JP5922700B2 - Filtration filter, filtration method, and method for producing cellulose acylate film - Google Patents

Description

The present invention is a filtration filter, filtration method, a manufacturing method of the cellulose acylate fill beam.

  In recent years, a plurality of optical films such as a protective film for a polarizing plate, a retardation film, and an antireflection film are used in liquid crystal display devices that have been widely used. A polymer film is used as these optical films. In particular, cellulose acylate films are widely used because they are excellent in handling during production and exhibit good optical characteristics.

  As a method for producing a cellulose acylate film, a melt film forming method and a solution film forming method are known. The melt film-forming method is a method for obtaining a cellulose acylate film by extruding molten cellulose acylate into a film. In the solution casting method, a cellulose acylate film is obtained by casting a solution obtained by dissolving cellulose acylate in a solvent (hereinafter referred to as a dope) onto a support such as a metal drum or a band and drying it. How to get. It is less likely that the cellulose acylate is subject to thermal damage when it is manufactured by the solution casting method than by the melt casting method, so that a film with high transparency and excellent flatness and optical properties can be manufactured stably. can do.

  The cellulose acylate used for the dope is synthesized by acylating cellulose obtained from natural products such as linter and pulp. Therefore, the cellulose acylate contains hemicellulose, unacylated cellulose (hereinafter referred to as unreacted cellulose), and the like as foreign matters that are not soluble in the solvent (hereinafter referred to as insoluble foreign matters). Unreacted cellulose becomes a foreign substance in the film, and when this film is used for a display device, a portion where the foreign substance is present on the display screen appears white and appears as a bright spot. Hereinafter, the foreign matter that causes such a bright spot is referred to as a bright spot foreign matter.

  In order to stably produce a film having high transparency and excellent flatness and optical properties, it is necessary to remove insoluble foreign matters such as hemicellulose and unreacted cellulose from the dope. Insoluble foreign matter is removed mainly by filtration. For the filtration, a hydrophobic filter made of a synthetic fiber such as polypropylene or a metal fiber such as stainless steel, a hydrophilic filter made of cellulose fiber or the like is used. For example, Patent Document 1 proposes a filtration filter in which the surface of the filtration filter is subjected to a hydrophobic treatment so that no hydrogen bond is generated between the insoluble foreign matter and the filtration filter.

JP 2004-292570 A

  However, the filter of Patent Document 1 has a problem that it is difficult to efficiently remove unreacted cellulose. Further, if a metal filter is used to remove unreacted cellulose instead of the filtration filter of Patent Document 1, the filtration pressure (filtration pressure) gradually increases after filtration is started, and the filtration pressure is constant. If it becomes above, it will be necessary to stop filtration and to replace a metal filter frequently. Therefore, there is a problem that costs are increased.

The present invention aims at providing a filtration filter for efficiently removing unreacted cellulose which is insoluble foreign matter, a filtration method, cellulose acylate having a small fill-time manufacturing method of a bright defect.

The filtration filter of the present invention, the cationic polymer layer comprising a cationic polymer to the filter paper is formed from a fiber body is coated is above cationic polymer layer is eclipsed set on the surface of the fiber body, the cationic polymer is of the formula The compound shown in (1), the amount of the above-mentioned compound with respect to 100 mass of the fiber body is in the range of 1 to 15 parts by mass, and unreacted cellulose in a solution obtained by dissolving cellulose acylate in a solvent. Used in the filtration step to remove .

Filtration method of the present invention, a solution in which cellulose acylate is dissolved in a solvent and filtered using a filtration over filter above SL, is intended to remove unreacted cellulose in the solution.

  In the method for producing a cellulose acylate film of the present invention, a dope containing cellulose acylate and a solvent is cast on a continuously running support to form a cast film, and the cast film is peeled off from the support. In the method for producing a cellulose acylate film, which is dried by a drying means while transporting the peeled film, the dope is filtered using the filtration method described above.

The filtration filter and filtration method of the present invention can efficiently remove unreacted cellulose which is an insoluble foreign matter. Therefore, a cellulose acylate film with few bright spot foreign matters can be produced. Moreover, since the filtration pressure rise is also suppressed, when the filtration filter and the filtration method of the present invention are used, it is not necessary to frequently exchange the filtration filter. Also, manufacturing process of the cellulose acylate fill arm of the present invention inhibit the bright spot in the display device.

It is explanatory drawing which shows the outline of dope manufacturing equipment. It is a schematic sectional drawing which shows an example of a filtration apparatus. It is a schematic enlarged view which shows a filtration filter. It is a schematic sectional drawing which shows the cationic fiber which comprises a filtration filter. It is explanatory drawing of the cationic expression mechanism in a cationic fiber. It is explanatory drawing of the unreacted cellulose adsorption | suction mechanism in a filtration filter. It is explanatory drawing of the 1st and 2nd bright spot foreign material. It is explanatory drawing which shows the outline of a film manufacturing equipment.

  A filtration filter, a filtration method, a cellulose acylate film with less bright spot foreign matter and a method for producing the same according to the present invention will be described with reference to embodiments. In addition, the form shown here is an example which concerns on this invention, and does not limit this invention.

  As shown in FIG. 1, the dope manufacturing facility 10 includes a solvent tank 11, an additive tank 12, a hopper 13, and a mixing tank 15. The solvent tank 11 stores a solvent as a dope raw material, and the additive tank 12 stores an additive solution obtained by mixing an additive with a solvent in advance. In addition, cellulose acylate is supplied to the hopper 13. These tanks 11, 12 and the hopper 13 are all connected to the mixing tank 15, so that appropriate amounts of various dope raw materials are fed into the mixing tank 15. The supply and stop of the raw materials from the solvent tank 11 and the additive tank 12 are adjusted by opening and closing the valves V1 and V2.

  The order in which the various dope raw materials are sent to the mixing tank 15 and the form of feeding are not particularly limited. For example, the order in which the various dope raw materials are sent may be sent simultaneously with various dope raw materials or a mixture in which a solvent and a polymer are mixed. The form which adds an additive may be sufficient. Further, the additive does not necessarily need to be a solution, and may be appropriately changed according to the form of the additive to be used. For example, when the additive is liquid at normal temperature, it may be added as it is, and when the additive is solid, it may be added using a hopper or the like. Examples of the additive include a matting agent and an ultraviolet absorber.

