exhibits the cormorants effect.
- inventions of claims 2 to 4 further limit the belt support used in the method for producing an optical film according to claim 1, and thereby, Deformation of both ends of the belt support after long-time operation can be further effectively suppressed.
- the invention of claim 5 is the method of manufacturing an optical film according to any one of claims 1 to 4, wherein the belt support is thin. It uses a belt support in which the left and right end portions and other thick portions including the width central portion are integrally formed by welding, whereby a belt support having a desired wide width can be used. It is possible to maintain a stable conveyance state with less meandering and to obtain stable high productivity without poor drying of the cast film (web) edge and deterioration of the flatness of the film. There is an effect that an optical film having the above can be manufactured.
- the invention of claim 6 is an optical film manufacturing method by a solution casting film forming method, wherein the belt support has a full width (W) from the left and right side edges of the belt support having a width of 1.8 m or more.
- the longitudinal elastic modulus (Ee) of the left and right end portions of the belt support having a width (We) of -25% is 5 to 5 more than the longitudinal elastic modulus (E) of the other portions including the width central portion of the belt support.
- the belt ends on both the left and right sides of the belt support are reduced in order to reduce the deformation at both ends of the film that occurs when a wide belt support is used for film production.
- the invention of claim 10 is the method for producing an optical film according to any one of claims 6 to 9, wherein the longitudinal elastic modulus of the belt support is small. It uses a belt support in which the left and right end portions and other portions having a large longitudinal elastic modulus including the width central portion are integrated by welding, thereby using a belt support having a desired wide width. It is possible to maintain a stable conveyance state with less meandering, and to obtain stable high productivity without poor drying at the end of the cast film (web) and deterioration of the flatness of the film. If an optical film having a high quality can be manufactured, the effect is obtained.
- the invention of claim 11 is the method of manufacturing an optical film according to any one of claims 1 to 10, wherein the width of the optical film is 1.7 m or more.
- the width of the optical film is 1.7 m or more.
- the invention of claim 12 is the method for producing an optical film according to any one of claims 1 to 11, wherein the thermoplastic resin film raw material is a cellulose ester.
- the thermoplastic resin film raw material is a cellulose ester.
- FIG. 1 is a partially enlarged perspective view showing a first embodiment of a belt support in a casting process of a solution casting film forming apparatus for carrying out the method for producing an optical film of the present invention.
- FIG. 2 is an enlarged cross-sectional view of the belt support shown in FIG.
- FIG. 3 is an enlarged cross-sectional view of the main part of FIG.
- FIG. 4 is an enlarged cross-sectional view of the main part showing a modified example of the belt support.
- FIG. 5 is a partially enlarged perspective view showing a second embodiment of the belt support in the casting process of the solution casting film forming apparatus for carrying out the method for producing an optical film of the present invention.
- FIG. 6 is a partially enlarged perspective view showing a third embodiment of the belt support in the casting process of the solution casting film forming apparatus for carrying out the method for producing an optical film of the present invention.
- FIG. 7a is a plan view showing a state in which the angle of the rotating shaft of the rotating drum is changed for the meandering adjustment during conveyance by the belt support in the casting process of the solution casting film forming apparatus.
- Fig. 7b is a side view of the same.
- FIG. 8 is an enlarged cross-sectional view of the main part of the end of the belt support showing the method for measuring the belt end deformation in Examples 1 to 17 of the present invention.
- FIG. 9 is a plan view of an experimental apparatus for measuring the amount of deformation of the belt support end by repeatedly applying a load to the belt test sample piece in Examples 18 to 23 of the present invention.
- FIG. 10 is a side view of the same.
- the present invention is a method for producing an optical film by a solution casting film forming method, in which a dope (solution) obtained by dissolving a thermoplastic resin film raw material in a solvent is rotated from a casting die by a width of 1.8 m or more.
- the optical film is produced by drying a web (film) cast on a metal endless belt (belt support) and peeled off the force on the belt support.
- the thickness (Te) of the left and right ends (lb) of the belt support having a predetermined width (We) from the left and right side edges of the belt support (1) It is thinner than the thickness (T) of the part (la).
- the width of the belt support is a dimension defined in Fig. 2 (cross-sectional view of the belt support).
- the difference in thickness of the belt support is a dimension defined in FIG.
- the invention described in claims 1 to 5 occurs when the belt support (1) having a width of 1.8 m or more is used for the production of an optical film.
- This is one of the methods for reducing the deformation of the left and right end portions (lb) of the belt support (1).
- Belt support (1) By reducing the thickness of both end portions (lb), the stress applied to the belt end portions (lb) during meandering control is reduced, and deformation of the belt end portions (lb) after a long period of operation is suppressed.
- the change in thickness may be stepped as shown in FIGS. 2 and 3, but it is preferable to be smooth in a taper as shown in FIG. In this case, the width and thickness of the belt end are defined as shown in FIG.
- the left and right ends of the belt support (1) may be machined. As shown in the figure, materials with different thicknesses may be welded to both ends.
- the width of the belt support (1) has an upper limit depending on the capability of the device manufacturer. As shown in Fig. 5, the side edges of the two belt supports (1A) (1B) are welded together. Thus, it can be used as a wide belt support (1). If a wider belt support (1) is required, the side edges of the three belt supports (1A) (IB) (1C) may be welded together as shown in FIG.
- the welded portion (Y) of the belt support (1) is polished to a mirror surface with no problem in terms of product quality even when transferred to a film. If the film quality of the weld (Y) is a problem, place the weld line so that the weld (Y) is outside the effective product.
- the belt support body (1) having a width of 1.8 m or more is predetermined from both left and right edges.
- the longitudinal elastic modulus (Young's modulus) (Ee) of the left and right end parts (lb) of the belt support having a width (We) is equal to the longitudinal elasticity of the other part (la) including the center of the width of the belt support. Smaller than the coefficient (E)! /.
- the width of the belt support is a dimension defined in Fig. 2 (cross-sectional view of the belt support).
- the longitudinal elastic modulus is defined by Ee as the longitudinal elastic modulus of the left and right end parts (lb) of the belt support, and E as the longitudinal elastic modulus of the other part (la) including the center of the width of the belt support.
- the invention described in claims 6 to 10 occurs when a belt support (1) having a width of 1.8 m or more is used for production of an optical film.
- This is another way to reduce the deformation of the left and right ends (lb) of the belt support (1).
- the deformation of the left and right ends (lb) of the belt support is suppressed.
- the left and right end portions (lb) of the belt support may be heat-treated, or In this way, metals of different materials may be welded to both ends. Further, a member having a cavity in the thickness direction may be welded to both ends. For example, as shown in FIG. 6, the side edges of three belt supports (1A) (IB) (1C) made of metals of different materials may be welded together.
- the welded portion (Y) of the belt support (1) is polished so as to have a mirror surface with no problem in product quality even when transferred to a film. If the quality of the welded part (Y) film is a problem, the weld line should be placed so that the welded part (Y) is outside the effective product.
- the rotation shafts of the pair of front and rear rotating drums (2) and (3) that rotationally drive the metal endless belt (1) are made. Change the angle. For example, this is performed by a method in which the rotational axis of one front rotating drum (2) is slightly shifted from the right angle with the traveling direction of the belt support (1).
- the width of the belt support becomes as large as 1.8 m or more, such meandering control becomes difficult, and the amount of meandering of the belt support (1) becomes large.
- the dope (resin solution) cast from the casting die (4) drips out of the belt support (1) and contaminates the production equipment.
- the belt support (1) when the belt support (1) is operated for a long time with the large meandering always controlled, a large force continues to be applied particularly to the left and right ends of the belt support (1).
- the left and right ends (or both side edges) of) are deformed into a waveform (so-called wakame-like shape) when viewed from the side. If the deformation of the left and right ends of the belt support (1) becomes large, the contact between the belt support end and the heating Z cooling drum will be weak, and heat transfer there will be less, resulting in poor drying of the film end, Bubble entrainment at the edge of the film occurs. Further, the poor drying of the film edge portion means that the film (web) partly remains on the belt support side when the film is peeled off. If the deformation at the left and right ends of the belt support is further increased, the flatness of the film product will deteriorate, the belt support (1) end will contact the casting die (4), and the equipment will be damaged. Will interfere with film production.
- the thickness (Te) of the left and right end portions (lb) of the belt support is the other portion (la) including the width center portion of the belt support. Thinner than the thickness (T). Therefore, the force applied to the left and right end portions (lb) of the belt support is weakened, and the deformation of the left and right end portions (lb) of the belt support can be reduced even by repeated control.
- the thickness (Te) of the left and right ends (lb) of the belt support is 5 (%) ⁇ (1 TeZ T) X 100 ⁇ 20 (%).
- the width (We) of lb) is 2 (%) ⁇ (We / W) X 100 ⁇ 25 (%), the left and right end portions (lb) of the belt support are less deformed and have poor peeling. The amount of meandering that occurs is also reduced.
- the longitudinal elastic modulus (Ee) of the left and right end portions (lb) of the belt support is the other portion including the width center portion of the belt support.
- the longitudinal elastic coefficient (Ee) of the left and right ends (lb) of the belt support is reduced, the thickness (Te) of the left and right ends (lb) of the belt support is reduced.
- film formation can be performed in a state where the left and right end portions (lb) of the belt support body are less deformed and the occurrence of peeling failure is less and the meandering amount is small.
- the width (We) of the small heel part of the longitudinal elastic modulus (Ee) of the left and right end parts (lb) of the belt support is 5 (%) ⁇ WeZWX 100 ⁇ 25 (%) and 10 (%) It is particularly preferable that ⁇ WeZWX 100 ⁇ 20 (%).
- the longitudinal elastic modulus (Ee) of the left and right ends (lb) of the belt support is 5 (%) ⁇ (1—EeZE) X 100 ⁇ 20 (%), and 8 (%) ⁇ (1 -Ee / E) X 100 ⁇ 1 5 (%) is particularly preferred.
- Examples of the resin preferably used in the method of the present invention include cellulose esters having a substitution degree of acyl groups of 1.8 to 2.80 such as cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate.
- Cellulose resin, and cellulose oleore group such as cellulose methyl etherol, senorelose cetinore ethenore, senorelose propino enotenole etc.
- cellulose ester-based resins such as cenorelose acetate, cellulose acetate propionate, and cellulose acetate butyrate, cycloolefin resin, norbornene-based resin, and polycarbonate resin are particularly preferable.
- two or more types of compatible polymers may be blended and dope dissolution described later may be performed, but the present invention is not limited to these.
- Examples of other resins preferably used in the present invention include homopolymers and copolymers having an ethylenically unsaturated monomer unit. More preferably, poly (methyl acrylate), poly (ethyl acrylate), poly (propyl acrylate), poly (hydroxy acrylate) hexyl, copolymers of alkyl acrylate, poly (methyl methacrylate), poly (ethyl methacrylate), poly (cyclomethacrylate). Examples include homopolymers or copolymers of acrylic acid or methacrylic acid esters such as xylyl and methacrylic acid alkyl ester copolymers.
- acrylic acid or methacrylic acid esters are excellent in transparency and compatibility
- homopolymers or copolymers having acrylate or methacrylate units particularly acrylic acid or methyl methacrylate units.
- homopolymers or copolymers having are preferred.
- polymethyl methacrylate is preferable.
- Alicyclic alkyl esters of acrylic acid or methacrylic acid such as polyacrylic acid or polymethacrylic acid cyclohexane have advantages such as high heat resistance, low hygroscopicity, low birefringence, etc. Power is preferable.
- the method for producing an optical film of the present invention is carried out by a solution casting method.
- a cellulose ester solution containing a cellulose ester and an organic solvent is referred to as a dope, which is used to form a cellulose ester film by solution casting.
- the cellulose used as a raw material for the cellulose ester used in the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Also from them The obtained cellulose esters can be used alone or in admixture at any ratio.
- the cellulose ester is an organic acid such as acetic acid when the acylating agent of the cellulose raw material is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride).
- the reaction is performed using an organic solvent such as methylene chloride and a protic catalyst such as sulfuric acid.
- the acylating agent is acid chloride (CH COCl, C H COCl, C H COC1)
- the reaction is carried out using a basic compound such as ammine as the catalyst. Specifically, it can be synthesized by the method described in JP-A-10-45804.
- the acyl group reacts with the hydroxyl group of the cellulose molecule.
- Cellulose molecules have the power of linking many glucose units, and there are three hydroxyl groups per glucose unit. The number of substituted acyl groups at these three hydroxyl groups is called the degree of substitution.
- cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit.
- the cellulose ester that can be used in the cellulose ester film preferably has a total acyl group substitution degree of 2.4 to 2.8.
- the molecular weight of the cellulose ester used in the present invention is 50, 0 in terms of number average molecular weight (Mn).
- the cellulose ester used in the present invention preferably has a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), and MwZMn is preferably 1.4 to 3.0, more preferably 1. 7 ⁇
- the average molecular weight and molecular weight distribution of the cellulose ester can be measured by a known method using high performance liquid chromatography. Using this, the number average molecular weight and the weight average molecular weight can be calculated, and the ratio (MwZMn) can be calculated.
- the cellulose ester used in the present invention is a carboxylic acid ester having about 2 to 22 carbon atoms, and is particularly preferably a lower fatty acid ester of cellulose.
- the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms, such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate phthalate, and the like.
- Mixed fatty acid esters such as V, such as cellulose acetate propionate and cellulose acetate butyrate described in Japanese Patent No. 45804, Japanese Patent Laid-Open No. 8-231761, and US Pat. No. 2,319,052 Can be used.
- an ester of an aromatic carboxylic acid and cellulose and cellulose acylate described in JP-A-2002-179701, JP-A-2002-265639, and JP-A-2002-265638 are also preferably used.
- the lower fatty acid esters of cellulose particularly preferably used are cellulose triacetate and cellulose acetate propionate. These cellulose esters can be used as a mixture.
- Preferred cellulose esters other than cellulose triacetate have an acyl group having 2 to 4 carbon atoms as a substituent, and the degree of substitution of the acetyl group is X, and the degree of substitution of the propiol group or petityl group is When Y, it is a cellulose ester that simultaneously satisfies the following formulas (a) and (b).
- Equation (a) 4. 4 ⁇ X + Y ⁇ 2.8
- the degree of substitution of these acyl groups can be measured according to the method prescribed in ASTM-D817-96.
- the degree of decomposition can be defined by the value of the weight average molecular weight (Mw) Z number average molecular weight (Mn) that is usually used. That is, in the process of cellulose triacetate vinegar, it is not too long to decompose too much
- weight average molecular weight (Mw) Z number average molecular weight (Mn) can be used as an index of the degree of reaction for allowing vinegar to react for a sufficient time.
- acetyl cellulose having a degree of acetyl substitution of 2.75. Obtained.
- This acetylcellulose had Mn of 92,000, Mw of 156,000, and MwZMn of 1.7.