  A jacket 17 is attached to the mixing tank 15 made of stainless steel. Due to the heating and heat retaining effect of the jacket 17, the temperature of the dope 27 in the mixing tank 15 is kept substantially constant within a range of −10 to 55 ° C. The mixing tank 15 is provided with a first stirrer 20 and a second stirrer 22 driven by motors 18 and 19, respectively. The dope 27 is prepared by continuously rotating the first stirrer 20 and the second stirrer 22 to stir and mix various dope materials.

  The dope 27 prepared in the mixing tank 15 is sent to the heating device 26 by the pump P1. The dope 27 is heated by the heating device 26 so as to have a substantially constant temperature within a range of 0 to 97 ° C., so that the solubility of cellulose acylate and the like in the solvent is increased. The method for increasing the solubility of the dope 27 is not limited to this, and other methods include a method in which the dope 27 is pressurized by a pressurizing unit, a method in which the dope 27 is cooled by a cooling unit, and the like.

  The dope 27 with increased solubility is sent to the temperature control device 29 and is brought to about room temperature. The dope 27 that has been brought to substantially room temperature by the temperature control device is sent to the first filtration device 30 through the pipe 31. The dope 27 does not have to contain all of the solid content contained in the solvent, and may have a form in which the solid content is dispersed in the solvent. Hereinafter, the concentration of solid content dissolved or dispersed in the solvent in the dope 27 is referred to as solid content concentration.

  The first filtration device 30 captures insoluble foreign matters such as hemicellulose, unreacted cellulose, and undissolved gel contained in the dope 27 (filtration step). A valve V3 provided in the pipe 32 switches the connection destination of the first filtration device 30 to the stock tank 33 or the flash device 40. Thereby, the dope 27 that has passed through the first filtration device 30 is sent to the stock tank 33 or the flash device 40 by the switchable valve V3. Details of the first filtration device 30 will be described later.

  When the solid content concentration of the filtered dope 27 satisfies a desired value, the dope 27 is sent to the stock tank 33 via the valve V3 whose opening degree is adjusted in advance, and stored therein. Similar to the mixing tank 15, the stock tank 33 is provided with a jacket 34 having a heating / warming effect and a stirrer 36 rotated by a motor 35, and the stock tank 33 is adjusted to a predetermined temperature inside the stock tank 33. The dope 27 is constantly stirred. Thereby, until it uses for casting, dope 27 is hold | maintained in a uniform state, suppressing that solid content etc. aggregate and a foreign material's producing | generating.

  Alternatively, the dope 27 having a concentration lower than the target solid content concentration may be prepared and then concentrated to increase the solid content concentration, thereby preparing the dope 27 having a desired solid content concentration. In this case, the dope 27 after being filtered by the first filtering device 30 is sent to the flash device 40 via the valve V3 whose opening degree is adjusted in advance. The flash device 40 evaporates a part of the solvent contained in the dope 27 and concentrates the dope 27. Along with the concentration, the solvent gas generated in the flash device 40 is condensed and liquefied by a condenser (not shown) and then recovered by the recovery device 41. Thereafter, impurities such as moisture contained in the condensed and liquefied solvent are removed by the regenerator 42. The solvent from which the impurities have been removed is used again as a dope raw material.

  The concentrated dope 27 is extracted from the flash device 40 by the pump P <b> 2 and then sent to the second filtration device 44. The second filtration device 44 is provided with a porous filtration filter having an average pore diameter of 100 μm or less. The material of the filter is not particularly limited, and for example, a metal filter such as stainless steel or a cellulose-based organic filter is preferably used. The pore size of the filter is appropriately selected in consideration of the filtration efficiency such as the time (filtering time) for filtering a certain amount of the dope 27. The dope 27 filtered by the second filtration device 44 is sent to the stock tank 33 and stored until it is cast.

  The dope 27 stored in the stock tank 33 is sent into the pipe 45 while the feed amount is adjusted by the pump P3. While the flow rate is confirmed by the flow meter 46, the dope 27 is sent to a third filtration device 49 arranged further downstream. The third filtering device 49 is preferably the same as the second filtering device 44. The dope 27 filtered by the third filtering device 49 is sent to the film manufacturing facility 50 and used for casting.

  The details of the first filtration device 30 will be described with reference to FIG. The first filtration device 30 is a multi-filter type filtration device. The outer shell of the first filtration device 30 is formed by a cylindrical body portion 30a and a pair of substantially disk-shaped lid portions 30b provided so as to cover both ends of the body portion 30a. In the flow direction of the dope 27, the pipe 31 is in the through hole provided in the substantially central portion of the upstream lid portion 30b, and the pipe 32 is in the through hole provided in the substantially central portion of the downstream lid portion 30b. It is connected substantially perpendicular to the portion 30b.

  A disc-shaped plate 30c having a plurality of substantially circular through holes is provided substantially in parallel to the lid portion 30b inside the trunk portion 30a. Each through hole is provided with a filter 62. Each of the filtration filters 62 is formed in a hollow cylindrical shape, and is fixed to the upstream side of the plate 30c in a posture that stands substantially perpendicular to the plate 30c. Thereby, each filtration filter 62 is being fixed inside the trunk | drum 30a. Each filtration filter 62 has a downstream end disposed around a corresponding through hole of the plate 30c. A lid member 30d that closes the hollow portion is provided at the upstream end of each filter 62. The dope 27 is introduced into the first filtration device 30 from the upstream pipe 31, filtered by passing through the filtration filter 62 and the through hole of the plate 30 c in this order, and sent to the downstream pipe 32.