- cellulose esters having different degrees of substitution and MwZMn ratios can be synthesized by adjusting the esterification conditions (temperature, time, stirring) and hydrolysis conditions of the cellulose ester.
- the synthesized cellulose ester is preferably purified to remove low molecular weight components or to remove components of non-acetic acid by filtration.
- the cellulose ester is also affected by a trace metal component in the cellulose ester. These are thought to be related to water used in the manufacturing process, but metal ions such as iron, calcium, and magnesium are preferred to contain fewer components that can form insoluble nuclei. Insoluble matter may be formed by salt formation with a polymer degradation product or the like that may be lost, and it is preferable that the amount is small.
- the iron (Fe) component is preferably 1 ppm or less.
- the calcium (Ca) component is abundant in groundwater, river water, etc., and if it is too much, it becomes hard water and is also unsuitable as drinking water.
- Acidic components such as carboxylic acids and sulfonic acids, and many more Coordination complexes with the ligands of, scum (insoluble starch, turbidity) derived from a large amount of insoluble calcium immediately form a complex.
- scum insoluble starch, turbidity
- the calcium (Ca) component is 60 ppm or less, preferably 0 to 30 ppm.
- the magnesium (Mg) component too much too much results in insoluble matter, so 0 to 70 ppm is preferable, and 0 to 20 ppm is particularly preferable.
- Metal components such as iron (Fe) content, calcium and a) content, and magnesium (Mg) content are pre-treated by microdigest wet cracking equipment (sulfuric acid decomposition) and alkali melting. This can be obtained by performing analysis using ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometer).
- Organic solvents useful for forming a dope (solution) by dissolving cellulose ester include chlorine-based organic solvents and non-chlorine-based organic solvents.
- Methylene chloride methylene chloride
- Non-chlorine organic solvents include, for example, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3 dioxolane, 1,4 dioxane, cyclohexanone, ethyl formate, 2, 2, 2 trifluoro Ethanol, 2, 2, 3, 3 Hexafluoro-1 propanol, 1, 3— Difluoro-2 propanol, 1, 1, 1, 3, 3, 3 Hexafluoro-2-methyl-2-prononore, 1, 1, 1, 3, 3, 3 Hexafnoroleol 2 prono nore, 2, 2, 3, 3, 3 pentafluoro-1-propanol, nitroethane and the like can be mentioned.
- a dissolution method at room temperature can be used, but by using a dissolution method such as a high-temperature dissolution method, a cooling dissolution method, or a high-pressure dissolution method. It is preferable because insoluble matter can be reduced.
- a dissolution method such as a high-temperature dissolution method, a cooling dissolution method, or a high-pressure dissolution method. It is preferable because insoluble matter can be reduced.
- Cell mouth For cellulose esters other than monotriacetate, methylene chloride can be used, but methyl acetate, ethyl acetate, and acetone are preferably used. In particular, methyl acetate is preferred.
- an organic solvent having a good solubility in the cellulose ester is referred to as a good solvent, and has a main effect on dissolution, and an organic solvent used in a large amount among them is a main (organic) solvent or a main ( Organic) solvent and ⁇ ⁇ .
- the dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent.
- the solvent starts to evaporate and the alcohol ratio increases, the dope film (web) gels, making the web strong and easy to peel off from the metal carrier. It is also used as a gelling solvent, and when these ratios are small, it also has a role of promoting dissolution of the cellulose ester of a non-chlorine organic solvent.
- the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec butanol and tert-butanol. Of these, ethanol is preferable because it has excellent dope stability, has a relatively low boiling point, and has good drying properties.
- Additives added to the dope include fine particles such as a plasticizer, an ultraviolet absorber, an antioxidant, a dye, and a matting agent.
- these additives may be added during the preparation of the cellulose ester solution, or may be added during the preparation of a fine particle dispersion such as a matting agent.
- the polarizing plate used in the liquid crystal image display device has a plasticizer, oxidation, and heat / moisture resistance. It is preferable to add an inhibitor, an ultraviolet absorber or the like. The additives are explained below.
- a cellulose ester solution or dope is prepared by adding a compound known as a so-called plasticizer for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor permeability, and adjusting retardation.
- plasticizer for the purpose of improving mechanical properties, imparting flexibility, imparting water absorption resistance, reducing water vapor permeability, and adjusting retardation.
- phosphoric acid esters and carboxylic acid esters are preferably used.
- Examples of phosphoric acid esters include triphenyl phosphate, tricresyl phosphate, and phenyl diphosphate.
- Examples of the carboxylic acid ester include phthalic acid ester and citrate ester.
- Examples of the phthalic acid ester include dimethyl phthalate, jetyl phosphate, dioctyl phthalate, and jetyl hexyl phthalate. Mention may be made of cetyl cetyl and acetyl butyl thioate. Other examples include butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate, and triacetin.
- Alkylphthalylalkyl glycolates are also preferably used for this purpose. The alkyl in the alkylphthalylalkyl glycolate is an alkyl group having 1 to 8 carbon atoms.
- alkyl phthalyl alkyl glycolates include methyl phthalyl methyl dallicoleate, ethyl phthalyl ethyl dallicolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl dallicolate, octyl phthalyl octyl dallicolate, methyl phthalyl Ethyl dallicolate, Ethyl phthalyl methyl dallicolate, Ethyl phthalyl propyl glycolate, Propyl phthalyl ethyl dallicolate, Methyl phthalyl propyl glycolate, Methyl phthalyl butyl dallicolate, Ethyl phthalyl butyl dallicolate , Butyl phthalyl methyl glycolate, butyl phthalyl ethyl dalicolate, propyl phthalyl butyl gallate, butyl phthalyl
- Polyhydric alcohol esters are also preferably used.
- the polyhydric alcohol used in the present invention is represented by the following general formula.
- R1 represents an n-valent organic group
- n represents a positive integer of 2 or more
- an OH group represents an alcoholic group
- the polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a divalent or higher aliphatic polyhydric alcohol and monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester
- Examples of preferable polyhydric alcohols include, for example, the following: The present invention is not limited to these. Aditol, arabitol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1, 2 propanediol, 1, 3 propanediol, dipropylene glycol, tripropylene glycol, 1,2 butanediol, 1, 3 Butanediol, 1,4 Butanediol, Dibutylene glycol, 1,2,4 Butanetriol, 1,5 Pentanediol, 1,6 Hexanediol, Hexanetriol, Galactitol, Mannitol, 3-Methylpentane 1, 3, 5 Examples include triol, pinacol, sorbitol, trimethylol bread, trimethylolethane, and xylitol. In particular, triethylene glycol, tetraethylenedaricol, dipropylene glycol, tripropylene glycol,
- the monocarboxylic acid used in the polyhydric alcohol ester known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like, which are not particularly limited, can be used. Use of alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferred in terms of improving moisture permeability and retention.
- Examples of preferable monocarboxylic acids include the following powers The present invention is not limited thereto.
- aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms Can be preferably used. More preferably, the carbon number is 1-20. Particularly preferred is LO.
- acetic acid is contained, the compatibility with the cellulose ester increases, so that it is also preferable to use a mixture of acetic acid and other monocarboxylic acid.
- aliphatic monocarboxylic acid acetic acid, propionic acid, butyric acid, valeric acid, cabronic acid, enanthic acid, strong prillic acid, pelargonic acid, strong puric acid, 2-ethylethylhexanoic acid, undecyl acid , Lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, araquinic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, rataceric acid, etc.
- unsaturated fatty acids such as saturated fatty acid, undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, and arachidonic acid.
- Examples of preferable alicyclic monocarboxylic acids include cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cyclooctanecarboxylic acid, and derivatives thereof.
- examples of the aromatic monocarboxylic acid include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, biphenylcarboxylic acid, naphthalene carboxylic acid, tetralin carboxylic acid and the like.
- An aromatic monocarboxylic acid having two or more benzene rings, or a derivative thereof can be exemplified.
- Benzoic acid is particularly preferable.
- the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably 300 to 1500, more preferably 350 to 750. Larger molecular weights are preferred because they are less likely to volatilize, and smaller ones are preferred in terms of moisture permeability and compatibility with cellulose esters.
- the carboxylic acid used in the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Further, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
- These compounds 1 to the cellulose ester 30 mass 0/0, preferably it is preferably contained so as to be 1 to 20 mass%. In order to suppress bleeding out during stretching and drying, a compound having a vapor pressure at 200 ° C. of 1400 Pa or less is preferable. [0114] These compounds may be added together with cellulose ester or a solvent during the preparation of the cellulose ester solution, or may be added during or after the solution preparation.
- These additives can be contained in the dope or fine particle dispersion.
- the cellulose ester film can contain an ultraviolet absorber.
- ultraviolet absorbers examples include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and triazine compounds.
- a benzotriazole-based compound with less coloring is preferable.
- ultraviolet absorbers described in JP-A-10-182621, JP-A-8-337574, JP-A-2001-72782, JP-A-6-148430, JP-A-2002-31715, JP Polymer ultraviolet absorbers described in 2 002-169020, JP 2002-47357, JP 2002-363420, and JP 2003-113317 are also preferably used.
- an ultraviolet absorber from the viewpoint of preventing deterioration of the polarizer and the liquid crystal, it has an excellent ability to absorb ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of liquid crystal display property, it absorbs less visible light having a wavelength of 400 nm or more. Things are preferred.
- UV absorbers useful in the present invention include 2- (2'-hydroxymonomethylphenol) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert- Butylphenol) benzotriazole, 2— (2 ′ —hydroxy—3 ′ —tert—butyl—5′-methylphenol) benzotriazole, 2— (2 ′ —hydroxy—3 ′, 5′—di—tert — Butylphenol) 1 5 Chronobenzobenzolazole, 2— (2 ′ —Hydroxy 1 3 ′ — (3, “, 5 Q” —Tetrahydrophthalimidomethyl) 5, —Methylphenyl) benzotriazole, 2, 2 —Methylenebis (4- (1, 1, 3, 3-tetramethylbutyl) 1- (2H—benzotriazole-2-yl) phenol), 2— (2 ′ —hydroxy 3 ′ —tert-butyl 1 5'-Methy
- TINUVIN 109 TINUVIN 171 and TINUVIN 326 (all manufactured by Ciba Specialty Chemicals) can be preferably used.
- a reactive ultraviolet absorber RUVA-93 manufactured by Otsuka Chemical Co., Ltd. can be given as an example.
- benzophenone compounds include 2, 4 dihydroxybenzophenone, 2, 2 '
- Examples thereof include, but are not limited to, dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-1-sulfobenzophenone, and bis (2 methoxy-4-hydroxy-5-benzoylmethane).
- the ultraviolet absorber described above preferably used in the present invention is a benzotriazole-based ultraviolet absorber or a benzophenone-based ultraviolet absorber excellent in the effect of preventing deterioration of a highly transparent polarizing plate or liquid crystal element.
- Benzotriazole-based ultraviolet absorbers are particularly preferably used because they have less unwanted coloration that is preferred by the agent.
- the method of adding the ultraviolet absorber to the dope is a power that can be used without limitation as long as the ultraviolet absorber is soluble in the dope.
- the ultraviolet absorber may be methylene chloride, acetic acid.
- Cellulose ester solution as a UV absorber solution by dissolving in a good solvent for cellulose esters such as methyl and dioxolane, or in a mixed organic solvent of a good solvent and a poor solvent such as lower aliphatic alcohol (methanol, ethanol, propanol, butanol, etc.) Can be added to the cocoon or directly into the dope composition! / ⁇ .
- a dissolver or sand mill is used in the organic solvent and the polymer and dispersed before adding to the dope.
- the content of the ultraviolet absorber is 0.01 to 5 mass%, particularly 0.5 to 3 mass%.
- these ultraviolet absorbers may be used alone or in a mixture of two or more different types.
- a hindered phenol compound is preferably used.
- 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3 (3-, 5-di-tert-butyl-4-hydroxyphenol) propionate], triethylene glycol-bis [3- (3-t Butyl-5-methyl-4-hydroxyphenol) propionate] is preferred.
- hydrazine-based metal deactivators such as N, N'-bis [3- (3,5-di-tert-butyl 4-hydroxyphenyl) propiol] hydrazine, tris (2,4-
- phosphorus-based processing stabilizers such as di (tbutylbutyl) phosphite.
- the amount of addition of these compounds is preferably lppm to l.0% by weight with respect to the cellulose ester, more preferably 10 to 1 OOOppm.
- the optical film of the present invention is for imparting slipperiness or improving physical properties.
- fine particles such as a matting agent can be added.
- the fine particles include fine particles of an inorganic compound or fine particles of an organic compound, and the shape may be spherical, flat, rod-like, needle-like, layered, or indefinite.
- Examples of the fine particles of the inorganic compound include silicon dioxide, titanium dioxide, acid aluminum, zirconium oxide, calcium carbonate, calcium carbonate, kaolin, talc, clay, calcined calcium carbonate, hydrated key Mention may be made of metal oxides, hydroxides, silicates, phosphates, carbonates such as calcium acid, aluminum silicate, magnesium silicate and calcium phosphate.
- Examples of the fine particles of the organic compound include fine particles of silicone resin, fluorine resin, acrylic resin, etc., and those having a three-dimensional network structure that silicone resin is preferred.
- Power S liked ⁇ For example, Tosuno Kunore 103, 105, 108, 120, 145, 3120 and 240 (manufactured by Toshiba Silicone Co., Ltd.) can be listed.
- silicon dioxide is preferable because it can reduce the haze of the film.
- Fine particles such as silicon dioxide are often surface-treated with organic substances, but such particles are preferred because they can reduce the haze of the film.
- Preferred organic materials include halosilanes, alkoxysilanes, silazanes, siloxanes and the like.
- the average particle diameter of the fine particles is in the range of 0.005 to 1. O / zm.
- These primary particles may be secondary particles formed by aggregation.
- the content of fine particles is preferably 0.01 to 20 g per lm 2 with respect to rosin.
- Examples of the silicon dioxide fine particles include Aerosil (AERO SIL) 200, 200V, 300, R972, R972V, R974, R202, R812, R805, OX50, and TT600 manufactured by Aerosil Co., preferably. Aerosil 200V, R972, R972V, R974, R202, R812. Two or more of these fine particles may be used in combination. When two or more types are used in combination, they can be mixed and used at an arbitrary ratio. In this case, fine particles having different average particle sizes and materials, for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.
- Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.
- the presence of fine particles in the film used as the matting agent has another purpose. It can be used to improve the strength of rummes.
- the dope or fine particle dispersion used in the present invention preferably contains a surfactant, and is not particularly limited to phosphoric acid, sulfonic acid, carboxylic acid, non-one, cationic and the like. These are described in, for example, JP-A-61-243837.