  Thus, the structure in which a plurality of filtration filters 62 formed in a hollow cylindrical shape are arranged in parallel does not change the size of the outline of the filtration device 30, and the area where the dope 27 is in contact with the filtration filter 62 (hereinafter referred to as filtration). (Referred to as “area”). In FIG. 2, the plate 30c is provided with three through holes, and the filter 30 is provided in each of them. However, the present invention is not limited to this, and the first filter 30 is filtered. Any number of the filters 62 may be provided. Moreover, the structure of the 1st filtration apparatus 30 is not restricted to this, What kind of structure may be sufficient if the filtration filter 62 is distribute | arranged inside.

  As shown in FIG. 3, the filtration filter 62 is formed by irregularly intertwining a plurality of cationic fibers 63. As shown in FIG. 4, each cationic fiber 63 is formed by a fiber main body 65 and a cationic polymer layer 66 that covers the surface of the fiber main body 65. The cationic polymer layer 66 is composed of a cationic polymer 67 as shown in FIG. Polyamide epichlorohydrin represented by the following formula (1) is used for the cationic polymer 67. Here, the average molecular weight of the polyamide epichlorohydrin is preferably in the range of 5000 to 80,000.

For the polyamide epichlorohydrin of the formula (1), for example, compounds represented by the following formulas (2) to (5) are preferably used. Here, the compound of the formula (2) is a compound in which m = 2 in the formula (1) and all of —A ₁ —, —A ₂ —, and —A ₃ — are —CH ₂ —. The compound of the formula (3) is a compound in which m = 4 in the formula (1) and all of —A ₁ —, —A ₂ —, and —A ₃ — are —CH ₂ —. The compound of the formula (4) is a compound in which m = 2 in the formula (1), -A _1- and -A ₂ -are both -CH _2- , and -A ₃ -is -NH-. . The compound of the formula (5) is a compound in which m = 2 in the formula (1) and all of —A ₁ —, —A ₂ —, and —A ₃ — are —NH—.

  For the fiber body 65, for example, a cellulose-based fiber of an organic natural polymer made from pulp or linter is preferably used. In addition, about what mixed pulp and linter, the compounding ratio is not specifically limited.

  The filter 62 is obtained by coating the surface of a filter paper obtained by forming each fiber body 65 with a cationic polymer 67. As a manufacturing method of the filtration filter 62 by the coating of the cationic polymer 67, for example, a cellulose fiber used as a raw material of the filter paper is used as the fiber main body 65, and the coating liquid containing the cationic polymer 67 is coated on the fiber main body 65, and the coated fiber. A method of making paper using the main body 65 and drying the obtained coated paper is used. Instead of this method, any other known method such as making filter paper with the fiber main body 65 and immersing the filter paper in a solution of the cationic polymer 67 may be used. By these methods, the filtration filter 62 of each cationic fiber 63 including the cationic polymer layer 66 on the surface of each fiber body 65 is formed.

  The average pore diameter of the filtration filter 62 is not particularly limited, and for example, the average pore diameter is preferably 100 μm or less. The smaller the average pore size of the filter 62 is, the finer insoluble foreign matter can be captured. However, if it is too small, the filtration time increases and the filtration pressure rises, and the filtration efficiency tends to decrease. On the other hand, if the average pore diameter is too large exceeding 100 μm, it may be difficult to capture fine insoluble foreign matters contained in the dope 27. Therefore, the pore diameter of the filtration filter is appropriately selected in consideration of filtration efficiency such as filtration time and filtration pressure.

  The inventors have estimated the mechanism by which the cationic fiber 63 constituting the filtration filter 62 efficiently captures insoluble foreign matters as follows.

  In the dope 27, the cationic polymer 67 is cationized by being positively charged at the nitrogen atom constituting the quaternary amine in the molecule. The state shown in the formulas (1) to (5) above is an extreme state when each cationic polymer 67 is cationized. Thereby, as shown in FIG. 5, the surface of the cationic fiber 63 is positively charged.

  When the surface of the cationic fiber 63 is positively charged, the surface of the filtration filter 62 is positively charged as shown in FIG. On the other hand, in the dope 27, the unreacted cellulose 70, which is an insoluble foreign matter, is negatively charged. For this reason, the unreacted cellulose 70 is adsorbed near the surface of the filtration filter 62.

  Thus, the positively charged filtration filter 62 chemically adsorbs the unreacted cellulose 70 having a negative charge. In addition, the filtration filter 62 chemically adsorbs other negatively charged foreign substances. Therefore, the filtration filter 62 efficiently captures and removes negatively charged foreign matters including the unreacted cellulose 70 from the dope 27. As a result, a cellulose acylate film (hereinafter referred to as a film) 90 (refer to FIG. 8) described later with less bright spot foreign matter is produced.

  By the way, the presence of bright spot foreign matter in the film is confirmed to be present in the first bright spot foreign matter that is not actually harmful and the display device when the film is incorporated in a display device such as a liquid crystal display device. There is a second bright spot foreign material. Since the second bright spot foreign matter can be visually recognized in the display device, it is sometimes called a visible foreign matter. In addition, the second bright spot foreign matter is sometimes called a real harmful foreign matter because it is actually harmful in the display device. Naturally, it is desirable that the film has less bright spot foreign matter, but among them, it is particularly required when the second bright spot foreign substance is used in a liquid crystal display device or the like.

  Here, the bright spot foreign matter is confirmed in the present embodiment as follows. First, a sheet-like film 90 is disposed between two polarizing plates arranged in crossed Nicols. Light is irradiated from one side and observed with an optical microscope (50 times) from the opposite side. Of the bright spots, those having a luminance L in the range of 30 cd or more and 255 cd or less are detected, and the detected bright spot is used as a bright spot foreign substance in the film. Note that the luminance L is standardized in 256 stages of integers from 0 cd to 255 cd. In addition, a liquid crystal display device is manufactured using this film, and the bright spot foreign matter recognized in the liquid crystal display device is used as the second bright spot foreign matter. On the other hand, a bright spot foreign material not recognized in this liquid crystal display device is defined as a first bright spot foreign material. In addition, each 1st, 2nd bright spot foreign material respond | corresponds with either of the bright spot foreign materials observed with the film.

  A graph as shown in FIG. 7 is obtained as follows. First, the horizontal axis of the graph is the bright spot size S (unit: μm), and the vertical axis is the luminance L (unit: cd). Here, the size of the bright spot refers to the diameter of the bright spot. Next, with respect to this graph, the first bright spot foreign matter is plotted with a diamond-shaped mark (in which ◇ is vertically long), and the second bright spot foreign matter is plotted with a star (*) mark. Thus, it can be seen that the second bright spot foreign matter is specified based on the criteria provided for the size S and the luminance L. In the example shown in FIG. 7, the second bright spot foreign matter has a size S of 10 μm or more, a luminance of 80 cd or more, and is plotted in a region above a predetermined curve U1 in the graph. Note that the reference (curve U1) for specifying the second bright spot foreign matter may vary depending on the display device.

  The filtration filter 62 efficiently removes bright spot foreign matter, and effectively removes second bright spot foreign matter. Therefore, the film 90 in which the bright spots are suppressed in the display device is manufactured.

  The amount of the cationic polymer 67 is preferably in the range of 1 part by mass or more and 15 parts by mass or less when the mass of the fiber main body 65 is 100 parts by mass. Here, the mass of the fiber main body 65 is calculated by subtracting the mass M2 of the cationic polymer layer 66 from the mass M1 of the cationic fiber 63. When the amount of the cationic polymer 67 is 1 part by mass or more with respect to 100 parts by mass of the fiber main body 65, the filter 62 adsorbs more insoluble foreign matters than when the amount is less than 1 part by mass. On the other hand, even if the cationic polymer 67 is larger than 15 parts by mass with respect to 100 parts by mass of the fiber main body 65, the amount of insoluble foreign matter that is chemically adsorbed is not much different from the case of 15 parts by mass or less. The cost of the filter 62 will increase.

  Various devices and members constituting the dope manufacturing facility 10 are connected by a stainless steel pipe because of advantages such as excellent corrosion resistance and heat resistance. Moreover, the number and installation location of the pumps and valves installed in the dope manufacturing facility 10 are not particularly limited, and may be changed as necessary.

<Cellulose acylate>
The cellulose acylate used in the present invention has a ratio in which the hydroxyl group of cellulose is esterified with carboxylic acid, that is, the substitution degree of acyl group (hereinafter referred to as acyl group substitution degree) is represented by the following formulas (1) to (3). Those satisfying all the conditions are particularly preferable. In (1) to (3), A and B are both acyl group substitution degrees, the acyl group in A is an acetyl group, and the acyl group in B has 3 to 22 carbon atoms.
2.4 ≦ A + B ≦ 3.0 (1)
0 ≦ A ≦ 3.0 (2)
0 ≦ B ≦ 2.9 (3)

  Glucose units constituting cellulose and having β-1,4 bonds have free hydroxyl groups at the 2nd, 3rd and 6th positions. The cellulose acylate 20 is a polymer in which part or all of the hydroxyl groups of cellulose are esterified, and the hydrogen of the hydroxyl groups is substituted with an acyl group having 2 or more carbon atoms. Since the degree of substitution is 1 when esterification of one hydroxyl group in the glucose unit is 100%, in the case of cellulose acylate, the hydroxyl groups at the 2nd, 3rd and 6th positions are each 100% ester. The degree of substitution is 3.

  Here, the total acyl group substitution degree obtained by “DS2 + DS3 + DS6”, where the acyl group substitution degree at the 2-position in the glucose unit is DS2, the acyl substitution degree at the 3-position is DS3, and the acyl substitution degree at the 6-position is DS6 is 2. It is preferably from 00 to 3.00, more preferably from 2.22 to 2.90, and even more preferably from 2.40 to 2.88. Furthermore, “DS6 / (DS2 + DS3 + DS6)” is preferably 0.32 or more, more preferably 0.322 or more, and further preferably 0.324 to 0.340.

  There may be only one kind of acyl group, or two or more kinds. When there are two or more acyl groups, it is preferable that one of them is an acetyl group. The sum of the substitution degrees of the hydrogen at the 2-, 3- and 6-position hydroxyl groups with acetyl groups is DSA, and the sum of the substitution degrees with acyl groups other than the acetyl groups at the 2-, 3- and 6-positions is DSB. In this case, the value of “DSA + DSB” is preferably 2.2 to 2.86, and particularly preferably 2.40 to 2.80. DSB is preferably 1.50 or more, and particularly preferably 1.7 or more. In DSB, 28% or more is preferably 6-position hydroxyl group substitution, more preferably 30% or more, further preferably 31% or more, particularly preferably 32% or more substitution of 6-position hydroxyl group. It is preferable. The value of “DSA + DSB” at the 6-position of cellulose acylate 20 is preferably 0.75 or more, more preferably 0.80 or more, and particularly preferably 0.85 or more. By using the cellulose acylate as described above, preferable solubility can be obtained in order to produce a polymer solution used for solution casting.

  The acyl group having 2 or more carbon atoms may be an aliphatic group or an aryl group, and is not particularly limited. For example, there are cellulose alkylcarbonyl ester, alkenylcarbonyl ester, aromatic carbonyl ester, aromatic alkylcarbonyl ester, etc., and these may each further have a substituted group. Propionyl group, butanoyl group, pentanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, hexadecanoyl group, octadecanoyl group, iso-butanoyl group, t-butanoyl group, cyclohexane Examples thereof include a carbonyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, and a cinnamoyl group. Among these, a propionyl group, a butanoyl group, a dodecanoyl group, an octadecanoyl group, a t-butanoyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, a cinnamoyl group, and the like are more preferable, and a propionyl group and a butanoyl group are particularly preferable.

  As a solvent used as a raw material of the dope 27, a known solvent can be used as a dope solvent when a cellulose acylate film is produced by solution casting. For example, dichloromethane, various alcohols, various ketones and the like. The solvent may be a mixture composed of a plurality of solvent components.

  The manufacturing method of the polymer film which concerns on this invention is demonstrated concretely, showing embodiment. In addition, this embodiment is an example which concerns on this invention to the last, and does not limit this invention.