- the amount of the surfactant is preferably is from 0.002 to 2 mass 0/0 to cellulose ⁇ shea rate instrument 0.01 to 1 mass% is more preferable. If the addition amount is less than 0.001% by mass, the effect of addition cannot be fully exerted, and if the addition amount exceeds 2% by mass, precipitation or insoluble matter may occur.
- the non-one surfactant is a surfactant having a non-ionic hydrophilic group of polyoxyethylene, polyoxypropylene, polyoxybutylene, polyglycidyl sorbitan.
- Examples of the cation surfactant include carboxylate, sulfate, sulfonate, and phosphate ester salt. Typical examples include fatty acid salts, alkylbenzene sulfonates, and alkyl naphthalene sulfonates.
- alkyl sulfonate alkyl sulfonate, a-olefin sulfonate, dialkyl sulfosuccinate, ⁇ -sulfonated fatty acid salt, ⁇ -methyl-oleyl taurine, petroleum sulfonate, alkyl sulfate, sulfate Fats and oils, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, naphthalene sulfonate form And aldehyde condensates.
- Examples of cationic surfactants include ammine salts, quaternary ammonium salts, pyridinium salts, etc., and primary to tertiary fatty amine salts, quaternary ammonium salts ( Tetraalkyl ammonium salts, trialkylbenzam salts, alkyl pyridinium salts, alkyl imi Dazolium salt, etc.).
- Examples of amphoteric surfactants include carboxybetaine and sulfobetaine, and N-trialkyl-N-carboxymethylammonium betaine, N-trialkylN sulfoalkylene ammonium betaine, and the like.
- the fluorosurfactant is a surfactant having a fluorocarbon chain as a hydrophobic group.
- a peeling accelerator for reducing the load during peeling may be added to the dope.
- surfactants are effective, and there are phosphoric acid-based, sulfonic acid-based, carboxylic acid-based, non-ionic, cationic and the like, but there is no particular limitation thereto.
- These peeling accelerators are described, for example, in JP-A-61-243837.
- Japanese Patent Application Laid-Open No. 57-500833 discloses polyethoxylated phosphate ester as a release accelerator.
- JP-A-1-299847 discloses that the peeling load can be reduced by adding a phosphate ester compound containing a non-esterified hydroxyl group and a propylene oxide chain and inorganic particles.
- thermal stabilizers such as inorganic fine particles such as kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, acidic titanium, and alumina, and alkaline earth metal salts such as calcium and magnesium can be added. Good.
- antistatic agents, flame retardants, lubricants, oils, etc. may be added.
- the method for producing an optical film according to the present invention is based on a solution casting method, and includes a dope preparation step, a casting step, a drying step, and a wrinkling step.
- cellulose ester will be described as an example of a thermoplastic resin film raw material (polymer material).
- Cellulose ester is dissolved by means such as a stirring dissolution method, a heating dissolution method, and an ultrasonic dissolution method in a dissolution vessel.
- a stirring dissolution method it is usually used, and under pressure, the boiling point is higher than the normal pressure of the solvent and the solvent does not boil! Heating at a temperature within a range, and the method of dissolving with stirring, it is more preferable in order to prevent the generation of massive undissolved material called gel or mako.
- a cooling dissolution method described in JP-A-9-95538 or a method of dissolving under high pressure described in JP-A-11-21379 may be used.
- a method in which a cellulose ester is mixed with a poor solvent to be moistened or swelled, and then mixed with a fine scouring good solvent and dissolved is also preferably used.
- a device for mixing or dissolving cellulose ester with a poor solvent and a device for mixing and dissolving with a good solvent may be separately provided.
- the type of the dissolution vessel (pressure vessel) used for dissolving the cellulose ester can withstand a predetermined pressure that is not particularly questioned, and can be heated and stirred under pressure. That's fine.
- instruments such as pressure gauges and thermometers will be appropriately installed in the melting pot (pressurized container).
- the pressurization may be performed by injecting an inert gas such as nitrogen gas or by increasing the vapor pressure of the solvent by heating. Heating is preferably performed by external force.
- the jacket type is preferable because temperature control is easy.
- the heating temperature after adding the solvent is equal to or higher than the boiling point of the solvent to be used. In the case of two or more mixed solvents, the heating temperature is higher than the boiling point of the lower solvent and A temperature in the range where the solvent does not boil is preferred. If the heating temperature is too high, the required pressure increases and productivity decreases. A preferable heating temperature range is 20 to 120 ° C, and 30 to 100 ° C is more preferable, and a range of 40 to 80 ° C is more preferable. The pressure is adjusted so that the solvent does not boil at the set temperature.
- the cellulose ester dope must be filtered to remove foreign matters, particularly foreign matters that are mistakenly recognized as images in a liquid crystal display device. It may be said that the quality as an optical film is determined by this filtration.
- Casting process The dope prepared in the melting pot is fed to the casting die by a conduit and is cast to a casting position on an endless support that is infinitely transported, for example, a support made of a rotationally driven stainless steel endless belt. Die force This is the process of casting the dope.
- the surface of the support is a mirror surface.
- the front drum (2) around which the belt support (1) is wound is, for example, a hot water drum
- the rear drum (3) is, for example, a cold water drum.
- a casting die (for example, a pressure die) (4) is preferable because the slit shape of the die portion can be adjusted and the film thickness can be uniformed.
- the casting die (4) includes a coat hanger die and a T die, and any of them is preferably used.
- two or more casting dies may be provided on the support, and the dope amount may be divided and overlaid. Then, the dope adjusted to have a dope viscosity of 1 to 200 boise is cast from the casting die (4) onto the belt support (1) so as to have a substantially uniform film thickness.
- a dope (solution) in which a cellulose ester-based resin is dissolved in a solvent is cast from a casting die (4) onto a traveling belt support (1).
- a dope solution in which a cellulose ester-based resin is dissolved in a solvent is cast from a casting die (4) onto a traveling belt support (1).
- a metal endless belt (belt support) wound around a pair of front and rear rotational drive drums (2) (3)
- the thickness (Te) of the left and right end portions (lb) of the belt support having a predetermined width (We) from the left and right side edges of (1) is the same as that of other portions (la) including the width center of the belt support. Thinner than thickness (T).
- the belt support having a predetermined width (We) from the left and right side edges of the wide belt support (1) having a width of 1.8 m or more.
- the longitudinal elastic modulus (Ee) of the left and right ends (lb) of the belt is smaller than the longitudinal elastic modulus (E) of the other part (la) including the center of the width of the belt support! / ⁇ .
- the web in which the solvent is evaporated on the belt support is peeled off by a peeling roll.
- the peeled web is sent to the next process. If the amount of residual solvent on the web at the time of peeling is too large, the web will be difficult to peel, or conversely, if the web is sufficiently dried on the belt support and then peeled off, A part of may come off.
- the present invention when a thin web is peeled off from the support, in order to prevent the flatness from being deteriorated or slipped, it is possible to peel it with a force within 170 NZm from the minimum tension that can be peeled off. The force within 140NZm is more preferable.
- gel casting As a method for increasing the film forming speed (the amount of residual solvent is as large as possible, and the film forming speed can be increased because of peeling).
- a poor solvent for cellulose ester is added to the dope, and after dope casting, the gelation is performed, and the temperature of the support is lowered to perform gelation.
- the speed of film formation can be increased by speeding up the peeling.
- the web can be peeled in the range of 5 to 150% by mass depending on the strength of the condition, the length of the support, etc.
- the temperature at the peeling position on the support is preferably 10 to 40 ° C, more preferably 15 to 30 ° C.