<Film production equipment>
As shown in FIG. 8, the dope 27 prepared in the dope manufacturing facility 10 is sent to a feed block 73 in the casting chamber 71 in the film manufacturing facility 50 through a pipe. Inside the feed block 73, a flow path of the dope 27 corresponding to the layer structure of the cast film 75 to be formed is provided, and the arrangement of the dope 27 is determined by this.

  Next, the dope 27 is sent to the casting die 76. The casting die 76 has an outlet for the dope 27, and the casting die 76 is installed so that the outlet is almost directly above the casting drum 77. From the viewpoint of durability, heat resistance, and the like, it is preferable to use precipitation hardening stainless steel as the material. A material having corrosion resistance substantially equivalent to that of SUS316 in a forced corrosion test with an aqueous electrolyte solution can also be suitably used.

  The casting drum 77 acting as a support has a function capable of continuous running. A flow path for a cooling medium is formed inside the casting drum 77. The cooling medium supply device 78 continuously supplies the cooling medium to the flow path of the casting drum 77 by circulating the cooling medium with the casting drum 77. Thereby, the surface temperature of the casting drum 77 is made substantially constant within a range of −40 ° C. to 30 ° C. From the outlet of the casting die 76, the dope 27 having a predetermined temperature is allowed to flow out onto the rotated casting drum 77. Here, the temperature of the dope 27 is made substantially constant within a range of −10 to 55 ° C. by adjusting the internal temperature of the feed block 73 and the casting die 76. The temperature of the dope 27 of this embodiment is set to −5 ° C. Thereby, the dope 27 cast on the surface of the casting drum 77 is efficiently and effectively cooled, and the gel-like casting film 75 is formed in a short time.

  In this embodiment, the casting drum 77 is used as a support, but the form of the support is not particularly limited. For example, the support may be a casting band that is wound around a pair of rollers including one drive roller and travels endlessly. The support is preferably made of stainless steel in view of corrosion resistance and high strength. Furthermore, in order to form the cast film 75 excellent in smoothness, it is preferable that the surface is polished as much as possible.

  Due to the decompression chamber 79 installed on the casting drum 77 side of the casting die 76, the pressure on the back surface of the dope 27 to be cast, that is, the upstream side of the casting drum 77 is (atmospheric pressure −2000 Pa) or more (atmospheric pressure −10 Pa). It is substantially constant within the following range. Thereby, since the dope 27 is drawn toward the casting drum 77 in a reduced pressure state, the air is suppressed from being caught between the casting film 75 and the casting drum 77. The internal temperature of the casting chamber 71 is adjusted to be substantially constant within a range of −10 to 57 ° C. by the temperature control device 80. The solvent gas evaporated from the dope 27 and the casting film 75 is condensed and liquefied by a condenser (condenser) 82 and then recovered by a recovery device 83. Thereafter, the solvent gas is sent to a regenerator (not shown) connected to the recovery unit 83 to remove impurities, thereby forming a regenerated solvent. This recycled solvent is reused as a solvent for preparing the dope.

  As the casting film 75 is further cooled on the casting drum 77, the gelation further proceeds. The cast film 75 that has been gelled until it has self-supporting properties is peeled off from the cast drum 77 with tension applied in the transport direction while being supported by the stripping roller 85. The cast film 75 immediately after being peeled off preferably has a residual solvent amount in the range of 10 to 200% by mass. The casting film 75 is sent to the crossing part 86 where a plurality of pass rollers are arranged. In the crossing part 86, while the casting film 75 is supported and conveyed by each pass roller, drying air at a desired temperature is blown from a drying device 87 which is one kind of drying means, and the casting film 75 is dried. Promoted.

  The cast film 75 is sent to the tenter 88. In the tenter 88, a plurality of pins are pierced at both end portions of the casting film 75 in the vicinity of the entrance. The tenter 88 is made substantially constant in the range of 120 ° C. or higher and 180 ° C. or lower by adjusting the internal temperature in advance by a temperature control device (not shown) which is another kind of drying means. Therefore, the drying of the casting film 75 is promoted while the casting film 75 with both side ends fixed is conveyed by the tenter 88. As the tenter 88 moves from the entrance to the exit, the width between the rails installed in the tenter 88 increases. Therefore, the casting film 75 is gradually expanded in the width direction while being conveyed according to the rail. As a result, the casting film 75 is controlled in the molecular orientation in the width direction and promoted to be a film 90. In addition, you may make it extend | stretch the width direction with a shrinkage machine, without performing expansion extending | stretching by a rail. In the vicinity of the exit of the tenter 88, the fixing of the film 90 by the pin is released. In this embodiment, a pin type tenter having a pin as a fixing means is shown. However, the pin type tenter is not particularly limited. For example, a plurality of clips for gripping both end portions of the casting film 75 are provided as the fixing means. A clip type tenter may be used.

  The edge-cutting device 92 cuts out both side ends of the film 90 where the pin puncture wound has occurred in the tenter 88. Both ends of the cut film 90 are fed into a crusher 94 and crushed as chips. In addition, although the said cutting process can also be abbreviate | omitted, in order to obtain the film 90 with few defects, it is preferable to carry out in either the casting chamber 71 to the winding chamber 95. FIG.

  The film 90 is sent to a drying chamber 97 where a large number of rollers 96 are arranged, and is supported and conveyed by each roller 96. During this time, the film surface temperature of the film 90 is adjusted to be substantially constant within a range of 60 to 145 ° C. by a temperature controller (not shown) which is another type of drying means. Thereby, drying of the film 90 is accelerated | stimulated without receiving a thermal damage. Further, in the drying chamber 97, after the solvent gas volatilized from the film 90 is recovered by the adsorption recovery device 99, the solvent component is removed and supplied again to the drying chamber 97 as drying air.

  The degree of drying of the casting film 75 and the film 90 can be grasped by using the residual solvent amount as a guide. The amount of residual solvent is {(xy) / y} × 100, where an object whose residual solvent amount is to be measured is a sample, x is the mass of this sample, and y is the mass after the sample is completely dried. The value is based on the dry weight calculated in (unit:%).