- the residual solvent amount when peeling force is 10 to 150% by mass, more preferably 70 to 150% by mass, and still more preferably 100 to 130% by mass.
- the proportion of the good solvent contained in the residual solvent is preferably 50 to 90%, more preferably 60 to 90%, and particularly preferably 70 to 80%.
- the amount of residual solvent can be expressed by the following formula.
- Residual solvent amount (mass%) ⁇ (M-N) / N ⁇ X 100
- M is a mass of the web at an arbitrary time point, and is a mass measured by the following gas chromatography.
- N is a mass when the M is dried at 110 ° C. for 3 hours. The measurement can be performed using, for example, Hewlett-Packard Gas Chromatography Model 5890 SERISII and Headspace Sampler Model HP7694.
- the web After peeling from the support, generally, the web is dried using a roll drying device that alternately passes the web through a plurality of transport rolls and a tenter device that grips and transports both ends of the web.
- a web (film) drying means it is common to blow warm air on the surface of the web (film).
- the stretching ratio when producing a cellulose ester film is 1.01 to 3 times, preferably 1.5 to 3 times, in the film forming direction or the width direction. It is.
- the side to be stretched at high magnification is 1.01 to 3 times, preferably 1.5 to 3 times, and the stretching ratio in the other direction is 0.8 to 1.5.
- the film can be stretched by a factor of preferably 0.9 to 1.2.
- These width maintenance or transverse stretching in the film forming process may be a pin tenter or a clip tenter, which is preferably performed by a tenter device.
- the film transport tension in the post-drying process is affected by the physical properties of the dope, the amount of residual solvent in the peeling and film transport processes, the temperature in the post-drying process, etc., but is preferably 30 to 250 NZm, 60 to 150 N / m force more preferred! 80 ⁇ 120N / m force ⁇ Most preferred!
- a tension cut opening for the purpose of preventing the film from stretching in the transport direction in the post-drying process. It is preferable to provide a tool. After drying, it is preferable to provide a slitter and cut off the end portion before winding to obtain a good shape.
- the web after drying is wound up as a film by a scooping device to obtain a base of the optical film.
- the film 14 having good dimensional stability can be obtained by setting the residual solvent amount of the film 14 after drying to 0.5% by mass or less, and preferably 0.1% by mass or less.
- the film winding method is a method of controlling tension such as a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, etc., using a commonly used winder. There is, and should just use them properly
- the film thickness of the optical film according to the present invention varies depending on the purpose of use, but from the viewpoint of thinning the liquid crystal display device, the finished film is preferably in the range of 10 to 150 / ⁇ ⁇ . The range of 40 ⁇ m is particularly preferable.
- the film thickness is too thin, for example, the required strength as a protective film for a polarizing plate may not be obtained. If the film is too thick, the advantage of the thin film over the conventional cellulose ester film is lost.
- control the dope concentration, pump feed volume, slit gap of the die of the casting die, the extrusion pressure of the casting die, the speed of the support, etc. Is good.
- a film thickness detection means as a means for making the film thickness uniform, and feed back the programmed feedback information to each of the above-mentioned devices.
- the atmosphere in the drying apparatus may be air, but is performed in an inert gas atmosphere such as nitrogen gas or carbon dioxide gas. May be. Of course, the danger of explosion limit of evaporating solvents in dry atmosphere must always be taken into account.
- the optical film according to the present invention is preferably used for a liquid crystal display member, more specifically, a protective film for a polarizing plate, from the viewpoint of good moisture permeability and dimensional stability.
- a protective film for polarizing plates which is strictly required for both moisture permeability and dimensional stability.
- An optical film is preferably used.
- the center line average roughness (Ra) of the cell mouth ester film is preferably 20 nm or less, more preferably lOnm or less, and particularly preferably 4 nm or less.
- the polarizing plate can be produced by a general method.
- the cell mouth ester film according to the present invention which has been subjected to alkali oxidation treatment, is a complete glass-type polyvinyl alcohol on at least one surface of a polarizer produced by immersing and stretching a polybulol alcohol film in a silicon solution. It is preferable to use an aqueous solution.
- the cellulose ester film according to the present invention may be used, or another polarizing plate protective film may be used.
- a commercially available cellulose ester film can be used as the polarizing plate protective film used on the other surface of the cell mouth ester film according to the present invention.
- KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY ⁇ KC12UR ⁇ KC8UY—HA ⁇ KC8UX—RHA ⁇ KC8UX—RHA—N (above, manufactured by Co-Caminoltop Co., Ltd.) and the like are preferably used as commercially available cellulose ester films. .
- a film such as cyclic olefin resin, acrylic resin, polyester, and polycarbonate other than the cellulose ester film may be used as the polarizing plate protective film on the other surface. This In this case, since the suitability is low, it is preferable to perform an adhesive process on the polarizing plate through an appropriate adhesive layer.
- the polarizing plate is obtained by using the cellulose ester film according to the present invention on at least one side of a polarizer as a polarizing plate protective film. At that time, it is preferable that the slow axis of the cellulose ester film is arranged so as to be substantially parallel or perpendicular to the absorption axis of the polarizer.
- the cellulose ester film according to the present invention is disposed on the liquid crystal display cell side as the polarizing plate on which the polarizing plate is disposed across the liquid crystal cell of the transverse electric field switching mode type.
- Examples of the polarizer preferably used for the polarizing plate include a polyvinyl alcohol-based polarizing film, which includes a polybutyl alcohol-based film dyed with iodine and a dichroic dye dyed.
- a polybutyl alcohol film a modified polyvinyl alcohol film modified with ethylene is preferably used.
- a polyvinyl alcohol aqueous solution is formed into a film, and this is uniaxially stretched for dyeing. After being uniaxially stretched, the polarizer is preferably subjected to a durability treatment with a boron compound.
- the thickness of the polarizer is 5 to 40 ⁇ m, preferably 5 to 30 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
- a polarizing plate On the surface of the polarizer, one side of the cellulose ester film according to the present invention is bonded to form a polarizing plate.
- a water-based adhesive mainly composed of complete poly-vinyl alcohol or the like.
- a resin film other than the cellulose ester film it can be bonded to the polarizing plate through an appropriate adhesive layer.
- the stretching direction (usually the longitudinal direction) shrinks and is orthogonal to the stretching. It stretches in the direction (usually the width direction).
- the direction of stretching of the polarizer is bonded to the casting direction (MD direction) of the polarizing plate protective film. Therefore, when the polarizing plate protective film is used as a thin film, it is particularly important to suppress the stretching rate in the casting direction. is there. Book Since the cell mouth ester film according to the invention is excellent in dimensional stability, it is suitably used as such a polarizing plate protective film.
- the polarizing plate can be constituted by further bonding a protective film on one surface of the polarizing plate and a separate film on the other 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.
- a liquid crystal display device using the optical film produced according to the present invention has excellent quality with no unevenness on the screen.
- Examples 1 to 17 correspond to the inventions of claims 1 to 4, and a cell having a target dry film thickness of 80 ⁇ m by the solution casting film forming method according to the optical film manufacturing method of the present invention.
- a dope was first prepared.
- Tinuvin 326 (Chinoku's Specialty Chemicals) 1 part by mass
- the above materials are sequentially put into a closed container, the temperature in the container is raised from 20 ° C to 80 ° C, and the mixture is stirred for 3 hours while maintaining the temperature at 80 ° C to obtain cellulose triacetate propionate. Dissolved completely. Thereafter, stirring was stopped and the liquid temperature was lowered to 43 ° C.