  The film 90 is sent to the cooling chamber 100 and cooled until it reaches substantially room temperature. The cooling method is not particularly limited, and for example, a method of allowing the film 90 to stand in the cooling chamber 100 at approximately room temperature and allowing it to cool naturally or a method of attaching a blower to the cooling chamber 100 and supplying cold air may be used. .

  Next, the charged voltage of the film 90 is adjusted by the forced static elimination device 103. The charged voltage of the film 90 is not particularly limited, but is preferably substantially constant within a range of −3 kV to +3 kV. Thereafter, knurling is imparted by embossing to both end portions of the film 90 by the knurling imparting roller 104. Finally, the film 90 is sent to the take-up chamber 95 and is taken up by the take-up roller 108 while applying a pressing pressure by the press roller 107 and adjusting the flatness.

  As described above, the film 90 with few bright spot foreign matters resulting from the unreacted cellulose 70 is produced. The film 90 has a small amount of bright spot foreign matter, and particularly has a small amount of second bright spot foreign matter. According to this method, the film 90 having a length in the transport direction of at least 100 m and a length in the width direction of 1400 to 1800 mm can be particularly preferably continuously produced. However, the present invention naturally exerts an effect on the film 90 having a length in the width direction larger than 1800 mm and the film 90 having a length in the width direction smaller than 1400 mm. Although the film thickness of the completed film 90 is not specifically limited, It is preferable to exist in the range of 20-500 micrometers. More preferably, it is in the range of 30 to 300 μm, and particularly preferably in the range of 35 to 200 μm, but also in the case of a thin film 90 having a film thickness in the range of 15 to 100 μm, the effect of the present invention. Is obtained.

  In the present embodiment, a multi-filter type filtration device is used as the first filtration device 30, but the present invention is not limited to this, and any filter filter 62 or cationic fiber 63 may be used. Form may be sufficient. Moreover, in this embodiment, although the filter 62 obtained by coating the cationic polymer 67 on the surface of the filter paper obtained by forming each fiber main body 65 is used, it is not restricted to this. You may use what is obtained by coating the surface of each fiber main body 65 with the cationic polymer 67, and forming in the shape of a filtration filter. In any filter, the unreacted cellulose 70 that causes the first bright spot foreign matter and the second bright spot foreign matter is suitably removed from the dope by the action of the cationic polymer layer 66 described above.

  Hereinafter, examples of experiments for confirming the effects of the present invention will be shown, and the present invention will be specifically described. However, the example shown here is only an example according to the present invention, and does not limit the present invention.

[Experiment 1] to [Experiment 8]
The present invention provides an unreacted cellulose 70 which is an insoluble substance that is negatively charged by providing a cationic polymer layer 66 on the surface of each fiber body 65 forming the filter 62 provided in the first filtration device 30. Is efficiently removed from the dope 27. The effects of the present invention were evaluated as follows.

The dope 27 was prepared by the dope manufacturing equipment 10 shown in FIG.
[Dope raw material]
Cellulose triacetate 100 parts by mass Dichloromethane 483 parts by mass Methanol 106 parts by mass 1-butanol 4.7 parts by mass Plasticizer A 7.0 parts by mass Plasticizer B 5.0 parts by mass Retardation control agent 1.8 parts by mass Fine particles 0.05 mass Part

  The cellulose triacetate has a degree of substitution of 2.84, a viscosity average degree of polymerization of 306, a water content of 0.2% by mass, a viscosity of 315 mPa · s of 6% by mass in a dichloromethane solution, an average particle size of 1.5 mm, and a standard deviation of 0.8. The plasticizer A is triphenyl phosphate, the plasticizer B is biphenyl phosphate, and the fine particles are silicon dioxide having an average particle diameter of 15 nm and a Mohs hardness of about 7. When preparing the dope, a retardation control agent (NN-di-m-toluyl-NP-methoxyphenyl-1,3,5-triazine-2,4,6-triamine) is added to the total solid content. It was added so that it might become 1.8 mass%.

[Production of dope]
Valves V 1 and V 2 were opened from the solvent tank 11 and additive tank 12, respectively, and appropriate amounts of solvent and additive solution were sent to the mixing tank 15, and appropriate amounts of cellulose acylate were sent from the hopper 13 to the mixing tank 15. . In the mixing tank 15, various dope materials were mixed by rotating the first stirrer 20 and the dissolver type second stirrer 22 equipped with anchor blades by the motors 18 and 19, thereby preparing the dope 27. At this time, the internal temperature of the mixing tank 15 was made substantially constant within a range of −10 to 55 ° C. The temperature of the mixing tank 15 was adjusted and maintained by circulating a heat transfer medium whose temperature was adjusted to the jacket 17 and then circulating it. After the dope 27 is extracted from the mixing tank 15 by the pump P1 and sent to the heating device 26 to increase the solubility of the solid content in the solvent, the temperature is adjusted to about room temperature by the temperature adjustment device 29, and the dope 27 (before filtration by the first filtration device 30) Dope before filtration) was obtained.

  This dope before filtration is sent to the first filtration device 30 provided with the filtration filter 62 and filtered by the first filtration device 30 to obtain a dope 27 (first dope after filtration) after filtration by the first filtration device 30. It was. The dope was sent to the flash unit 40 after the first filtration by adjusting the valve V3, and the solvent was evaporated and concentrated. After the concentration, the dope was obtained. After the concentration, the dope 27 is extracted from the flash device 40 by the pump P2, and further filtered by the second filtration device 44, thereby obtaining the dope 27 (second dope after filtration) after the filtration by the second filtration device 44. It was. The dope after the second filtration was stored in the stock tank 33 with stirring until it was used for casting. An appropriate amount of the second post-filter dope stored in the stock tank 33 was sent to the pipe 45, filtered by the third filtration device 49, and sent to the film manufacturing facility 50.

  In each experiment, the filtration filter 62 used in the first filtration device 30 includes a filter having a model number indicated by “Non-applied filter” in Table 1 (manufactured by Toyo Roshi Kaisha, Ltd.) and a column of “Compound” in Table 1. A compound coated with the compound shown in the following was used. Here, the filters whose model numbers are “63LB”, “63LS”, and “63” are all organic filters made of cellulose fibers made from linter and pulp, and the average pore diameters are about 21 μm, about 20 μm, about 12 μm.

The applied compounds include the compound of formula (2) in experiments 1 and 4, the compound of formula (3) in experiment 2, the compound of formula (4) in experiment 3, and the compound of formula (5) in experiment 5. Each compound was used. In Experiment 6, Experiment 7, and Experiment 8, no compound was applied. What applied the compound added 10 mass parts with respect to 100 mass parts of fibers in a filter paper. In the “m” and “n” columns in the “Compound” column of Table 1, “the value of m” and “the number of NH groups in the repeating unit of the compound” in the formula (1) are numerical values, respectively. Indicated. Moreover, about the experiment (Experiment 6,7,8) which did not apply | coat a compound to a non-application filter, it indicated "-" and "-" in the column of "m" and "n" of a compound. In all experiments, the second filter device 44 and the third filter device 49 were metal filters made of stainless steel and having an average pore diameter of 10 μm. In any of the first to third filtration devices 30, 44, and 49, the filtration area was set to 30 m ² .

[Film production]
The film 90 was manufactured from the dope 27 made by the dope manufacturing facility 10 by the above method using the film manufacturing facility 50 shown in FIG. First, after a suitable amount of the dope 27 is fed from the dope production facility 10 to the casting die 76 via the feed block 73, the casting drum 77 is continuously rotated on the casting drum 77, from the casting port of the casting die 76. The casting film 75 was formed by flowing out the dope 27. During casting, the decompression chamber 79 decompressed the dope 27 on the casting drum 77 side, and the outflow amount of the dope 27 was adjusted so that the thickness of the dried film 90 was 60 μm.

  The casting drum 77 is a stainless steel drum whose rotational speed can be controlled by a driving device (not shown), and the surface temperature is −10 ° C. by supplying a refrigerant from a heat transfer medium supply device (not shown). And the rotational speed during film formation is 100 r / min. (Unit: r / min. Is unit: number of rotations / minute). In addition, the casting die 76 uses a form having an outlet having a slit with a width of 1.8 m and a jacket (not shown) for adjusting the internal temperature, and the temperature of the dope 27 to be cast is 30 ° C. It was. A form having a temperature adjustment function was used for the feed block 73 and the pipes serving as the channels of the dope 27, and the internal temperatures were all kept at 30 ° C.

  The casting film 75 that had been cooled and gelled until it had self-supporting property was peeled off from the casting drum 77 while being supported by the peeling roller 85. Next, while the casting film 75 is sent to the crossing part 86 and conveyed while being supported by a plurality of pass rollers, drying air adjusted to 40 ° C. is supplied from the drying device 87 to promote drying of the casting film 75. It was. Subsequently, while the casting film 75 is carried into a tenter 88 having a plurality of pins, both ends of the casting film 75 are fixed with a plurality of pins, and then the casting film 75 is conveyed while being stretched in the width direction. The film 90 was dried by supplying 100 ° C. drying air from a drying apparatus (not shown) for 20 minutes.

The position of 50 mm was cut | disconnected inward from the both ends of the film 90 using the edge cutting device 92 provided with the NT type cutter distribute | arranged within 30 second from the exit of the tenter 88. FIG. Both side ends of the cut film 90 were sent to a crusher 94 by a cutter blower (not shown) and crushed into chips of about 80 mm ² on average.

  A pre-drying chamber (not shown) was provided between the ear opener 92 and the drying chamber 97, and the film 90 was preheated by supplying dry air at 100 ° C. and then carried into the drying chamber 97. In the drying chamber 97, the film 90 is conveyed while being wound around a plurality of rollers 96 in the drying chamber 97 whose internal temperature is adjusted by a temperature adjusting device (not shown) so that the film surface temperature of the film 90 becomes 140 ° C. In the meantime, the film 90 was dried. The drying time of the film 90 in the drying chamber 97 was 10 minutes. Here, the film surface temperature of the film 90 was measured using a thermometer (not shown) provided just above the conveyance path of the film 90 and in the vicinity of the surface. In the drying chamber 97, after recovering the solvent gas volatilized from the film 90 using an adsorption recovery device 99 having an adsorbent composed of activated carbon and a desorbent composed of dry nitrogen, the water content is reduced to 0.3 mass% or less. The water in the solvent gas was removed until

  A humidity control chamber (not shown) is provided between the drying chamber 97 and the cooling chamber 100, and air having a temperature of 50 ° C. and a dew point of 20 ° C. is supplied to the film 90. % Air was blown to adjust the humidity, and the curl generated on the film 90 was corrected. Next, the film 90 was sent to the cooling chamber 100 and gradually cooled until it became 30 ° C. or lower, and then the charged voltage of the film 90 was set within a range of −3 kV to +3 kV using the forced static eliminator 103. . Then, knurling was imparted to both end portions of the film 90 using the knurling imparting roller 104 to correct irregularities generated on the surface. The film 90 has a width for imparting knurling of 10 mm, and the embossing is applied to the film 90 by adjusting the pressing force by the knurling imparting roller 104 so that the uneven height is 12 μm higher than the average thickness of the film 90 on average. Processing was performed.

  The film 90 was sent to the take-up chamber 95 and taken up by the take-up roller 108 having a diameter of 169 mm while applying a pressing pressure of 50 N / m to the film 90 by the press roller 107. At the time of winding, the tension at the beginning of winding of the film 90 was 300 N / m, and the tension at the end of winding was 200 N / m. From the above, a roll-shaped film 90 was obtained. The completed film 90 had a film thickness of 60 μm. In addition, the average drying rate of the cast film 75 and the film 90 was 20 mass% / min throughout the film forming process.