- the dope was fed to a filter and filtered using a filter paper (Azumi filter paper No. 244, manufactured by Azumi Filter Paper Co., Ltd.) to obtain a dope for casting.
- the dope prepared as described above was cast on a belt support made of a stainless steel endless belt through a casting die kept at 35 ° C to form a film (web).
- the film After drying on the belt support until the amount of residual solvent reaches 80% by mass, the film is peeled off with a peeling roll using a peeling roll, and then dried while being transported by a roll, and wound up by a scraper. Finally, a cellulose triacetate propionate film having a width of 1700 mm was produced.
- the belt support (1) shown in FIG. 1 has a width of 1900 mm, and as shown in Table 1 below, the belt support full width (W The thickness (Te) of the left and right ends (lb) of the belt support having a width (We) of 2 to 25% ) was used, and the belt support (1) within the scope of the present invention having a thickness of 5 to 20% was used.
- Belt end deformation amount The height difference (d) between the belt end (lb) and the belt center (la) was measured as shown in FIG.
- laser displacement meter LK-010 manufactured by Keyence Corporation was used, and 1000 points were measured every 10mm in length at the belt end (lb) and belt center (la). Plot the height difference (d) between lb) and the belt center (la), and pick 10 peak heights in descending order of maximum force, and take the average value as the belt end deformation.
- the belt end deformation is evaluated by the difference in height between the belt end (lb) and the belt center (la).
- (D) 1S 300 ⁇ m or less ⁇ , 500 ⁇ m or less ⁇ , 1000 ⁇ m
- the evaluation was made by classifying m or less as ⁇ , V larger than 1000 ⁇ m, and X being ranked as X.
- Belt meandering amount As shown in Fig. 7, a pair of front and rear rotating drums (2) and (3) for rotating the belt support (1) for meandering control during conveyance by the belt support (1) The angle between the rotating shafts of the two was changed, and the rotating shaft of one front rotating drum (2) was slightly shifted from the direction of travel of the belt support (1). The position of the belt end (lb) was measured with Keyence Corporation LS3000, just before the drive drum (2) under control, and the amount of meandering relative to the entire belt width (W) was calculated. [0193] The evaluation of the belt meandering amount is as follows.
- the belt meandering amount is ⁇ 0.2% or less, the meandering amount is less and the conveying property is ⁇ , and the belt meandering amount is ⁇ 0. Evaluations were made by classifying 3% or less as ⁇ , belt meandering amount of ⁇ 0.5% or less as ⁇ , and belt meandering amount as ⁇ 0.5% as X.
- a cellulose acetate propionate film having a width of 1700 mm is prepared using a belt support having a width of 1900 mm as in the case of Example 1 above.
- the difference from Example 1 is as follows. As shown in Table 2, the width (We) of the left and right end portions (lb) of the belt support (1), and the thickness (Te) of Z or the left and right end portions (lb) of the belt support (1) The ratio is out of the scope of the invention (marked with *).
- Example 1 5% 2% ⁇ ⁇ ⁇ Example 2 5% 12% ⁇ ⁇ ⁇ Example 3 5% 25% ⁇ ⁇ ⁇ Example 4 8% 10% ⁇ ⁇ ⁇ Example 5 8% 12% ⁇ ⁇ Implementation Example 6 8% 20% ⁇ ⁇ Example 7 10% 2% ⁇ ⁇ ⁇ Example 8 10% 10% ⁇ ⁇ o Example 9 10% 12% ⁇ ⁇ ⁇ Example 10 10% 20% ⁇ ⁇ o Implementation Example 11 10% 25% ⁇ ⁇ ⁇ Example 12 15% 10% ⁇ ⁇ ⁇ Example 13 15% 12% ⁇ ⁇ ⁇ Example 14 15% 20% ⁇ ⁇ ⁇ Example 15 20% 2% ⁇ ⁇ ⁇ Example 16 20% 12% ⁇ ⁇ ⁇ Example 17 20% 25% ⁇ ⁇ ⁇ ⁇
- Comparative Examples 1 to 25 either one or two of the belt end deformation amount, the belt meandering amount (belt transportability), and the belt end observation (belt end drying) In all Comparative Examples 1 to 25, poor drying occurs at the end of the cast film (web), and depending on the comparative example, the state of conveyance with a large amount of belt meandering is unstable. there were.
- Examples 1 to 17 and Comparative Examples 1 to 25 a belt support having a width of 1900 mm was used to produce a film having a width of 1700 mm. Depending on the film forming conditions after peeling, a wider film was produced. Is possible. In addition, when the width of the belt support is larger than 1900 mm, a wider film can be produced.
- Examples 18 to 23 correspond to the inventions of claims 6 to 10 and prepared a belt test sample piece (belt support) (11) having a total width of 50 Omm and a length of 1000 mm.
- the sample piece end (lib) is welded to one edge of the sample piece body (11a) of each belt test sample piece (11)!
- the material of the belt test sample piece (11) was SUS316 (longitudinal elastic modulus 220 [GPa]).
- the sample piece end part (l ib) is made of two types of materials with different processing temperatures of SUS316 (longitudinal elastic modulus 220, 200 [GPa]), SUS304 (longitudinal elastic modulus 190 [GPa]), and processing temperature of SUS405. Two different materials (longitudinal elastic modulus 180, 175 [GPa]) were appropriately combined to adjust the longitudinal elastic modulus.
- the sample piece end portion (l ib) extends from one side edge of the belt test sample piece (belt support) (11) to the belt test sample piece (belt support).
- Body) (11) with a width (We) of 2 to 25% of the total width (W), and the longitudinal elastic modulus (Young's modulus) (Ee) of the sample piece end (1 lb) It is smaller than the longitudinal elastic modulus (E) of the piece body (1 la) by 5 to 20% within the scope of the present invention.
- These belt test sample pieces (11) are set in the equipment shown in Fig. 9 and Fig. 10, and repeated load is applied. And measured the amount of deformation at the end of the belt test sample piece (belt support) (11)
- the belt test sample piece (belt support) (11) is placed on a roll (12) having a diameter of 100 mm with a wrap angle of 180. And fasten both ends of the belt test sample piece (belt support) (11) to the wall (14).
- the roll (12) is swung by a reciprocating drive source (not shown) with the end (13a) on one side of the roll shaft (13) as a fulcrum.
- a tension meter (15) is attached to the end (13b) on the working side of the roll shaft (13), so that the tension applied to the end of the belt test sample piece (belt support) (11) can be measured.
- the belt is fixed so that this tension is 9800N.
- a belt test sample piece (belt support) (11) having a total width of 500 mm and a length of 1000 mm is used as in the case of Example 18 above, but is different from that in Example 18.
- the points are the width (We) of the sample piece end portion (l ib) and the thickness of the Z or sample piece end portion (1 lb) (Te) 1S. It is in the point which was made a good thing (* mark is described).
- These belt test sample pieces (11) are set in the apparatus shown in FIG. 9 and FIG. 10 in the same manner as in Examples 18 to 23, and repeatedly subjected to load, and then the belt test sample pieces (belt support). The amount of deformation at the end of (11) was measured, and the results obtained are shown in Table 3 below.
- the belt test sample piece (belt support) (11) having a high evaluation of the belt end deformation amount was obtained.