The filtration efficiency of the filtration filter used in the first filtration device 30 in each experiment was determined as follows. Filtration efficiency was calculated from the number of particles before and after filtration by filtering the dispersed water in which JIS 8 type powder (including clay mineral, soil of Kanto Loam layer) was dispersed in water at a constant flow rate. The concentration of JIS 8 seed powder in the dispersed water was 5 ppm. The flow rate when filtered at a constant flow rate is 6.6 ml / min. - it was cm ^2. “Ml / min. · Cm ² ” is a unit of flow rate representing the volume (ml) through which dispersed water flows per 1 cm ² per minute. The filtration efficiency is calculated by {(number of particles before filtration) − (number of particles after filtration)} ÷ (number of particles before filtration) × 100 (unit:%). The result of the filtration efficiency is shown in the column of “JIS powder filtration efficiency” in Table 1.

  Since the amount of unreacted cellulose contained in the raw material cannot be directly measured, it is difficult to directly calculate the filtration efficiency for unreacted cellulose. For this reason, first, as described above, the filtration efficiency of the JIS type 8 powder with respect to the dispersed water was evaluated as a filter filter specification. In addition, as will be described later, by evaluating the number of bright spot foreign matter and the number of second bright spot foreign matter on the film 90 made from the dope 27 when the filter 62 of the present invention is used, “brightness” The effect of the present invention was confirmed that it is possible to efficiently remove unreacted cellulose that is a factor of spot foreign matter, particularly second bright spot foreign matter, and is an insoluble foreign matter.

In each experiment, the number of bright spot foreign materials in the film 90 was determined as follows. First, a sheet-like film 90 is disposed between two polarizing plates arranged in crossed Nicols. Light is irradiated from one side and observed with a microscope from the other side. Then, among the bright spots, those having a luminance L in the range of 30 cd or more and 255 cd or less were detected, and the number of bright spot foreign matters per 1 cm ² was determined as the bright spot foreign substances in the film 90 with the detected bright spots. The microscope conditions at this time were a transmission light source with a magnification of 50 times. And this number was applied to the following criteria and evaluated in four stages of A to D. The evaluation results are shown in the column of “bright spot foreign matter” in Table 1.
A: Less than 10 B: 10 or more and less than 20 C: 20 or more and less than 50 D: 50 or more

In addition, a liquid crystal display device of the same type as described above is manufactured using this film 90, and the second bright spot foreign matter per cm ^{2 is used} as the second bright spot foreign matter in the film 90 with the bright spot recognized in this liquid crystal display device. I asked for a number. This number was applied to the following criteria and evaluated in four stages of A to D. The evaluation results are shown in the column of “second bright spot foreign matter” in Table 1.
A: 3 or less B: More than 3 and 4 or less C: More than 4 and 5 or less D: More than 5

  Moreover, when the size S and the luminance L were measured for the second bright spot foreign matter visually recognized by the above-described method under the measurement conditions of the bright spot foreign matter, the size S was 10 μm or more and the brightness was 80 cd. As described above, it was confirmed that the bright spot foreign matter is in the region above the predetermined curve U1 in the graph.

In each experiment, the degree of increase in the internal pressure (filter pressure) of the first filtration device 30 (hereinafter referred to as “filter pressure increase”) was evaluated as follows. The preset temperature of the heating device 26 was adjusted to 90 ° C., and the maximum filtration pressure (filtration pressure) value in the first filtration device 30 was measured. Using this maximum filtration pressure value, the filtration pressure increase was evaluated according to the following criteria. The evaluation results are shown in the respective “filter pressure increase” columns of Table 1.
A: Maximum filtration pressure value is less than 0.3 MPa B: Maximum filtration pressure value is 0.3 MPa or more and less than 0.5 MPa C: Maximum filtration pressure value is 0.5 MPa or more

  From the above results, the filtration filter 62 in which the cationic polymer layer 66 is provided on the surface of each fiber body 65 has better filtration efficiency with respect to the dispersed water of the JIS type 8 powder than the filter without the cationic polymer layer 66. Was confirmed.

  In addition, when manufactured using the dope 27 filtered using the filter 62 in which the cationic polymer layer 66 is provided on the surface of each fiber main body 65, compared to the case where the dope 27 without the cationic polymer layer 66 is used. Further, it was confirmed that the bright spot foreign matter in the cellulose acylate film 90 was reduced, and in particular, the second bright spot foreign matter was reduced. Thereby, it is confirmed that the filtration filter 62 in which the cationic polymer layer 66 is provided on the surface of each fiber body 65 efficiently captures and removes the unreacted cellulose 70 that is a negatively charged insoluble matter from the dope 27. did it.

  Moreover, even if the filtration filter 62 in which the cationic polymer layer 66 is provided on the surface of each fiber body 65 is used in the first filtration device 30, the first filtration is performed in the same manner as in the case of using the filter without the cationic polymer layer 66. It was also confirmed that the filtration pressure in the device 30 did not increase too much.

DESCRIPTION OF SYMBOLS 10 Dope manufacturing equipment 27 Dope 30 1st filtration apparatus 50 Film manufacturing equipment 62 Filtration filter 63 Cationic fiber 65 Fiber main body 66 Cationic polymer layer 67 Cationic polymer 70 Unreacted cellulose 75 Casting film 77 Casting drum 90 Film

Claims (3)

Cationic polymer layer comprising a cationic polymer to the filter paper is formed from a fiber body is coated is, the cationic polymer layer is eclipsed set on the surface of the fiber body,
The cationic polymer is a compound represented by the following formula (1):
The amount of the compound with respect to 100 mass of the fiber body is in the range of 1 part by mass or more and 15 parts by mass or less,
A filtration filter, which is used in a filtration step for removing unreacted cellulose in a solution obtained by dissolving cellulose acylate in a solvent .

A filtration method, wherein a solution obtained by dissolving cellulose acylate in a solvent is filtered using the filtration filter according to claim 1 to remove unreacted cellulose in the solution. A dope containing cellulose acylate and a solvent is cast on a continuously running support to form a cast film, and the cast film is peeled off from the support to form a film, and the peeled film is conveyed. In the method for producing a cellulose acylate film that is dried by a drying means,
The said dope is filtered using the filtration method of Claim 2 , The manufacturing method of the cellulose acylate film characterized by the above-mentioned.

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