- the stress applied to the belt support (11) during meander control is reduced, and deformation of the belt support end after prolonged operation is reduced. It was confirmed that it was possible to maintain a stable conveyance state with less meandering.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Moulding By Coating Moulds (AREA)
- Polarising Elements (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
Description
Claims
Priority Applications (4)
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JP2008513118A JP4883083B2 (ja) | 2006-04-28 | 2007-04-02 | 光学フィルムの製造方法 |
KR1020087026071A KR101285476B1 (ko) | 2006-04-28 | 2007-04-02 | 광학 필름의 제조 방법 |
CN2007800149103A CN101432114B (zh) | 2006-04-28 | 2007-04-02 | 光学膜的制造方法 |
US12/226,587 US7727445B2 (en) | 2006-04-28 | 2007-04-02 | Method for manufacturing optical film |
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JP2006-125871 | 2006-04-28 | ||
JP2006125871 | 2006-04-28 |
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WO2007125729A1 true WO2007125729A1 (ja) | 2007-11-08 |
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PCT/JP2007/057388 WO2007125729A1 (ja) | 2006-04-28 | 2007-04-02 | 光学フィルムの製造方法 |
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US (1) | US7727445B2 (ja) |
JP (1) | JP4883083B2 (ja) |
KR (1) | KR101285476B1 (ja) |
CN (1) | CN101432114B (ja) |
TW (1) | TWI453109B (ja) |
WO (1) | WO2007125729A1 (ja) |
Cited By (8)
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CN102344574A (zh) * | 2010-07-30 | 2012-02-08 | 富士胶片株式会社 | 干燥装置及溶液制膜方法 |
JP2012061842A (ja) * | 2010-08-16 | 2012-03-29 | Fujifilm Corp | 溶液製膜方法及び流延装置 |
EP2439040A1 (en) * | 2009-06-04 | 2012-04-11 | SK Innovation Co. Ltd. | Wide casting belt, method for manufacturing a wide film, and wide film |
JP2012194140A (ja) * | 2011-03-18 | 2012-10-11 | Fujifilm Corp | エンドレスバンドの検査方法及び装置 |
JP2013063511A (ja) * | 2011-09-15 | 2013-04-11 | Fujifilm Corp | 金属ドラム、流延装置、流延膜の形成方法及び溶液製膜方法 |
JP2013075432A (ja) * | 2011-09-30 | 2013-04-25 | Fujifilm Corp | 環状バンドの移動方向制御装置、流延設備、及び溶液製膜方法 |
US20130189508A1 (en) * | 2012-01-23 | 2013-07-25 | Sk Innovation Co., Ltd. | Method for manufacturing a wide film, and wide film |
JP2013252614A (ja) * | 2012-06-05 | 2013-12-19 | Fujifilm Corp | 溶液製膜方法及び設備 |
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US9273195B2 (en) | 2010-06-29 | 2016-03-01 | Eastman Chemical Company | Tires comprising cellulose ester/elastomer compositions |
US20110319531A1 (en) | 2010-06-29 | 2011-12-29 | Eastman Chemical Company | Cellulose ester compositions |
KR101307307B1 (ko) * | 2010-08-16 | 2013-09-11 | 후지필름 가부시키가이샤 | 용액 제막 방법 및 유연 장치 |
KR101317970B1 (ko) * | 2011-01-28 | 2013-10-14 | 후지필름 가부시키가이샤 | 용액 제막 방법 및 용액 제막 설비 |
EP2742372B1 (en) * | 2011-08-12 | 2015-09-16 | Dow Global Technologies LLC | Optical retardation film and method of manufacturing |
JP5568541B2 (ja) * | 2011-11-07 | 2014-08-06 | 富士フイルム株式会社 | 溶液製膜方法 |
US20130150499A1 (en) | 2011-12-07 | 2013-06-13 | Eastman Chemical Company | Cellulose esters in highly-filled elastomeric systems |
US10077342B2 (en) | 2016-01-21 | 2018-09-18 | Eastman Chemical Company | Elastomeric compositions comprising cellulose ester additives |
JP6686620B2 (ja) | 2016-03-29 | 2020-04-22 | コニカミノルタ株式会社 | エンドレスベルトの製造方法 |
WO2018070146A1 (ja) * | 2016-10-12 | 2018-04-19 | コニカミノルタ株式会社 | 光学フィルムの製造方法 |
JP7301452B2 (ja) * | 2019-09-27 | 2023-07-03 | エルジー・ケム・リミテッド | マーキングを用いた光学フィルム、光学フィルムの製造装置および製造方法 |
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- 2007-04-02 KR KR1020087026071A patent/KR101285476B1/ko active IP Right Grant
- 2007-04-02 US US12/226,587 patent/US7727445B2/en not_active Expired - Fee Related
- 2007-04-02 CN CN2007800149103A patent/CN101432114B/zh active Active
- 2007-04-02 WO PCT/JP2007/057388 patent/WO2007125729A1/ja active Application Filing
- 2007-04-25 TW TW096114640A patent/TWI453109B/zh active
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Publication number | Priority date | Publication date | Assignee | Title |
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EP2439040A1 (en) * | 2009-06-04 | 2012-04-11 | SK Innovation Co. Ltd. | Wide casting belt, method for manufacturing a wide film, and wide film |
US9884461B2 (en) | 2009-06-04 | 2018-02-06 | Berndorf Band Gmbh | Wide casting belt, method for manufacturing a wide film, and wide film |
EP2439040A4 (en) * | 2009-06-04 | 2014-07-02 | Sk Innovation Co Ltd | BROAD CASTING BELT, PROCESS FOR PRODUCING WIDE FILM, AND BROAD FILM |
TWI426994B (zh) * | 2010-07-30 | 2014-02-21 | Fujifilm Corp | 乾燥裝置及溶液製膜方法 |
CN102344574A (zh) * | 2010-07-30 | 2012-02-08 | 富士胶片株式会社 | 干燥装置及溶液制膜方法 |
CN102344574B (zh) * | 2010-07-30 | 2014-05-28 | 富士胶片株式会社 | 干燥装置及溶液制膜方法 |
JP2012061842A (ja) * | 2010-08-16 | 2012-03-29 | Fujifilm Corp | 溶液製膜方法及び流延装置 |
JP2012194140A (ja) * | 2011-03-18 | 2012-10-11 | Fujifilm Corp | エンドレスバンドの検査方法及び装置 |
JP2013063511A (ja) * | 2011-09-15 | 2013-04-11 | Fujifilm Corp | 金属ドラム、流延装置、流延膜の形成方法及び溶液製膜方法 |
JP2013075432A (ja) * | 2011-09-30 | 2013-04-25 | Fujifilm Corp | 環状バンドの移動方向制御装置、流延設備、及び溶液製膜方法 |
US20130189508A1 (en) * | 2012-01-23 | 2013-07-25 | Sk Innovation Co., Ltd. | Method for manufacturing a wide film, and wide film |
US9428624B2 (en) | 2012-01-23 | 2016-08-30 | Sk Innovation Co., Ltd. | Method for manufacturing a wide film, and wide film |
JP2013252614A (ja) * | 2012-06-05 | 2013-12-19 | Fujifilm Corp | 溶液製膜方法及び設備 |
Also Published As
Publication number | Publication date |
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JP4883083B2 (ja) | 2012-02-22 |
KR101285476B1 (ko) | 2013-07-12 |
CN101432114B (zh) | 2011-01-12 |
TWI453109B (zh) | 2014-09-21 |
TW200808515A (en) | 2008-02-16 |
CN101432114A (zh) | 2009-05-13 |
KR20080113425A (ko) | 2008-12-30 |
US20090230576A1 (en) | 2009-09-17 |
JPWO2007125729A1 (ja) | 2009-09-10 |
US7727445B2 (en) | 2010-06-01 |
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